CN102612541A - Polycarbonate resin composition - Google Patents

Polycarbonate resin composition Download PDF

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Publication number
CN102612541A
CN102612541A CN2010800512226A CN201080051222A CN102612541A CN 102612541 A CN102612541 A CN 102612541A CN 2010800512226 A CN2010800512226 A CN 2010800512226A CN 201080051222 A CN201080051222 A CN 201080051222A CN 102612541 A CN102612541 A CN 102612541A
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China
Prior art keywords
mass parts
flame retardant
resin composition
polycarbonate resin
graft copolymer
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Inventor
竹内敬直
前场诚一
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a polycarbonate resin composition which is characterized by being prepared by adding 30-100 parts by mass of artificial graphite, (C) 3-13 parts by mass of a graft copolymer containing polyorganosiloxane, and (D) 1-5 parts by mass of polytetrafluoroethylene to 100 parts by mass of (A) a polycarbonate resin, and which is excellent in flame retardancy (particularly thin-wall flame retardancy), thermal conductivity, and impact properties even when a chlorine-based flame retardant, a bromine-based flame retardant, and a phosphorus-based flame retardant are not used.

Description

Poly carbonate resin composition
Technical field
The moulding article that the present invention relates to poly carbonate resin composition and constitute by this resin combination; Do not use chlorine-based flame retardant, bromide fire retardant and phosphorus flame retardant even relate to, the poly carbonate resin composition that also has excellent flame (particularly thin-wall flame retardance), thermal conductivity, impact characteristics reaches by its moulding article that constitute.
Background technology
In the goods exploitation in electric and electronic field, be accompanied by the high pixelation high speed processingization of digital camera DV, the miniaturized of projector, the high speed processingization of PC mobile equipment, the LEDization of various light sources etc., cooling measure becomes to attach most importance to gradually.
Though taked to constitute the measure of heat-radiation loop with metal parts; But equipment for miniaturized; Because it is complicated that heat-radiation loop becomes, need also to make that resin framework and heat-radiation loop are integrally formed, excellent thermal conductivity and as the physical strength of the framework also resin material of excellence.
In addition, for miniaturized electronics, framework, casing also need thin-walled property, and the consequent is that the shaping thin wall body also need have flame retardant resistance.
General in the framework of above-mentioned electronics etc. is polycarbonate resin, reaches fire-retardantization in order to make the moulding article that are made up of poly carbonate resin composition, knownly needs to add halogen flame retardants such as chlorine-based flame retardant, bromide fire retardant.But, during recently from security, the discarded burning aspect that influences of environment is considered, need to utilize not halogen-containing fire retardant to realize fire-retardant method on the market.As this non-halogen flame retardant, organic phosphorus flame retardant, particularly organophosphorus compounds are allocated in the poly carbonate resin composition, in order to reach fire-retardantization, need allocate more a large amount of phosphate compounds into.Because the mold temperature of polycarbonate resin is high, melt viscosity is also high, mold temperature is raise.Therefore,, occur the generation of the burn into gas of mould during forming process etc., also have deficiency in appearance sometimes at moulding environment and moulding article although phosphate compound can promote flame retardant resistance usually.
Therefore; Also need find halogen flame retardant, phosphorus flame retardants such as not using chlorine-based flame retardant, bromide fire retardant; Just can reach the flame retardant resistance (particularly thin-wall flame retardance) of needed moulding article, also have the poly carbonate resin composition of excellent thermal conductivity simultaneously.
As the means of giving the above-mentioned thermal diffusivity of thermoplastic resin, be known that and allocate graphite (referring to patent documentation 1, patent documentation 2) into.Disclose in the patent documentation 1 through in thermoplastic resin, allocating specific graphite into; It is little to obtain metal protection; And the thermoplastic resin composition of excellent thermal conductivity; But wherein put down in writing to improving flame retardant resistance, preferably used organic halogen flame retardant and SULPHOSUCCINIC ACID ESTER flame retardants such as halogenated carbonate ester oligomer, halogenation epoxy compounds and the unexposed technology of not using chlorine-based flame retardant, bromide fire retardant and phosphorus flame retardant.
In addition; Though relate to the radiating frame that accommodates heating element in the patent documentation 2; But the needed flame retardant resistance of framework to electronics etc. is not is not recorded and narrated; Though disclose fire retardants such as organic bromine flame retardant and phosphorus flame retardant as the additive of allocating in case of necessity, the unexposed technology that does not adopt chlorine-based flame retardant, bromide fire retardant and phosphorus flame retardant is not energetically added fire retardant, Antidrip agent can expect not having sufficient flame retardant resistance in addition from embodiment.
