WO2011013645A1 - Polycarbonate resin composition and molded article thereof - Google Patents
Polycarbonate resin composition and molded article thereof Download PDFInfo
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- WO2011013645A1 WO2011013645A1 PCT/JP2010/062577 JP2010062577W WO2011013645A1 WO 2011013645 A1 WO2011013645 A1 WO 2011013645A1 JP 2010062577 W JP2010062577 W JP 2010062577W WO 2011013645 A1 WO2011013645 A1 WO 2011013645A1
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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
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- 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
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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
- 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
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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
- 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
- C08L83/04—Polysiloxanes
Abstract
Description
金属部品での放熱回路での対策も取られているが、小型化される機器では、放熱回路が複雑になってしまうため、樹脂筐体と放熱回路を一体化可能な、熱伝導性に優れ、かつ、筐体としての機械的強度にも優れる樹脂材料が要求されている。
また、小型電子機器においては、筐体、シャーシにおいても薄肉化が要求され、それに伴って薄肉での難燃性も要求されている。
このような要求に応じるために関連した技術として、特許文献1~4が挙げられる。
特許文献1には、(A)熱可塑性樹脂100質量部、(B)平均粒子径が5μm~300μmである黒鉛5~100質量部、(C)有機スルホン酸アルカリ(土類)金属塩0.001~1質量部からなる難燃性樹脂組成物が開示され、特許文献2には、(A)熱可塑性樹脂(A成分)99~20質量部、(B)見掛け密度が0.15g/cm3以下でありかつ、黒鉛粉末5gを水100gに分散した時の水層のpHが4~10である黒鉛1~80質量部からなる熱可塑性樹脂組成物が開示されているが、この組成物では、難燃性が不十分であった。
特許文献3には、(A)芳香族ポリカーボネート樹脂60~90質量部と、(B)黒鉛10~40質量部の合計100質量部に対し、(C)アミノ基及び/又はエポキシ基をもつ、シラン化合物及び/又はシリコーン化合物0.001~5質量部を含んでなる芳香族ポリカーボネート樹脂組成物が開示されているが、この技術でも、電子機器等の筐体に要求される1.5mm程度の肉厚で十分な難燃性が得られていない。
特許文献4には、発熱体が収容される放熱筐体であって、熱可塑性樹脂〔A〕と特定の熱伝導フィラー〔B〕とから成り、熱可塑性樹脂〔A〕100質量部に対する熱伝導フィラー〔B〕の配合量が10~1000質量部である熱伝導性樹脂組成物にて構成されている放熱筐体が開示されているが、電子機器等の筐体に要求される難燃性に関する記述はなく、難燃剤、ドリップ防止剤の添加がないことから、十分な難燃性を有していないと考えられる。 In product development in the electrical and electronic field, focus on heat countermeasures by increasing the number of pixels and speed in digital cameras and digital video cameras, downsizing projectors, speeding up in personal computers and mobile devices, and using LEDs for various light sources. Has been placed.
Although measures have been taken with heat dissipation circuits for metal parts, the heat dissipation circuit becomes complicated in devices that are miniaturized, so the resin housing and heat dissipation circuit can be integrated, and it has excellent thermal conductivity. In addition, a resin material having excellent mechanical strength as a housing is required.
Further, in a small electronic device, the casing and the chassis are required to be thin, and accordingly, the flame resistance is also required.
Patent documents 1 to 4 can be cited as technologies related to satisfying such requirements.
Patent Document 1 includes (A) 100 parts by mass of a thermoplastic resin, (B) 5 to 100 parts by mass of graphite having an average particle size of 5 to 300 μm, (C) an alkali (earth) metal salt of an organic sulfonate. A flame retardant resin composition comprising 001 to 1 part by mass is disclosed. Patent Document 2 discloses (A) a thermoplastic resin (component A) 99 to 20 parts by mass, and (B) an apparent density of 0.15 g / cm. 3 or less and and, although thermoplastic resin composition pH of the aqueous layer when the graphite powder 5g dispersed in water 100g consists of graphite 1-80 parts by weight of 4 to 10 is disclosed, the composition Then, the flame retardancy was insufficient.
