JPH0480249A - Production of filled resin composition - Google Patents
Production of filled resin compositionInfo
- Publication number
- JPH0480249A JPH0480249A JP19533490A JP19533490A JPH0480249A JP H0480249 A JPH0480249 A JP H0480249A JP 19533490 A JP19533490 A JP 19533490A JP 19533490 A JP19533490 A JP 19533490A JP H0480249 A JPH0480249 A JP H0480249A
- Authority
- JP
- Japan
- Prior art keywords
- melt
- resin composition
- weight
- parts
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 239000011256 inorganic filler Substances 0.000 claims abstract description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 16
- 229920006351 engineering plastic Polymers 0.000 claims abstract description 14
- 239000004417 polycarbonate Substances 0.000 claims abstract description 8
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 7
- 239000004952 Polyamide Substances 0.000 claims abstract description 6
- 229920002647 polyamide Polymers 0.000 claims abstract description 6
- 229920001230 polyarylate Polymers 0.000 claims abstract description 6
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 5
- 229920000728 polyester Polymers 0.000 claims abstract description 4
- 229920001971 elastomer Polymers 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 11
- 239000005060 rubber Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 14
- 238000004898 kneading Methods 0.000 abstract 3
- 239000000178 monomer Substances 0.000 description 19
- 238000002156 mixing Methods 0.000 description 18
- 229920002554 vinyl polymer Polymers 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 8
- -1 polybutylene terephthalate Polymers 0.000 description 8
- 229920000578 graft copolymer Polymers 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920001890 Novodur Polymers 0.000 description 3
- 229920001893 acrylonitrile styrene Polymers 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012765 fibrous filler Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- VUKHQPGJNTXTPY-UHFFFAOYSA-N but-2-enylbenzene Chemical compound CC=CCC1=CC=CC=C1 VUKHQPGJNTXTPY-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 235000015115 caffè latte Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical compound CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は、充填剤配合樹脂組成物の製造方法に関する。[Detailed description of the invention] <Industrial application field> The present invention relates to a method for producing a filled resin composition.
サラに詳しくは、各種エンジニアリングプラスチックと
ゴム強化スチレン系樹脂および非繊維状無機充填剤から
なる充填剤を配合してなる樹脂組成物の改良された製造
方法に関するものである。More specifically, the present invention relates to an improved method for producing resin compositions made by blending various engineering plastics with fillers consisting of rubber-reinforced styrene resins and non-fibrous inorganic fillers.
〈従来の技術〉
ＡＢＳ樹脂、ＡＢＳ樹脂に代表されるゴム強化スチレン
系樹脂は、耐衝撃性、加工性等の物性バランスに優れる
ことから、自動車分野、事務機器分野等、広範囲な用途
に使用されている。これらの中でも、特に自動車分野に
おいて要求される性能は年々過酷になってきており、こ
れらゴム強化スチレン系樹脂単独では、その性質上、改
良できる物性にも限界があるため、近年、各種エンジニ
アリングプラスチックとのブレンド、すなわちポリマー
アロイが行われている。<Conventional technology> ABS resin, rubber-reinforced styrene resin represented by ABS resin, has an excellent balance of physical properties such as impact resistance and processability, and is therefore used in a wide range of applications such as the automobile field and office equipment field. ing. Among these, the performance requirements particularly in the automotive field are becoming more severe year by year, and due to the nature of these rubber-reinforced styrene resins, there are limits to the physical properties that can be improved, so in recent years, various engineering plastics and Blends, or polymer alloys, are being carried out.
例えば、ポリカーボネート、ポリアミド、ポリブチレン
テレフタレート、ポリフェニレンエーテル、ポリアリレ
ート等とブレンドすることにより、それらポリマーのも
つ優れｔζ−物性をゴム強化スチレン系樹脂に付与でき
るものである。For example, by blending it with polycarbonate, polyamide, polybutylene terephthalate, polyphenylene ether, polyarylate, etc., the excellent tζ-physical properties of these polymers can be imparted to the rubber-reinforced styrenic resin.
一方、一般に、これら熱可塑性樹脂の物性を改善する目
的で、各種の無機充填剤を配合することが知られており
、前記ゴム強化スチレン系樹脂とエンジニアリングプラ
スチックとのポリマーアロイにおいても必要に応じて無
機充填剤が配合されている。On the other hand, it is generally known that various inorganic fillers are blended in order to improve the physical properties of these thermoplastic resins, and they are also used in polymer alloys of the rubber-reinforced styrene resin and engineering plastics as necessary. Contains inorganic fillers.