In addition, be known as and give polycarbonate resin static resistance and electroconductibility and allocate graphite into and allocated the poly carbonate resin composition (referring to patent documentation 3, patent documentation 4) of fire retardant simultaneously into.Disclose in the patent documentation 3 and made the aromatic copolycarbonate resin composition that contains specific silicone compounds in the title complex of forming by aromatic polycarbonate resin and graphite and form; And estimated static resistance and flame retardant resistance, but do not put down in writing the technology contents that obtains sufficient flame retardant resistance for the thin-walled about the needed 1.5mm of frameworks such as electronics.In addition; In patent documentation 4; As the technology of not using chlorine-based flame retardant, bromide fire retardant and phosphorus flame retardant energetically; Disclose the flame retardant resin composition that is made up of polycarbonate resin, graphite and organic sulfonic acid alkali (soil) metal-salt, carrying out flame retardant resistance is that the moulding article of 2.5mm are estimated to thickness only when estimating, and equally with patent documentation 3 does not obtain competent flame retardant resistance for the thin-walled about the needed 1.5mm of frameworks such as electronics.
TP formerly
Patent documentation
Patent documentation 1: TOHKEMY 2007-31611 communique
Patent documentation 2: TOHKEMY 2008-31358 communique
Patent documentation 3: TOHKEMY 2007-126499 communique
Patent documentation 4: TOHKEMY 2006-273931 communique
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide flame retardant resistance (the thickness 1.2mm that does not use chlorine-based flame retardant, bromide fire retardant and phosphorus flame retardant and thin molded article; Below be called " thin-wall flame retardance ") reach V-0, have high thermal conductivity and impact characteristics excellent poly carbonate resin composition and moulding article.
The means of dealing with problems
The inventor furthers investigate repeatedly; The result finds; Through cooperating aromatic polycarbonate resin, synthetic graphite by specific ratios and containing the graft copolymer of organopolysiloxane, can obtain thin-wall flame retardance is 1.2mm, V-0; And the also excellent poly carbonate resin composition of thermal conductivity, thermostability, impact characteristics, thereby accomplished the present invention.
That is, the present invention provides
(1) poly carbonate resin composition; It is characterized in that it being relative (A) polycarbonate resin 100 mass parts, allocate into graft copolymer 3～13 mass parts that (B) synthetic graphite 30～100 mass parts, (C) contain organopolysiloxane, and (D) tetrafluoroethylene 1～5 mass parts form
(2) poly carbonate resin composition of record in above-mentioned (1); It is characterized in that the graft copolymer that (C) contains organopolysiloxane is in the presence of 40～90 mass parts (C-1) organopolysiloxane particle; Make comprise 0.5～10 mass parts by (c-2-1) but multi-functional monomer 100～50 quality % and (c-2-2) (C-2) ethene base system monomer of monomer 0～50 quality % of other copolymerization carry out polymerization, make 5～50 mass parts (C-3) ethene base system monomer (C-1～C-3 is total up to 100 mass parts) carry out polymerization again and the graft copolymer that obtains.
(3) poly carbonate resin composition of record in above-mentioned (1) or (2) is carried out moulding and the electric/electronic device that forms with the moulding article.
(4) electric/electronic device of record is with the moulding article in above-mentioned (3), and it uses framework for electric/electronic device.
(5) electric/electronic device of record is with the moulding article in above-mentioned (3), and it uses casing for electric/electronic device.
The invention effect
According to the present invention, can not damaged mechanical properties that polycarbonate had originally and thin-wall flame retardance (1.2mm, V-0) and the resin combination of excellent thermal conductivity and moulding article.
Embodiment
Below the present invention is elaborated.
Polycarbonate resin of the present invention (following abbreviate as sometimes " PC resin ") compsn be with (A) aromatic polycarbonate resin, (B) synthetic graphite, (C) contain organopolysiloxane graft copolymer, and (D) tetrafluoroethylene as poly carbonate resin composition that must composition.
(A) polycarbonate resin as among the present invention has no particular limits, and can enumerate various polycarbonate resins.