Patent Document 3 includes (C) an amino group and / or an epoxy group for a total of 100 parts by mass of (A) 60 to 90 parts by mass of an aromatic polycarbonate resin and (B) 10 to 40 parts by mass of graphite. Although an aromatic polycarbonate resin composition comprising 0.001 to 5 parts by mass of a silane compound and / or a silicone compound is disclosed, even in this technique, the size of about 1.5 mm required for a housing of an electronic device or the like is disclosed. Thickness does not provide sufficient flame retardancy.
Patent Document 4 discloses a heat-dissipating housing in which a heating element is accommodated, which is composed of a thermoplastic resin [A] and a specific heat-conductive filler [B], and conducts heat to 100 parts by mass of the thermoplastic resin [A]. Although a heat dissipating case composed of a thermally conductive resin composition having a filler [B] blending amount of 10 to 1000 parts by mass is disclosed, flame retardancy required for a case such as an electronic device is disclosed. There is no description about it, and since there is no addition of a flame retardant or an anti-drip agent, it is considered that the flame retardant is not sufficient.
すなわち、本発明は、(A)ポリカーボネート樹脂100質量部に対して、(B)人造黒鉛を30~100質量部、(C)フェニル基、メトキシ基及びビニル基から選ばれる基を有するオルガノポリシロキサン0.01~5質量部、(D)フッ素化合物0.01~5質量部を含有するポリカーボネート樹脂組成物、該ポリカーボネート樹脂組成物を成形してなる成形体、その成形体を含む電気・電子機器用部品、電気・電子機器用筐体、電気・電子機器用シャーシを提供するものである。 As a result of intensive studies to achieve the above object, the present inventors have found that the above problems can be solved by using a polycarbonate resin composition having the following components and ratios, and the present invention has been completed. It came to do.
That is, the present invention relates to (A) an organopolysiloxane having 100 to 100 parts by weight of a polycarbonate resin and (B) 30 to 100 parts by weight of artificial graphite and (C) a group selected from a phenyl group, a methoxy group and a vinyl group. A polycarbonate resin composition containing 0.01 to 5 parts by mass, (D) 0.01 to 5 parts by mass of a fluorine compound, a molded product formed by molding the polycarbonate resin composition, and an electric / electronic device including the molded product Parts, electrical / electronic equipment casings, electrical / electronic equipment chassis.
以下、各成分について説明する。
前記(A)成分のポリカーボネート樹脂(PC)としては、特に制限はなく種々のものが挙げられる。
通常、2価フェノールとカーボネート前駆体との反応により製造される芳香族ポリカーボネートを用いることができる。例えば、2価フェノールとカーボネート前駆体とを溶液法又は溶融法、具体的には、2価フェノールとホスゲンの反応、2価フェノールとジフェニルカーボネートなどとのエステル交換反応により製造されたものを使用することができる。 The polycarbonate resin composition of the present invention has a group selected from 30 to 100 parts by mass of (B) artificial graphite, (C) a phenyl group, a methoxy group, and a vinyl group with respect to (A) 100 parts by mass of the polycarbonate resin. A polycarbonate resin composition containing 0.01 to 5 parts by mass of an organopolysiloxane and (D) 0.01 to 5 parts by mass of a fluorine compound.
Hereinafter, each component will be described.
There is no restriction | limiting in particular as polycarbonate resin (PC) of the said (A) component, A various thing is mentioned.
Usually, an aromatic polycarbonate produced by a reaction between a dihydric phenol and a carbonate precursor can be used. For example, a dihydric phenol and a carbonate precursor are used by a solution method or a melting method, specifically, a reaction of a dihydric phenol and phosgene, or a transesterification reaction of a dihydric phenol and diphenyl carbonate or the like. be able to.
これらの中でも、特に好ましい2価フェノールとしては、ビス(ヒドロキシフェニル)アルカン系、特にビスフェノールAを主原料としたものである。
この他、2価フェノールとしては、ハイドロキノン、レゾルシン、カテコール等が挙げられる。これらの2価フェノールは、それぞれ単独で用いてもよいし、2種以上を混合して用いてもよい。
また、カーボネート前駆体としては、カルボニルハライド、カルボニルエステル、又はハロホルメートなどであり、具体的にはホスゲン、2価フェノールのジハロホーメート、ジフェニルカーボネート、ジメチルカーボネート、ジエチルカーボネートなどが挙げられる。 Examples of the dihydric phenol include various ones such as 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4- Hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) sulfide Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone and the like.