例えば、剛性の向上や低線膨張係数を有する樹脂を得る
ために、タルクや炭酸カルシウム等を配合することが知
られている。For example, it is known to add talc, calcium carbonate, etc. to improve rigidity and obtain a resin with a low coefficient of linear expansion.
従来、これら無機充填剤を配合する場合には、通常、配
合に供される樹脂と一括にて混合されている。Conventionally, when these inorganic fillers are blended, they are usually mixed all at once with the resin used for blending.
〈発明が解決しようとする問題点〉
しかしながら、前記エンジニアリングプラスチックとゴ
ム強化スチレン系樹脂からなる組成物の物性改良を目的
として無機充填剤を配合するに際し、８者−括にて混合
した場合には、無機充填剤未配合に比べて期待する程物
性が向上しないという以外な問題が生じる。<Problems to be Solved by the Invention> However, when blending an inorganic filler for the purpose of improving the physical properties of a composition consisting of the engineering plastic and rubber-reinforced styrene resin, when mixing in a group of 8 parts, However, other problems arise in that the physical properties are not as improved as expected compared to the case where no inorganic filler is added.
く問題点を解決するための手段〉
本発明者らは、上記の問題点につき鋭意検討した結果、
まず、ゴム強化スチレン系樹脂と非繊維状無機充填剤を
溶融混合し、次いで得られた混合物とエンジニアリング
プラスチックを溶融混合することにより、大幅な物性の
向上が計れるという事実を見い出し、本発明に到達した
。Means for Solving the Problems〉 As a result of intensive study on the above problems, the present inventors have found that
First, we discovered that by melt-mixing a rubber-reinforced styrene-based resin and a non-fibrous inorganic filler, and then melt-mixing the resulting mixture with an engineering plastic, it was possible to significantly improve physical properties, leading to the present invention. did.
すなわち、本発明は、
ポリカーボネート、ポリアミド、飽和ポリエステル、ポ
リフェニレンエーテル、ポリアリレートから選ばれた１
種又は２種以上のエンジニアリングプラスチック（Ａ）
５〜６０重量部、ゴム強化スチレン系樹脂（Ｂ） １０
〜９４重量部および非繊維状無機充填剤（Ｃ）１〜５０
重量部（ただし、（Ａ）＋（Ｂ） ＋（Ｃ）の合計量を
１００重量部とする。）からなる充填剤配合樹脂組成物
を製造するにあたり、まず、上記（Ｂ）成分と（Ｃ）成
分を溶融混合し、次いで、得られた混合物と上記（Ａ）
成分とを溶融混合することを特徴とする充填剤配合樹脂
組成物の製造方法を提供するものである。That is, the present invention provides one material selected from polycarbonate, polyamide, saturated polyester, polyphenylene ether, and polyarylate.
Species or two or more types of engineering plastics (A)
5 to 60 parts by weight, rubber reinforced styrene resin (B) 10
~94 parts by weight and non-fibrous inorganic filler (C) 1-50
In producing a filler-containing resin composition consisting of parts by weight (however, the total amount of (A) + (B) + (C) is 100 parts by weight), the above (B) component and (C) are first combined. ) components are melt-mixed, and then the obtained mixture and the above (A) are mixed together.
The present invention provides a method for producing a filler-containing resin composition, which comprises melt-mixing the filler-containing resin compositions.
以下に本発明について詳細に説明する。The present invention will be explained in detail below.