Usually can use the aromatic copolycarbonate of making through the reaction of 2 yuan of phenol and carbonate precursor.For example, can use 2 yuan of phenol and carbonate precursor through solution method or scorification, the polycarbonate resin that the transesterification reaction of the reaction through 2 yuan of phenol photoreactive gas specifically, 2 yuan of phenol and diphenyl carbonate etc. is made.
As 2 yuan of phenol; Can enumerate various kinds, for example can enumerate 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) of 2-, two (4-hydroxy phenyl) methane, 1; Two (4-hydroxy phenyl) ethane, 2 of 1-; Two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane, 4,4 of 2-'-dihydroxybiphenyl, two (4-hydroxy phenyl) naphthenic hydrocarbon, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) ether, two (4-hydroxy phenyl) ketone etc.
In these materials, preferred especially 2 yuan of phenol are the kinds that form as main raw material with two (hydroxy phenyl) alkane system, particularly dihydroxyphenyl propane.
As other 2 yuan of phenol, can enumerate Resorcinol, Resorcinol, catechol etc.These 2 yuan of phenol can be distinguished independent use, also can mix and use more than 2 kinds.
In addition, carbonate precursor is carbonyl halide, carbonyl ester or haloformate etc., can enumerate two haloformates, diphenyl carbonate, methylcarbonate, diethyl carbonate of phosgene, 2 yuan of phenol etc. specifically.
As the molecular weight regulator that is used as the molecular end base in this (A) PC resin,, can use various monohydric phenols so long as the molecular weight regulator that uses in the polymerization of common polycarbonate gets final product.Specifically, for example can enumerate phenol, p-cresol, p-tert-butylphenol, to tert-octyl phenol, to cumyl phenol, bromophenol, tribromophenol, nonylphenol etc.
In PC resin combination of the present invention; Except that aforementioned PC resin; Can also be in the scope of not damaging the object of the invention; Suitably contain polycarbonate-poly organo alkyl copolymer with organopolysiloxane part, form at 2 functionality carboxylic acids such as terephthalic acid or its ester ester precursor such as property verivate in the presence of carry out the polymerization of polycarbonate and the copolymer resinses such as polyester-polycarbonate resin that obtain, or other polycarbonate resin.
For above-mentioned (A) PC resin that uses among the present invention, consider that from obtaining the high impact aspect viscosity-average molecular weight (Mv) is preferably 19,000～30,000, consider more preferably 19,000～27,000 from the formability aspect.
This viscosity-average molecular weight (Mv) is to use Ubbelohde viscometer, measures the viscosity of 20 ℃ dichloromethane solution, obtains limiting viscosity [η] by it, calculates by following formula again.
[η]＝1.23×10 -5Mv 0.83
In poly carbonate resin composition of the present invention, mainly be in order to give thermal conductivity, flame retardant resistance, to allocate (B) synthetic graphite into.
As (B) composition synthetic graphite, have no particular limits, use known, commercially available product to get final product.Synthetic graphite is that decolorizing carbon is heat-treated, and makes the small graphite crystal of irregular alignment carry out artificial orientation and the material that forms, except the synthetic graphite that uses in the common carbon material, also comprises kish graphite, decomposes graphite, and thermolysis graphite etc.The synthetic graphite that uses in the common carbon material is to make through common refinery coke, coal class pitch coke are carried out graphitization processing as main raw material.
Also having, for the present invention, is not natural graphite, and the reason that must be synthetic graphite is in order to obtain thin-wall flame retardance.
As the use level of (B) synthetic graphite that uses among the present invention, be 30～100 mass parts with respect to aforementioned (A) polycarbonate resin 100 mass parts, be preferably 30～70 mass parts.If less than 30 mass parts just can not obtain enough thermal conductivitys, if surpass 100 mass parts, then can not obtain thin-wall flame retardance, the molecular weight and molecular weight in the time of can causing shock strength reduction, granulation.
In the present invention, as the particle diameter of graphite, preferably using 50% accumulation particle diameter is the material of 30～180 μ m.The fixed carbon amount of graphite is preferably more than the 80 weight %, more preferably more than the 90 weight %, further is preferably more than the 98 weight %.In addition, the volatile matter of graphite of the present invention is preferably below the 3 weight %, more preferably below the 1.5 weight %, further is preferably below the 1 weight %.
In addition, for graphite surface,, can apply surface treatment, for example epoxidation processing, carbamate processing, silane coupled processing and oxide treatment etc. for the affinity of enhancing in the scope of not damaging compsn characteristic of the present invention with thermoplastic resin.