Among these, particularly preferred dihydric phenols are bis (hydroxyphenyl) alkanes, particularly those using bisphenol A as a main raw material.
In addition, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or in combination of two or more.
Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples include phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate.
なお、本発明において、天然黒鉛ではなく、人造黒鉛を必須とする理由は、薄肉での難燃性を得るためである。
本発明で用いる(B)人造黒鉛は、前記ポリカーボネート樹脂100質量部に対して30~100質量部であり、30~70質量部が好ましい。30質量部未満であると十分な熱伝導率が得られず、100質量部を超えると薄肉での難燃性が得られず、衝撃強度の低下、造粒時の分子量低下を引き起こす。 The artificial graphite as the component (B) is not particularly limited and may be a known one or a commercially available one. Artificial graphite is obtained by heat-treating amorphous carbon and artificially aligning irregularly arranged fine graphite crystals. In addition to artificial graphite used for general carbon materials, Kish graphite, cracked graphite, and Includes pyrolytic graphite. Artificial graphite used for general carbon materials is usually produced by graphitization treatment using petroleum coke or coal-based pitch coke as a main raw material.
In the present invention, the reason why artificial graphite is essential instead of natural graphite is to obtain flame retardancy with a thin wall.
The artificial graphite (B) used in the present invention is 30 to 100 parts by weight, preferably 30 to 70 parts by weight, based on 100 parts by weight of the polycarbonate resin. If it is less than 30 parts by mass, sufficient thermal conductivity cannot be obtained, and if it exceeds 100 parts by mass, flame retardancy with a thin wall cannot be obtained, causing a reduction in impact strength and a decrease in molecular weight during granulation.
また、フェニル基、メトキシ基及びビニル基から選ばれる基を必須として有するオルガノポリシロキサンを用いることにより、難燃性が向上する。
本発明で用いる(C)オルガノポリシロキサンは、前記ポリカーボネート樹脂100質量部に対して0.01~5質量部であり、1~4質量部が好ましい。0.01質量部未満であると十分な難燃性が得られず、5質量部を超えると燃焼時に滴下を起こしやすくなる。 The organopolysiloxane of component (C) is not particularly limited as long as it has a group selected from a phenyl group, a methoxy group, and a vinyl group. For example, KR-511 manufactured by Shin-Etsu Chemical Co., Ltd. BY16-161 and the like.
Moreover, flame retardance improves by using the organopolysiloxane which has as essential a group chosen from a phenyl group, a methoxy group, and a vinyl group.
The organopolysiloxane (C) used in the present invention is 0.01 to 5 parts by weight, preferably 1 to 4 parts by weight, based on 100 parts by weight of the polycarbonate resin. If it is less than 0.01 part by mass, sufficient flame retardancy cannot be obtained, and if it exceeds 5 parts by mass, dripping tends to occur during combustion.
本発明で用いる(D)フッ素化合物は、前記ポリカーボネート樹脂100質量部に対して0.01~5質量部であり、0.5~4質量部が好ましい。0.01質量部未満であると滴下防止効果がなく、5質量部を超えると難燃性を低下させる。 The (D) fluorine compound is used as an anti-drip agent and is not particularly limited as long as it is a fluorine-containing compound. For example, a fluorine-containing polymer having a fibril-forming ability can be mentioned. Examples thereof include tetrafluoroethylene, tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer), partially fluorinated polymers, and polycarbonate resins produced from fluorinated diphenols. Of these, polytetrafluoroethylene (PTFE) is preferred.
The fluorine compound (D) used in the present invention is 0.01 to 5 parts by mass, preferably 0.5 to 4 parts by mass with respect to 100 parts by mass of the polycarbonate resin. If it is less than 0.01 part by mass, there will be no dripping prevention effect, and if it exceeds 5 parts by mass, flame retardancy will be reduced.
前記(E)成分のアルカリ金属又はアルカリ土類金属[以下、両者を合わせて「アルカリ(土類)金属」と記載することがある]の有機スルホン酸塩としては、パーフルオロアルキルスルホン酸とアルカリ金属又はアルカリ土類金属との金属塩のようなフッ素置換アルキルスルホン酸の金属塩、並びに芳香族スルホン酸とアルカリ金属又はアルカリ土類金属塩との金属塩等が挙げられる。 In addition to the components (A) to (D), the polycarbonate resin composition of the present invention includes (E) an organic sulfonate of an alkali metal or alkaline earth metal as a flame retardant, and (F) an antioxidant that is a phosphorus-containing compound. It is preferable to contain an agent.