本発明で用いられるエンジニアリングプラスチック（Ａ
）とは、ポリカーボネート、ポリアミド、飽和ホＩＪエ
ステル、ポリフェニレンエーテルオヨびポリアリレート
からなる群より選ばれた１種又は２種以上であり、二価
フェノールとカーボネート先駆体、例えばホスゲン、ジ
フェニルカーボネートなどの反応によって得られる芳香
族ポリカーボネート、６−ナイロン、６ローナイロン、
６／６６共重合ナイロン、４６−ナイロン、１２−ナイ
ロン等のポリアミド、ポリエチレンテレフタレート、ポ
リブチレンテレフタレート等の飽和ポリエステル、−形
成
（Ｒ１，Ｒ２，Ｒ８は同一の又は異なるアルキル基、ア
リール基、ハロゲン、水素などの一価の残基を示す。）
で表されるポリフェニレンエーテル、二価フェノールと
芳香族ジカルボン酸、例えばテレフタル酸、イソフタル
酸などとの反応によって得られるポリアリレートが示さ
れ、各々１種又は２種以上用いることができる。Engineering plastic used in the present invention (A
) is one or more selected from the group consisting of polycarbonate, polyamide, saturated IJ ester, polyphenylene ether, polyarylate, and dihydric phenol and carbonate precursors such as phosgene and diphenyl carbonate. Aromatic polycarbonate obtained by reaction, 6-nylon, 6-row nylon,
6/66 copolymerized nylon, polyamide such as 46-nylon, 12-nylon, saturated polyester such as polyethylene terephthalate, polybutylene terephthalate, -formation (R1, R2, R8 are the same or different alkyl groups, aryl groups, halogens, (Indicates monovalent residues such as hydrogen.)
These are polyphenylene ethers and polyarylates obtained by reacting dihydric phenols with aromatic dicarboxylic acids, such as terephthalic acid and isophthalic acid, and one or more types of each can be used.
本発明におけるゴム強化スチレシ系樹ｍ（Ｂ）とは、ゴ
ム状重合体の存在下に芳香族ビニル系単量体および必要
に応じて共重合可能な他のビニル系単量体を重合して得
られるグラフト共重合体または該グラフト共重合体と、
芳香族ビニル系単量体および必要に応じて共重合可能な
他のビニル系単量体を重合して得られる芳香族ビニル系
重合体との混合物である。In the present invention, the rubber-reinforced styrene resin m(B) is obtained by polymerizing an aromatic vinyl monomer and, if necessary, other copolymerizable vinyl monomers in the presence of a rubbery polymer. The obtained graft copolymer or the graft copolymer,
It is a mixture of an aromatic vinyl monomer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl monomer and, if necessary, another copolymerizable vinyl monomer.
ゴム強化スチレン系樹脂（Ｂ）を構成するゴム状重合体
としては、ポリブタジェン、ブタジェンスチレン共重合
体、ブタジェン−アクリロニトリル共重合体等のジエン
系ゴム状重合体およびエチレシープロピレン共重合体、
エチレン−プロピレン−非共役ジエン共重合体、アクリ
ル系ゴム状重合体、塩素化ポリエチレン等の非ジエン系
ゴム状重合体が例示され、１種又は２種以上使用するこ
とができる。これらのゴム状重合体は乳化重合、溶液重
合、懸濁重合、塊状重合等により製造される。Examples of the rubbery polymer constituting the rubber-reinforced styrene resin (B) include diene rubbery polymers such as polybutadiene, butadiene styrene copolymer, butadiene-acrylonitrile copolymer, and ethylene propylene copolymer;
Non-diene rubbery polymers such as ethylene-propylene-nonconjugated diene copolymer, acrylic rubbery polymer, and chlorinated polyethylene are exemplified, and one type or two or more types can be used. These rubbery polymers are produced by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, and the like.
なお、乳化重合により製造する場合におけるゴム状重合
体の粒子径およびゲル含有率については特に制限はない
が、平均粒子径０．１〜１μｍおよびゲル含有率０〜９
５％であることが好ましい。There are no particular restrictions on the particle size and gel content of the rubbery polymer when produced by emulsion polymerization, but the average particle size is 0.1 to 1 μm and the gel content is 0 to 9.
Preferably it is 5%.
芳香族ビニル系単量体としては、スチレン、α−メチル
スチレン、０−メチルスチレン、ｍ−メチルスチレン、
ｐ−メチルスチレン、ｔ−ブチルスチレン、α−メチル
ビニルトルエン、ジメチルスチレン、クロルスチレン、
ジクロルスチレン、ブロムスチレン、ジブロムスチレン
等が例示され、１種又は２種以上用いることができる。Examples of aromatic vinyl monomers include styrene, α-methylstyrene, 0-methylstyrene, m-methylstyrene,
p-methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorstyrene,
Dichlorostyrene, bromstyrene, dibromstyrene, etc. are exemplified, and one type or two or more types can be used.
特にスチレン、α−メチルスチレンが好ましい。Particularly preferred are styrene and α-methylstyrene.