In poly carbonate resin composition of the present invention, mainly, allocate the graft copolymer that (C) contains organopolysiloxane in order to give flame retardant resistance.
(C) of the present invention composition has no particular limits; As preferred object lesson; Can be set forth under the existence of (C-1) organopolysiloxane particle 40～90 mass parts; Make by (c-2-1) multi-functional monomer 100～50 quality %, and (c-2-2) (C-2) ethene base system monomer 0.5～10 mass parts of forming of other copolymerisable monomer 0～50 quality % carry out polymerization, make (C-3) ethene base system monomer 5～50 mass parts (C-1～C-3 adds up to 100 mass parts) carry out polymerization and the graft copolymer that contains organopolysiloxane that obtains again.
In addition; Preferably (C) composition is in the presence of (C-1) organopolysiloxane particle 60～80 mass parts; Make 1～5 mass parts polymerization of (C-2) ethene base system monomer; Make (C-3) ethene base system monomer 15～39 mass parts carry out polymerization and obtain again, wherein making (C-2) and total amount (C-3) is 100 mass parts.
Aforementioned (c-2-1) multi-functional monomer is the compound that intramolecularly contains 2 above polymerizability unsaturated link(age)s; As object lesson; Can enumerate allyl methacrylate(AMA), triallyl cyanurate, triallyl isocyanurate, Phthalic acid, diallyl ester, TGM 1, dimethacrylate 1,3 butylene glycol ester, Vinylstyrene etc.These monomers can use separately, also can be also with more than 2 kinds.In these monomers, see from economy and effect, preferably use allyl methacrylate(AMA).
As the object lesson of aforementioned (c-2-2) copolymerisable monomer, for example can enumerate, vinylbenzene, alpha-methyl styrene, p-methylstyrene, (methyl) acrylic ester monomer, methylene-succinic acid, (methyl) vinylformic acid, fumaric acid, toxilic acids etc. such as nitrilation ethene base system monomer, methyl acrylate, ethyl propenoate, propyl acrylate, Bing Xisuandingzhi, ethyl acrylate, glycidyl acrylate, Hydroxyethyl Acrylate, vinylformic acid hydroxyl butyl ester, TEB 3K, Jia Jibingxisuanyizhi, NSC 20956, lauryl methacrylate(LMA), SY-Monomer G, methylacrylic acid hydroxyl ethyl esters such as aromatic vinyl base system monomer, vinyl cyanide, methacrylonitriles such as butylstyrene contained ethene base system monomer of carboxyl etc.These monomers can use separately or and with more than 2 kinds.
Aforementioned (C-3) ethene base system monomer is the composition that uses in order to obtain containing the graft copolymer of organopolysiloxane; When this graft copolymer is allocated into aromatic polycarbonate resin and is improved flame retardant resistance and shock-resistance; Also be consistency, graft copolymer be dispersed in the aromatic polycarbonate resin and the composition that uses in order to ensure graft copolymer and aromatic polycarbonate resin.Therefore, as (C-3) ethene base system monomer, it is 9.15～10.15 [(cal/cm that preferred selection makes the SP of this ethene base system polymer of monomers 3) 1/2], 9.17～10.10 [(cal/cm more preferably 3) 1/2], be preferably 9.20～10.05 [(cal/cm especially 3) 1/2].If SP is in the aforementioned range, just can improve flame retardant resistance.About the details of said SP, TOHKEMY 2003-238639 communique is put down in writing.
As the median size of (C) composition, the value of obtaining through electron microscope observation is 0.1～1.0 μ m, if this median size is 0.1～1.0 μ m, then can obtain enough flame retardant resistances, rigidity and shock strength.
Above-mentioned (C) composition can use separately or make up and use more than 2 kinds.
Containing the use level of the graft copolymer of organopolysiloxane as (C), is 3～13 mass parts with respect to (A) polycarbonate resin 100 mass parts, is preferably 4～11 mass parts, more preferably 5～10 mass parts.If use level less than 3 mass parts, then flame retardant resistance, shock-resistance are not enough, if surpass 13 mass parts, then the dispersiveness of (C) composition descends, Young's modulus, flame retardant resistance, and shock strength reduce.
In poly carbonate resin composition of the present invention,, allocate polytetrafluoroethylene (PTFE) into as (D) composition in order to improve flame retardant resistance.Should give resin combination of the present invention to prevent the effect of fusion drippage by (D) composition, and make it show excellent thin-wall flame retardance.