As the organic sulfonate of the alkali metal or alkaline earth metal of the component (E) [hereinafter sometimes referred to as “alkali (earth) metal” together ”, perfluoroalkylsulfonic acid and alkali Examples include metal salts of fluorine-substituted alkyl sulfonic acids such as metal salts with metals or alkaline earth metals, and metal salts of aromatic sulfonic acids with alkali metals or alkaline earth metal salts.
本発明で用いる(F)リン含有化合物は、前記ポリカーボネート樹脂100質量部に対して通常0.001~1質量部であり、0.001質量部以上であれば造粒工程・成形工程での熱安定性が良好であり、1質量部以下であれば分子量低下を引き起こすことが無い。 Examples of the antioxidant that is the phosphorus-containing compound (F) include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Among these, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, triorganophosphate compound, and acid phosphate compound are particularly preferable. The organic group in the acid phosphate compound includes any of mono-substituted, di-substituted, and mixtures thereof. Any of the following exemplified compounds corresponding to the compound is similarly included.
The phosphorus-containing compound (F) used in the present invention is usually 0.001 to 1 part by mass with respect to 100 parts by mass of the polycarbonate resin. The stability is good, and if it is 1 part by mass or less, the molecular weight is not lowered.
例えば、前記(A)~(D)成分、及び必要に応じ(E)、(F)成分及び離型剤を添加し、V型ブレンダー、ヘンシェルミキサー、メカノケミカル装置、押出混合機などの予備混合手段を用いて充分に混合した後、必要に応じて、押出造粒器やブリケッティングマシーンなどにより予備混合物の造粒を行い、その後、ベント式二軸押出機に代表される溶融混練機で溶融混練し、次いでペレタイザーによりペレット化する方法が挙げられる。
また、上記各成分をそれぞれ独立に、ベント式二軸押出機に代表される溶融混練機に供給する方法や、各成分の一部を予備混合した後、残りの成分と独立に溶融混練機に供給する方法なども挙げられる。
各成分の一部を予備混合する方法としては、例えば、ポリカーボネート樹脂(A)成分以外の成分を予め予備混合した後、ポリカーボネート樹脂(A)成分に混合又は押出機に直接供給する方法が挙げられる。 The method for producing the polycarbonate resin composition of the present invention is not particularly limited, and may be a known method.
For example, the components (A) to (D), and the components (E) and (F) and a release agent, if necessary, are added and premixed in a V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc. After thorough mixing using means, if necessary, granulate the pre-mixture with an extrusion granulator or briquetting machine, and then use a melt kneader typified by a vent type twin screw extruder. A method of melt-kneading and then pelletizing with a pelletizer can be mentioned.
In addition, a method of supplying each of the above components independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then the melt kneader independently of the remaining components. Examples include a method of supplying.
Examples of the method of premixing a part of each component include a method in which components other than the polycarbonate resin (A) component are premixed in advance and then mixed with the polycarbonate resin (A) component or directly supplied to the extruder. .
さらに、ある一成分を独立に溶融押出機の途中から供給する方法なども挙げられる。
なお、配合する成分に液状のものがある場合には、溶融押出機への供給に所謂液注装置又は液添装置を使用することができる。
押出機としては、原料中の水分や、溶融混練ポリカーボネート樹脂組成物から発生する揮発ガスを脱気できるベントを有するものが好ましく使用できる。
ベントからは発生水分や揮発ガスを効率よく押出機外部へ排出するための真空ポンプが好ましく設置される。
また、押出原料中に混入した異物などを除去するためのスクリーンを押出機ダイス部前のゾーンに設置し、異物を樹脂組成物から取り除くことも可能である。
スクリーンとしては、金網、スクリーンチェンジャー、焼結金属プレート(ディスクフィルターなど)などを挙げることができる。
溶融混練機としては、二軸押出機の他に、バンバリーミキサー、混練ロール、単軸押出機、3軸以上の多軸押出機などを挙げることができる。 As a premixing method, for example, when a polycarbonate resin (component A) having a powder form is included, a master batch of an additive diluted with a powder by blending a part of the powder with an additive to be blended is used. The method of manufacturing and using a masterbatch is mentioned.