芳香族ビニル系単量体と共重合可能な他のビニル系単量
体としては、アクリロニトリル、メタクリレートリル等
のシアン化ビニル系単量体、メチルアクリレート、エチ
ルアクリレート、ブチルアクリレート、２−エチルへキ
シルアクリレート、メチルメタクリレート、エチルメタ
クリレート、プロピルメタクリレート、２−エチルへキ
シルメタクリレート等の不飽和カルボン酸アルキルエス
テル、マレイミド、Ｎ−フェニルマレイミド、Ｎメチル
マレイミド、Ｎ−シクロへキシルマレイミド等のマレイ
ミド系単量体が例示され各々１種又は２種以上用いるこ
とができる。特にアクリロニトリル、メチルメタクリレ
ートおよびＮ−フェニルマレイミドが好ましい。Other vinyl monomers that can be copolymerized with aromatic vinyl monomers include vinyl cyanide monomers such as acrylonitrile and methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl. Unsaturated carboxylic acid alkyl esters such as acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and 2-ethylhexyl methacrylate; maleimide monomers such as maleimide, N-phenylmaleimide, N-methylmaleimide, and N-cyclohexylmaleimide; are exemplified, and each can be used alone or in combination of two or more. Particularly preferred are acrylonitrile, methyl methacrylate and N-phenylmaleimide.
グラフト重合方法としては、公知の乳化重合、懸濁重合
、溶液重合、塊状重合またはこれらを組合わせた方法が
用いられる。As the graft polymerization method, known methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination thereof are used.
グラフト共重合体と混合して用いられる芳香族ビニル系
重合体を構成する芳香族ビニル系単量体および共重合可
能な他のビニル系単量体としては、各々グラフト共重合
体に用いられるものと同一の群から任意の１種又は２種
以上を選択して用いることができる。また、該重合体の
重合方法としては、公知の乳化重合、懸濁重合、溶液重
合、塊状重合またはこれらを組合わせた方法が用いられ
る。The aromatic vinyl monomer constituting the aromatic vinyl polymer used in combination with the graft copolymer and other copolymerizable vinyl monomers include those used in the graft copolymer. Any one type or two or more types can be selected and used from the same group as . Further, as a method for polymerizing the polymer, known methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination thereof are used.
ゴム強化スチレン系樹脂におけるゴム状重合体と単量体
との構成比には制限はないが、好ましくはゴム状重合体
２０〜８０重量％、単量体８０〜２０重量％である。ま
たかかる単量体における芳香族ビニル系単量体と他のビ
ニル系単量体との構成比にも特に制限はないが、芳香族
ビニル系単量体１０〜１００重量％、特に３０〜７０重
量％、他のビニル系単量体９０〜０重量％、特に７０〜
３０重量％が好ましい。Although there is no restriction on the composition ratio of the rubbery polymer and monomer in the rubber-reinforced styrenic resin, it is preferably 20 to 80% by weight of the rubbery polymer and 80 to 20% by weight of the monomer. There is also no particular restriction on the composition ratio of the aromatic vinyl monomer and other vinyl monomers in such monomers, but the aromatic vinyl monomer is 10 to 100% by weight, particularly 30 to 70% by weight. % by weight, other vinyl monomers 90-0% by weight, especially 70-0% by weight
30% by weight is preferred.
本発明にて用いられる非繊維状無機充填剤としては、例
えば、タルク、炭酸カルシウム、カーボンブラック、ホ
ワイトカーボン、硫酸バリウム、カオリンクレー、カル
シウムメタシリケート、ケイソウ土、グラファイトガラ
ス等が挙げられる。Examples of the non-fibrous inorganic filler used in the present invention include talc, calcium carbonate, carbon black, white carbon, barium sulfate, kaolin clay, calcium metasilicate, diatomaceous earth, and graphite glass.
これらの充填剤は非繊維状のものが使用される。These fillers are non-fibrous.
すなわち、パウダー、ビーズのような球状、立方体のよ
うな等方性の形状をもつものや、板状などの異方性の形
状をもつもの等が挙げられる。That is, examples include those having a spherical shape such as powder or beads, isotropic shapes such as a cube, and those having an anisotropic shape such as a plate shape.