(D) composition is preferably and has the kind that protofibril forms ability." protofibril formation ability " here is meant to demonstrate through shearing force etc. and adds effect that resin mutually combines and becomes fibrous tendency.As (D) of the present invention composition, can enumerate for example tetrafluoroethylene, tetrafluoroethylene based copolymer (for example, tetrafluoroethylene/hexafluoropropylene copolymer etc.) etc.In these materials, preferably polytetrafluoroethylene.
Have the PTFE that protofibril forms ability and have high molecular weight, the number-average molecular weight of being obtained by standard specific gravity is generally more than 500,000, is preferably 500,000～1,500 ten thousand, and more preferably 1,000,000～10,000,000.Specifically, can be through in aqueous solvent, in the presence of Sodium persulfate, potassium or ammonium,, make tetrafluoroethylene carry out polymerization under preferred 20～100 ℃ and obtain in about 0～200 ℃ of the pressure about 7～700kPa, temperature.
In addition, except solid shape, can also use the aqueous liquid dispersion form, can use according to the ASTM criteria classification is the 3rd type kind.As the commercially available article that are categorized as the 3rd type; Can enumerate for example " Teflon 6-J " [trade(brand)name; Du Pont-Mitsui Fluorochemicals Company, Ltd. system], " Port リ Off ロ Application D-1 " reach " Port リ Off ロ Application F-103 " [trade(brand)name, Daikin Industries (strain) system] etc.In addition, except that the 3rd type, can also enumerate " Algoflon F5 " [trade(brand)name, Solvaysolexis society system] and " Port リ Off ロ Application MPAFA-100 " [trade(brand)name, Daikin Industries (strain) system] etc.
Above-mentioned PTFE can use separately or make up and use more than 2 kinds.
As the use level of (D) polytetrafluoroethylene (PTFE), be 1～5 mass parts with respect to aforementioned (A) polycarbonate resin 100 mass parts, be preferably 1～4 mass parts.If its use level less than 1 mass parts then can not be guaranteed the thin-wall flame retardance as target, if surpass 5 mass parts, then shock strength step-down.
For poly carbonate resin composition of the present invention, in order to improve formability, shock-resistance, outward appearance, to improve weathering resistance and rigidity etc., the composition of aforementioned except comprising (A)～(D) can also contain phenol is, phosphorus is, sulphur is inhibitor, releasing agent.
For the use level of inhibitor, be preferably 0.001～0.5 mass parts during phosphorous antioxidant.If be more than 0.001 mass parts, then can keep the thermostability in granulating working procedure, the molding procedure, if less than 0.5 mass parts then is not easy to cause molecular weight and molecular weight.In addition, be inhibitor for phenol, preferably add 0.001～0.5 mass parts, improve shock strength easily.
As releasing agent, so long as the material of the release property when allocating polycarbonate resin into and can improve moulding just has no particular limits.Particularly organic cpds such as beeswax, Zerol, tristearin, pentaerythritol monostearate, tetramethylolmethane tristearate, pentaerythritol tetrastearate, montanic acid ester type waxes, carboxylicesters demonstrate excellent release property, the suitable use.
These materials can be enumerated " Licowax E ", " the Loxiol EP-32 " that Gognis Japan society makes of " beeswax Golden Brand ", " RIKEMAL S-100A ", " the RIKEMAL SL-900 " that reason is ground vitamin b6 usp (strain) manufacturing of the for example industrial society of three wooden chemistries manufacturing, " the Loxiol VPG861 " that reach " リ ケ ス タ one EW-440A ", the manufacturing of Gognis Japan society, the manufacturing of Clariant Japan society.Its use level is preferably 0.001～2 mass parts.
In addition, can also further contain other additive component commonly used in synthetic resins, elastomerics, the thermoplastic resin as required.As above-mentioned additive, can enumerate the UV light absorber of static inhibitor, polymeric amide polyether block copolymer (giving permanent antistatic performance), benzotriazole system and benzophenone series, photostabilizer (weather resisting agent), softening agent, antiseptic-germicide, compatibility agent and the tinting material (dyestuff, pigment) etc. of hindered amine system.
As the use level of above-mentioned optional member,, just have no particular limits as long as in the characteristic range that can keep poly carbonate resin composition of the present invention.