Furthermore, the method etc. which supply a certain component independently from the middle of a melt extruder are also mentioned.
In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.
As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded polycarbonate resin composition can be preferably used.
From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder.
It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die.
Examples of the screen include a wire mesh, a screen changer, and a sintered metal plate (such as a disk filter).
Examples of the melt-kneader include a banbury mixer, a kneading roll, a single-screw extruder, a triaxial or more multi-screw extruder, in addition to a twin-screw extruder.
本発明のポリカーボネート樹脂組成物は、通常、上記のように製造されたペレットを射出成形して成形品を得ることにより各種製品を製造することができる。
射出成形においては、通常の成形方法だけでなく、射出圧縮成形、射出プレス成形、ガスアシスト射出成形、発泡成形(超臨界流体を注入する方法を含む)、インサート成形、インモールドコーティング成形、断熱金型成形、急速加熱冷却金型成形、二色成形、サンドイッチ成形及び超高速射出成形などを挙げることができる。 The extruded polycarbonate resin composition is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer and pelletized.
The polycarbonate resin composition of the present invention can usually produce various products by injection-molding the pellets produced as described above to obtain molded products.
In injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, and heat insulation gold Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding.
実施例1~5及び比較例1~8
各配合成分をそれぞれ乾燥した後、表1及び表2に示す配合割合及び配合比率で、二軸押出機(東芝機械(株)製、商品名TEM35)を用い、バレル温度300~320℃、スクリュ回転数100~600回転、吐出10~30kg/hrにて溶融混練し、評価用サンプルを得た。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.
Examples 1 to 5 and Comparative Examples 1 to 8
After each compounding component was dried, using a twin screw extruder (trade name TEM35, manufactured by Toshiba Machine Co., Ltd.) at the compounding ratio and compounding ratio shown in Tables 1 and 2, the barrel temperature was 300 to 320 ° C., the screw. An evaluation sample was obtained by melt-kneading at a rotational speed of 100 to 600 and a discharge of 10 to 30 kg / hr.
成分(A):FN1900A[MV=19500]、FN2200A[MV=21500]、FN2600A[MV=25500][商品名、出光興産(株)製]
仕込み分子量(粘度平均分子量)[MV]19000~30000に調整
成分(B):
・天然黒鉛:鱗片黒鉛粉末CB-150[商品名、日本黒鉛工業(株)製]:鱗片状、粒度分布63μm以下77~87質量%、106μm以上5質量%以下、見かけ密度0.2~0.3g/cu・cm、50質量%累積径31~48μm、固定炭素98質量%以上、灰分1質量%以下、揮発分1%以下
・人造黒鉛:人造黒鉛粉末PAG-420[商品名、日本黒鉛工業(株)製]:不定形、50質量%累積径30~40μm(50μm以上 50%以下)、見かけ密度0.29-0.37g/cu・cm、固定炭素99.4以上、揮発分0.3以下、灰分0.3以下
成分(C):
KR-511(メトキシ基及びビニル基を有するオルガノシロキサン)[商品名、信越化学工業(株)製]
SH-6040(グリシドキシプロピルトリメトキシシラン)[商品名、東レ・ダウコーニング(株)製]
BY16-161[商品名、東レ・ダウコーニング(株)製](メトキシ基が2価炭化水素を介してケイ素原子に結合したメトキシシリル基を含むシリコーン)
成分(D):高分子量ポリテトラフルオロエチレン(PTFE):
CD076[商品名、旭硝子株式会社(株)製]
アルゴフロンF5[商品名、ソルベイ ソレクシス(株)製]
成分(E):パーフルオロブタンスルホン酸カリウム塩[三菱マテリアル(株)製 エフトップ、商品名KFBS]
成分(F):
JC263(トリフェニルホスフィン)[商品名、城北化学工業(株)製]
アデカスタブ C(ジフェニルイソオクチルフォスファイト)(ADK StabC)[商品名、ADEKA(株)製]
Irganox1076(オクタデシル-3-(3,5-ジ-t-ブチル- ヒドロキシフェニル)プロピオネ-ト)[商品名、チバ・ジャパン(株)製]
離型剤:
S-100A[商品名、理研ビタミン(株)製]
EW-440A[商品名、理研ビタミン(株)製] The composition materials used in Examples and Comparative Examples are as follows.