なお、繊維状の充填剤は、一般に、溶融混合時に繊維鎖
が破断しやすく、この繊維鎖の破断が著しい場合には、
繊維状充填剤としての効果を発揮することができなくな
るため、充填剤を２段階にて溶融混合する本発明の製造
方法には適さないものである。In general, the fiber chains of fibrous fillers tend to break during melt mixing, and if the fiber chains break significantly,
Since it is no longer effective as a fibrous filler, it is not suitable for the production method of the present invention in which the filler is melt-mixed in two stages.
本発明の充填剤配合樹脂組成物は、前述のエンジニアリ
ングプラスチック（Ａ）５〜６０重量部、ゴム強化スチ
レン系樹脂（Ｂ） １０〜９４重量部および非繊維状無
機充填剤（Ｃ） １〜５０重量部から構成される。The filler-containing resin composition of the present invention includes 5 to 60 parts by weight of the above-mentioned engineering plastic (A), 10 to 94 parts by weight of the rubber-reinforced styrene resin (B), and 1 to 50 parts by weight of the non-fibrous inorganic filler (C). Consists of parts by weight.
構成比が上記の範囲外では十分な耐衝撃性が得られない
。If the composition ratio is outside the above range, sufficient impact resistance cannot be obtained.
本発明における上記充填剤配合樹脂組成物の製造方法と
は、まず、（Ｂ）成分と（Ｃ）成分を溶融混合し、次い
で得られた混合物と（Ａ）成分を溶融混合するものであ
る。The method for producing the above-mentioned filler-containing resin composition in the present invention is to first melt-mix components (B) and (C), and then melt-mix the resulting mixture and component (A).
これらの溶融混合方法としては、それぞれｌ軸または２
軸押用機、バンバリーミキサ−、ロール等の公知の方法
を採用することができる。These melt mixing methods include l-axis or 2-axis, respectively.
Known methods such as a screw press, a Banbury mixer, and a roll can be employed.
前記（Ｂ）成分と（Ｃ）成分との溶融混合物に（Ａ）成
分を混合する方法としては、あらかじめ（Ｂ）成分と（
Ｃ）成分を混合するこＬによってペレット化して、得ら
れたペレットと（Ａ）成分とを混合する方法、またはシ
リンダーの中間部および後部に材料供給口を有する押出
機を用いて、まず（Ｂ）成分と（Ｃ）成分をシリンダー
後部に供給することによって溶融混合させ、次いで（Ａ
）成分をシリンダー中間部に供給することにより混合す
る方法が採用できる。As a method of mixing the (A) component into the molten mixture of the (B) component and (C) component, the (B) component and (
C) A method of pelletizing the components by mixing L and mixing the obtained pellets with the component (A), or using an extruder having material supply ports in the middle and rear part of the cylinder, first (B) ) component and (C) component are melted and mixed by supplying them to the rear of the cylinder, and then (A
) can be mixed by supplying the components to the middle of the cylinder.
なお、（Ｂ）成分と（Ｃ）成分を溶融混合する前にあら
かじめミキサーあるいはタンブラ−などで予備混合して
おくことが好ましい。Note that it is preferable to premix components (B) and (C) in a mixer, tumbler, or the like before melt-mixing them.
なお、本発明の樹脂組成物には、必要に応じて酸化防止
剤、紫外線吸収剤、光安定剤、帯電防止剤、滑剤、染料
、顔料、可塑剤、難燃剤を添加できる。Note that antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants, dyes, pigments, plasticizers, and flame retardants can be added to the resin composition of the present invention, if necessary.
次に実施例および比較例により本発明を具体的に説明す
るが、本発明はこれらによって何ら制限を受けるもので
はない。EXAMPLES Next, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited by these in any way.
尚、部数およびパーセントについてはいずれも重量基準
で示した。Note that all parts and percentages are expressed on a weight basis.