Then, the method for manufacture to poly carbonate resin composition of the present invention describes.
Poly carbonate resin composition of the present invention can be through cooperating aforesaid (A)～(D) composition according to the above ratio, cooperates the various optional members that use as required by proper proportion again, and mix and obtain.
For cooperating and mixing; The equipment of common employing capable of using; For example ribbon mixer, rotary drum etc. carry out pre-mixing, implement through the method for using Henschel mixer, banbury mixers, single screw extrusion machine, twin screw extruder, multiple screw extruder and common kneader etc.Heating temperature when mixing is suitably selected in 240～320 ℃ scope usually.As this fusion moulding of mixing, preferably use extrusion shaping machine, particularly the exhaust extrusion shaping machine.
In addition, also can the composition that contains beyond the polycarbonate resin be carried out fusion with polycarbonate resin or other thermoplastic resin in advance and mixes, that is, form masterbatch and add.
Poly carbonate resin composition of the present invention can through above-mentioned fusion mix shaper or with the material grain that obtains as raw material, process various moulding article through injection moulding, injection compression molding method, extrusion moulding, blow molding method, compression moulding method, vacuum forming and foaming method etc.Suitablely especially be used to use the material grain that obtains, make injection-molded article through injection molding and injection compression molding.
The formed body that is made up of poly carbonate resin composition of the present invention is applicable to for example
(1) electric/electronic device parts such as television set, cassette radio recorder, video camera, video tape recorder, player, DVD player, air conditioner, portable phone, display, computer, register, electronic calculator, duplicator, printer, facsimile machine;
(2) electric, the framework that electronics is used of above-mentioned (1);
(3) electric, the casing that electronics is used of above-mentioned (1); Deng.
Embodiment
Below, list embodiment and comparative example is explained the present invention particularly, but the present invention never receives the restriction of these instances.
The raw material of method of evaluating performance and use is following.
(method of evaluating performance)
(1) viscosity-average molecular weight
Utilize the Ubbelohde viscosity tube to measure the limiting viscosity (η) of 20 ℃ of following dichloromethane solutions, calculate through following relational expression (formula of Schnell).
〔η〕＝1.23×10 -5×Mv 0.83
Also have,, will dissolve with methylene dichloride with particle, separate not solvent components, measure the molecular weight of the polycarbonate resin that extracts with the evaluation that the twin screw extrusion shaping machine is processed for material grain molecular weight.
(2) thin-wall flame retardance
Use the test film of the test film of making by UL standard 94 (long 127mm, wide 12.7mm, thick 1.2mm) to carry out testing vertical flammability.Go out the grade of UL94 V-0, V-1 or V-2 based on evaluation of test result, the sample that does not reach V-2 is regarded as V-2out.
Also have, UL standard 94 is that test film vertical with maintenance from the flame that makes burner and that have a specified dimension contacts flame residence time after 10 seconds and estimates the method for flame retardant resistance.
(3) thermal conductivity
Use thermal conductivity determinator " TPA-501 " [capital of a country electronic industry (strain) system], measure through heat dish method.
(4) density
Measure by JIS K7112:0.
(5) curved characteristic
5-a) flexural strength
Measure according to ASTM D790.
5-b) bending elastic modulus
The thick 4mm that use is made by injection moulding machine, the test film of long 130mm according to ASTM standard D-790, carry out 3 pliability tests under length of support 90mm, loading velocity 20mm/min, by the gradient of its load-deflection curve, calculate bending elastic modulus.
(6) impact characteristics
6-a) notched IZOD shock strength (IZOD)
The test film of the thick 3.2mm (1/8 inch) that use is made by injection moulding machine according to ASTM standard D-256, is determined at the shock strength of measuring under 23 ℃ of the temperature.
6-b) unnotched IZOD shock strength (IZOD)
The test film of the thick 3.2mm (1/8 inch) that use is made by injection moulding machine according to ASTM standard D-256, is determined at the shock strength of measuring under 23 ℃ of the temperature.
6-c) Charpy (keeping flat method) shock strength
Thick 3.2mm (1/8 inch) test film that use is made by injection moulding machine according to JIS K7111, is measured shock strength by keeping flat method.
(7) flow characteristics (yield point value)
Use high formula flowing test appearance,, under 320 ℃ temperature, measure with 100kg load according to JIS-K7210.