Component (A): FN1900A [MV = 19500], FN2200A [MV = 21500], FN2600A [MV = 25500] [trade name, manufactured by Idemitsu Kosan Co., Ltd.]
Preparation molecular weight (viscosity average molecular weight) [MV] 19000-30000 Adjustment component (B):
Natural graphite: scale graphite powder CB-150 [trade name, manufactured by Nippon Graphite Industry Co., Ltd.]: scale, particle size distribution 63 μm or less 77 to 87% by mass, 106 μm or more and 5% by mass or less, apparent density 0.2 to 0 .3 g / cu · cm, 50 mass% cumulative diameter 31 to 48 μm, fixed carbon 98 mass% or more, ash content 1 mass% or less, volatile content 1% or less ・ Artificial graphite: artificial graphite powder PAG-420 [trade name, Nippon Graphite Manufactured by Kogyo Co., Ltd.]: amorphous, 50% by mass cumulative diameter 30 to 40 μm (50 μm to 50%), apparent density 0.29 to 0.37 g / cu · cm, fixed carbon 99.4 or more, volatile content 0 .3 or less, Ash content 0.3 or less Component (C):
KR-511 (organosiloxane having a methoxy group and a vinyl group) [trade name, manufactured by Shin-Etsu Chemical Co., Ltd.]
SH-6040 (glycidoxypropyltrimethoxysilane) [trade name, manufactured by Toray Dow Corning Co., Ltd.]
BY16-161 [trade name, manufactured by Toray Dow Corning Co., Ltd.] (silicone containing a methoxysilyl group in which a methoxy group is bonded to a silicon atom via a divalent hydrocarbon)
Component (D): high molecular weight polytetrafluoroethylene (PTFE):
CD076 [trade name, manufactured by Asahi Glass Co., Ltd.]
Algoflon F5 [trade name, manufactured by Solvay Solexis Co., Ltd.]
Ingredient (E): potassium perfluorobutanesulfonate [Mitsubishi Materials Co., Ltd. F-top, trade name KFBS]
Ingredient (F):
JC263 (triphenylphosphine) [trade name, manufactured by Johoku Chemical Industry Co., Ltd.]
ADK STAB C (diphenylisooctyl phosphite) (ADK StabC) [trade name, manufactured by ADEKA Corporation]
Irganox 1076 (octadecyl-3- (3,5-di-t-butyl-hydroxyphenyl) propionate) [trade name, manufactured by Ciba Japan Co., Ltd.]
Release agent:
S-100A [trade name, manufactured by Riken Vitamin Co., Ltd.]
EW-440A [trade name, manufactured by Riken Vitamin Co., Ltd.]
(1)難燃性
12.7mm×127mm×(1.35mmt、1.2mmt、1.0mmt)の試験片を射出成形にて成形。UL94 V試験に準拠した方法にて燃焼試験を行い、難燃性のランク(V-0,V-1,V-2)を判定した。
なお、表1及び表2において、NOTとは、UL94 V試験に準拠した方法において、試験結果がV-0~V-2の基準に満たないことを示す。
(2)引張破断強度[MPa]
ASTM D638に準拠して測定した。
(3)伸び[%]
ASTM D638に準拠して測定した。
(4)曲げ強度[MPa]
ASTM D790に準拠して測定した。
(5)曲げ弾性率[MPa]
ASTM D790に準拠して測定した。
(6)IZOD衝撃強度(ノッチ有)[kJ/m2]
ASTM D256に準拠して測定した。
(7)IZOD衝撃強度(ノッチなし)[kJ/m2]
ASTM D256に準拠して測定した。
(8)熱伝導率[W/m・K]
ホットディスク法にて測定した。 The following evaluation was performed about the obtained sample. The results are shown in Tables 1 and 2.
(1) Flame retardance 12.7 mm × 127 mm × (1.35 mmt, 1.2 mmt, 1.0 mmt) test pieces were formed by injection molding. A combustion test was performed by a method based on the UL94 V test, and the flame retardance rank (V-0, V-1, V-2) was determined.
In Tables 1 and 2, “NOT” indicates that the test result does not satisfy the criteria of V-0 to V-2 in the method based on the UL94 V test.
(2) Tensile breaking strength [MPa]
Measured according to ASTM D638.
(3) Elongation [%]
Measured according to ASTM D638.