参考例１ エンジニアリングプラスチック（Ａ）ＰＣ：
住友ノーガタック■社製ポリカーボネート“カリバー３
００−１０
ＰＡ：ユニチカ■社製６−ナイロン“Ａ−１０３０ＢＲ
Ｌガ
ＰＢＴ：ポリフ゛チレンテレフタレート（平均分子量４
００００）
参考例２ ゴム強化スチレン系樹脂（Ｂ）の製造ＡＢＳ
−１：
平均粒子径０，４１μ、ゲル含有率８８％のポリブタジ
ェンラテックス５０部（固形分）の存在下、乳化重合法
によりアクリロニトリル１５部およびスチレン３５部を
共重合させてＡＢＳグラフト共重合体ラテックス（グラ
フト率４５％、遊離のアクリロニトリル−スチレン共重
合体の固有粘度０．４８）を製造した。尚、固有粘度は
ジメチルホルムアミド中、３０℃で測定した。Reference example 1 Engineering plastic (A) PC:
Polycarbonate manufactured by Sumitomo Naugatac “Caliber 3”
00-10 PA: Unitika ■ 6-nylon "A-1030BR"
L-Ga PBT: Polyethylene terephthalate (average molecular weight 4
0000) Reference Example 2 Production of rubber reinforced styrenic resin (B) ABS
-1: ABS graft copolymerization by copolymerizing 15 parts of acrylonitrile and 35 parts of styrene by emulsion polymerization in the presence of 50 parts (solid content) of polybutadiene latex with an average particle size of 0.41μ and a gel content of 88%. A combined latex (grafting ratio 45%, free acrylonitrile-styrene copolymer intrinsic viscosity 0.48) was produced. Note that the intrinsic viscosity was measured in dimethylformamide at 30°C.
（以下同じ、単位１００ｍ７／ｆ）
又、別途乳化重合法によりアクリロニトリル２５部、ス
チレン７５部よりなる共重合体ラテ、ンクス（固有粘度
０．５６ ）を製造し、ゴム分３０％となるようＡＢＳ
グラフト共重合体ラテックスと混合した後、硫酸マグネ
シウムを用いて塩析、分離、回収を行った。(The same applies hereinafter, unit: 100 m7/f) Separately, a copolymer latte (intrinsic viscosity: 0.56) consisting of 25 parts of acrylonitrile and 75 parts of styrene was produced by an emulsion polymerization method, and ABS was added so that the rubber content was 30%.
After mixing with the graft copolymer latex, salting out, separation, and recovery were performed using magnesium sulfate.
ＡＢＳ−２：
ＡＢＳ−１の方法で得られたＡＢＳグラフト共重合体ラ
テックスと、別途乳化重合により得られたアクリロニト
リル２５部、α−メチルスチレン７５部よりなる共重合
体ラテックス（固有粘度０．５８）とを、ゴム分３０％
となるように混合した後、硫酸マグネシウムを用いて塩
析、分離、回収を行った。ABS-2: A copolymer latex (intrinsic viscosity: 0.58 ) with a rubber content of 30%
After mixing so that the following results were obtained, salting out, separation, and recovery were performed using magnesium sulfate.
ＡＥＳ：
エチレン−プロピレン−エチリデンノルボルネン共重合
体（ＥＰＤＭ、ヨウ素価２１、ムーニー粘度７５、プロ
ピレン含量５０％）５０部、アクリロニトリル１５部お
よびスチレン３５部よりなるＡＥＳグラフト共重合体（
グラフト率５２％、遊離のアクリロニトリル−スチレン
共重合体の固有粘度０．６８ ）を溶液重合法にて製造
した。重合後、メタノール中へ沈澱させ、分離、回収し
た。AES: AES graft copolymer consisting of 50 parts of ethylene-propylene-ethylidene norbornene copolymer (EPDM, iodine number 21, Mooney viscosity 75, propylene content 50%), 15 parts of acrylonitrile and 35 parts of styrene (
A free acrylonitrile-styrene copolymer with a graft ratio of 52% and an intrinsic viscosity of 0.68 was produced by a solution polymerization method. After polymerization, it was precipitated into methanol, separated and collected.
別途、ＡＢＳ−１で示されたアクリロニトリル−スチレ
ン共重合体ラテックスを硫酸マグネシウムで塩析、分離
、回収を行い、共重合体を得た。Separately, an acrylonitrile-styrene copolymer latex indicated by ABS-1 was salted out with magnesium sulfate, separated, and recovered to obtain a copolymer.
その後、ゴム分３０％となるようＡＥＳグラフト共重合
体と共重合体とを混合した。Thereafter, the AES graft copolymer and the copolymer were mixed so that the rubber content was 30%.