(use raw material)
(A) aromatic polycarbonate resin
Aromatic polycarbonate resin [the emerging product of bright dipping (strain) system, " FN2500A ", Mv=24,500]
(B) graphite
B-1: synthetic graphite [Japanese graphite industry society's system " PAG-420 "; Amorphous, 50% accumulation particle diameter is 30～40 μ m (being below 50% more than the 50 μ m), apparent density 0.29～0.37g/cm 3, fixed carbon is more than the 99.4 quality %, ash content is below the 0.3 quality %, volatilization is divided into below the 0.3 quality %]
B-2: natural graphite [Japanese graphite industry society's system " CB-150 "; Flakey, size-grade distribution: be to be below 5% more than 77～87%, the 106 μ m below the 63 μ m, apparent density is 0.2～0.3g/cm 3, 50% accumulation particle diameter is that 31～48 μ m, fixed carbon are more than the 98 quality %, ash content is below the 1 quality %, volatilization is divided into below the 1 quality %]
Fire retardant
(C) contain the graft copolymer of organopolysiloxane
C-1: graft copolymer [trade(brand)name " kane Ace MR-01 ", (strain) Kaneka system] the median size 0.3 μ m that contains organopolysiloxane
C-2: the graft copolymer that contains organopolysiloxane that obtains through following manufacturing example 1
(C) fire retardant beyond the composition
C-3; P-sulfonic acid sodium [DAH DIING CHEMICAL INDUSTRY society system]
Make example 1
(manufacturing of organopolysiloxane particle)
For the aqueous solution of forming by pure water 251 mass parts, X 2073 (SDBS) 1 mass parts, octamethylcyclotetrasiloxane 95 mass parts, sulfydryl propyl group dimethoxy-methyl silane 5 mass parts; With mixing machine 10; 000rpm stirred 5 minutes down, was mixed with emulsion.With this emulsion disposable add to possess whisking appliance, reflux cooler, nitrogen are blown into mouthful, monomer appends mouthful, in 5 mouthfuls of flasks of TM.One side stirring system, Yi Bian add the Witco 1298 Soft Acid aqueous solution 1 mass parts (solids component) of 10 quality %, process was reacted 6 hours after being warmed up to 80 ℃ in about 40 minutes again.Then, be cooled to 25 ℃, place after 20 hours, using sodium hydroxide to make intrasystem pH is 6.5, stops polymerization, obtains containing the emulsion of organopolysiloxane particle.
Polymerisation conversion is 88%; The median size of the emulsion of organopolysiloxane particle is 0.14 μ m; Toluene insoluble becomes component (will at room temperature be impregnated in the toluene of 80ml 24 hours by the organopolysiloxane particle solid 0.5g that the emulsion drying obtains; 12, spinning is 60 minutes under the 000rpm, measures the weight fraction (%) that the toluene insoluble of organopolysiloxane particle divides and obtains) be 0%.(containing the manufacturing of the graft copolymer of organopolysiloxane)
Possess that whisking appliance, reflux cooler, nitrogen are blown into mouthful, monomer appends mouthful and 5 mouthfuls of flasks of TM in; Add pure water 300 mass parts, sodium sulfoxylate formaldehyde (SFS) 0.2 mass parts, Calcium Disodium Versenate (EDTA) 0.01 mass parts, ferrous sulfate 0.0025 mass parts and above-mentioned organopolysiloxane particle 70 mass parts that make, on one side stirring system under nitrogen gas stream, be warmed up to 60 ℃ on one side.After reaching 60 ℃, disposable appending as monomeric allyl methacrylate(AMA) 3 mass parts of ethene base system with as radical polymerization begins the mixture of cumene hydroperoxide 0.01 mass parts of agent, continues down to stir 1 hour at 60 ℃ then.
Then, appended with 3 hours again and splash into monomeric TEB 3K of ethene base system and radical base polymerization starter cumene hydroperoxide 0.06 mass parts, append end continued stirring 1 hour, thereby obtain the emulsion of graft copolymer.Then, use the pure water diluting emulsion, make solid component concentration be 15 quality % after, calcium chloride water 2 mass parts (solids component) of adding 10 quality % obtain solidifying paste.After will solidifying paste and being heated to 80 ℃, be cooled to 50 ℃ and dewater, make it dry and obtain the powder of poly organo methane series graft copolymer.The polymerisation conversion of the graft copolymer that obtains is 99%, and median size is 0.5 μ m, and the acetone insoluble components amount is 88 quality %.