(4) Bending strength [MPa]
Measured according to ASTM D790.
(5) Flexural modulus [MPa]
Measured according to ASTM D790.
(6) IZOD impact strength (notched) [kJ / m 2 ]
Measured according to ASTM D256.
(7) IZOD impact strength (no notch) [kJ / m 2 ]
Measured according to ASTM D256.
(8) Thermal conductivity [W / m · K]
Measurement was performed by the hot disk method.
このため、難燃性が求められる各種の成形体として有用であり、特に、放熱部品、熱伝達用部品、例えば、電気電子機器用部品、例えば、筐体やシャーシとして有用である。 As described above in detail, a molded product obtained by molding the polycarbonate resin composition of the present invention has high thermal conductivity, high mechanical strength, and is thin but highly flame retardant.
For this reason, it is useful as various molded products that require flame retardancy, and is particularly useful as a heat radiating component, a component for heat transfer, for example, a component for electric and electronic equipment, for example, a casing or a chassis.
Claims (8)
- (A)ポリカーボネート樹脂100質量部に対して、(B)人造黒鉛を30~100質量部、(C)フェニル基、メトキシ基及びビニル基から選ばれる基を有するオルガノポリシロキサン0.01~5質量部、(D)フッ素化合物0.01~5質量部を含有するポリカーボネート樹脂組成物。 (A) 30 to 100 parts by mass of (B) artificial graphite with respect to 100 parts by mass of the polycarbonate resin, (C) 0.01 to 5 parts by mass of an organopolysiloxane having a group selected from a phenyl group, a methoxy group and a vinyl group Part, (D) a polycarbonate resin composition containing 0.01 to 5 parts by mass of a fluorine compound.
- さらに、(E)難燃剤としてアルカリ金属又はアルカリ土類金属の有機スルホン酸塩を含有し、その含有量が0.01~1質量部である請求項1に記載のポリカーボネート樹脂組成物。 The polycarbonate resin composition according to claim 1, further comprising (E) an organic sulfonate of an alkali metal or alkaline earth metal as a flame retardant, wherein the content is 0.01 to 1 part by mass.
- さらに、成分(F)リン含有化合物である酸化防止剤を含有し、その含有量が0.001~1質量部である請求項1に記載のポリカーボネート樹脂組成物。 The polycarbonate resin composition according to claim 1, further comprising an antioxidant which is a component (F) phosphorus-containing compound, and the content thereof is 0.001 to 1 part by mass.
- 請求項1~3のいずれかに記載のポリカーボネート樹脂組成物を成形してなる成形体。 A molded article formed by molding the polycarbonate resin composition according to any one of claims 1 to 3.
- 請求項4に記載の成形体を含む放熱部品、熱伝達用部品。 A heat dissipating part and a heat transfer part including the molded body according to claim 4.
- 請求項4に記載の成形体を含む電気・電子機器用部品。 A part for electrical and electronic equipment including the molded product according to claim 4.
- 請求項4に記載の成形体を含む電気・電子機器用筐体。 A casing for an electric / electronic device including the molded body according to claim 4.
- 請求項4に記載の成形体を含む電気・電子機器用シャーシ。 A chassis for electrical and electronic equipment including the molded body according to claim 4.
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WO2012174574A2 (en) | 2011-06-15 | 2012-12-20 | Bayer Materialscience Llc | Thermally conductive thermoplastic compositions |
US20150165064A1 (en) * | 2013-06-21 | 2015-06-18 | Innate Pharma | Enzymatic conjugation of polypeptides |
JP2018125264A (en) * | 2017-02-03 | 2018-08-09 | オムロン株式会社 | Abnormality detection device |
WO2018164666A1 (en) | 2017-03-07 | 2018-09-13 | Covestro Llc | Two shot injection molding process for thermoplastic parts |
US10156352B2 (en) | 2013-04-19 | 2018-12-18 | Covestro Llc | In mold electronic printed circuit board encapsulation and assembly |
WO2021076561A1 (en) | 2019-10-15 | 2021-04-22 | Covestro Llc | Three part headlamp assembly |
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- 2010-07-27 WO PCT/JP2010/062577 patent/WO2011013645A1/en active Application Filing
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Also Published As
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CN102471568A (en) | 2012-05-23 |
JPWO2011013645A1 (en) | 2013-01-07 |
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