(D)PTFE
PTFE [Solvaysolexis society system, " Algoflon F5 "; Because the easy aggegation of Algoflon F5, thus with the PC thin slice carry out masterbatchization (mixture ratio (quality) PC: PTFE=90: 10～80: mix again 20)]
(E) other additive antioxidants
E-1: phosphorous antioxidant (phenylbenzene iso-octyl phosphorous acid ester) [ADEKA society system, " ア デ カ ス タ Block C "]
E-2: phenol is inhibitor (octadecyl-3-(3,5-di-t-butyl-hydroxy phenyl) propionic ester) [Ciba Japan (strain) system, " Irganox1076 "]
(F) other additive releasing agent
F-1: glyceryl monostearate [reason is ground vitamin b6 usp (strain) system, " RIKEMAL S-100A "]
F-2: pentaerythritol tetrastearate [reason is ground vitamin b6 usp (strain) system, " リ ケ ス タ one EW-440A "]
Embodiment 1～12 and comparative example 1～8
According to the various compositions of mixed shown in table 1 and the table 2; Be provided to exhaust twin screw extrusion shaping machine (toshiba machine society system; TEM35), under 300～320 ℃ of barrel zone temperatures, 200～600 commentaries on classics of screw rod revolution, output 10～30kg/hr, carries out fusion and mix, obtain estimating and use particle sample.Use to estimate and use particle, under 80 ℃ of 320 ℃ of moulding resin temperature, die temperature, carry out injection molding with injection moulding machine [machine name: IS100EN, toshiba machine (strain) is made], the test film that making is used to carry out various tests carries out various tests.In addition, use this evaluation to measure viscosity-average molecular weight with particle sample.Its result is shown in table 1 and the table 2.
[table 1]
Figure BDA00001629349200141
[table 2]
Figure BDA00001629349200151
Can clear and definite following content by table 1 and table 2.
Can know by table 1; For the embodiment 1～12 that satisfies (A) composition to (D) composition fully of the present invention; It is all excellent to obtain thin-walled (thickness 1.2mm) flame retardant resistance, is V-0, in addition thermal conductivity, curved characteristic, and the also excellent poly carbonate resin composition of shock strength.Can know that by table 2 for the comparative example 1 that uses natural graphite as graphite, thin-wall flame retardance can not reach V-0.For the comparative example 2 that does not use (C) of the present invention composition as fire retardant, the molecular weight of the polycarbonate resin of moulding article descends significantly.For the few comparative example 3 of usage quantity of (C) of the present invention composition, thin-wall flame retardance can not reach V-0.For the too much comparative example 4 of usage quantity of (C) of the present invention composition, shock strength is low.For the poor comparative example 5 of electrographite, thermal conductivity is low, and for the too much comparative example 6 of the content of electrographite, shock strength is low, and the molecular weight of the polycarbonate resin of the article of moulding simultaneously descends significantly.For the poor comparative example 7 of (D) composition PTFE, thin-wall flame retardance can not reach V-0.For the too much comparative example 8 of (D) composition, shock strength is low.

Claims (5)

1. poly carbonate resin composition; It is characterized in that; Be with respect to (A) polycarbonate resin 100 mass parts, cooperate (B) synthetic graphite 30～100 mass parts, (C) contain organopolysiloxane graft copolymer 3～13 mass parts, and (D) tetrafluoroethylene 1～5 mass parts form.
2. poly carbonate resin composition according to claim 1; It is characterized in that; (C) graft copolymer that contains organopolysiloxane is in the presence of 40～90 mass parts (C-1) organopolysiloxane particle; Make comprise 0.5～10 mass parts by (c-2-1) but multi-functional monomer 100～50 quality % and (c-2-2) (C-2) ethene base system monomer of monomer 0～50 quality % of other copolymerization carry out polymerization; The graft copolymer that makes 5～50 mass parts (C-3) ethene base system monomer carry out polymerization again and obtain, C-1～C-3 is total up to 100 mass parts.
3. an electric/electronic device is with the moulding article, and moulding forms in order claim 1 or 2 described poly carbonate resin compositions are carried out for it.
4. electric/electronic device according to claim 3 is characterized in that with the moulding article, for electric/electronic device is used framework.
5. electric/electronic device according to claim 3 is with the moulding article, and it uses casing for electric/electronic device.
CN2010800512226A 2009-11-27 2010-11-11 Polycarbonate resin composition Pending CN102612541A (en)

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