参考例３ 無機充填剤（Ｃ）
ｃ−１、タルク（林化成■ミクロンホワイト＃５０００
Ｓ）
Ｃ−２：炭酸カルシウム（白石カルシウム■ホワイトン
５ＳＢ）
実施例
エンジニアリングプラスチック（Ａ）、ゴム強化スチレ
ン系樹脂（Ｂ）および無機充填剤（Ｃ）を表−Ｉに示す
配合比にて以下の方法にてそれぞれ混合し、組成物Ｎｕ
ｌｌ〜８を得た。Reference example 3 Inorganic filler (C) c-1, talc (Hayashi Kasei Micron White #5000
S) C-2: Calcium carbonate (Shiraishi Calcium ■ Whiten 5SB) Example engineering plastic (A), rubber reinforced styrene resin (B) and inorganic filler (C) in the following blending ratios shown in Table I. The composition Nu
ll~8 was obtained.
０組成物Ｎα１〜４
（Ｂ）および（Ｃ）を１軸押出機を用いて溶融混合し、
ペレット化した。次いで、得られたペレットと（Ａ）を
Ｉ軸押出機にて溶融混合し、組成物嵩１〜４を得た。0 compositions Nα1-4 (B) and (C) were melt-mixed using a single-screw extruder,
Pelleted. Next, the obtained pellets and (A) were melt-mixed in an I-screw extruder to obtain compositions with bulks of 1 to 4.
０組成物Ｎ［１５〜８．ｌｏ
（Ａ）、（Ｂ）および（Ｃ）を１軸押出機を用いて一括
溶融混合し、組成物漱５〜８，１０を得た。0 composition N [15-8. lo (A), (B) and (C) were melt-mixed all at once using a single screw extruder to obtain compositions 5 to 8 and 10.
０組成物漱９
シリンダーの中間部および後部に材料供給口を有する押
出機を用いて、まず（Ｂ）と（Ｃ）をシリンダー後部の
材料供給口に供給して溶融混合させ、次いで、（Ａ）を
シリンダー中間部の材料供給口に供給して溶融混合し、
組成物Ｎ［１９を得た。0 Composition 9 Using an extruder having material supply ports at the middle and rear of the cylinder, first (B) and (C) are supplied to the material supply ports at the rear of the cylinder to melt and mix them, and then (A ) is supplied to the material supply port in the middle of the cylinder and melted and mixed.
Composition N[19 was obtained.
上記の方法によって得られた樹脂組成物Ｎｎ ｌ〜１０
を３５オンス射出成形機を用いて品質評価用の試験片を
作製した。試験結果は表−１に示す。Resin composition Nnl~10 obtained by the above method
A test piece for quality evaluation was prepared using a 35-ounce injection molding machine. The test results are shown in Table-1.
なお、試験方法は以下のとおり。The test method is as follows.
く衝撃強度〉
ＡＳＴＭ−Ｄ２５６
０ ｌ／４インチ、ノツチ付アイゾツト ２３℃
０ −３０℃０
１／８インチ ノツチなしアイゾツト ２３℃０
−３０℃〈曲げ
たわみ率〉
長さ５インチ、幅１／２インチ、厚み１／８インチの試
験片を、オートグラフにて、曲げ速度５０■／刺、スパ
ン５０１１＋１１の条件にて測定し、下記の式より曲げ
たわみ率を算出した。Impact strength> ASTM-D256 0 l/4 inch, notched Izot 23℃
0 -30℃0
1/8 inch Izot without notch 23℃0
-30℃〈Bending deflection rate〉 A test piece with a length of 5 inches, a width of 1/2 inch, and a thickness of 1/8 inch was measured using an autograph at a bending speed of 50 cm/strip and a span of 5011+11. The bending deflection rate was calculated from the following formula.
ｄ：試験片の厚み
△ｌ：破壊時のたわみ量
Ｌニスパン
〈表面外観〉
１５０■×９０■×３甑の平板を射出成形によ肉
り成形し、成形品表面の肌荒れの状態を■眼にて判定し
た。d: Thickness of test piece △l: Amount of deflection at breakage L Nispan (Surface appearance) A flat plate of 150×90×3 pots was molded by injection molding, and the state of roughness on the surface of the molded product was visually inspected. Judgment was made.
○；肌荒れが認められず良好
△；やや肌荒れが認られる
×；肌荒れが著しく不良
〔発明の効果〕
以上のとおり、エンジニアリングプラスチックとゴム強
化スチレン系樹脂および非繊維状無機充填剤からなる充
填剤配合樹脂組成物を製造するに際し、本発明の製造方
法を採用することにより、従来の一括溶融混合法に比べ
て、優れた物性を有する樹脂組成物が得られるものであ
る。○: Good with no rough skin observed △: Slightly rough skin ×: Significantly poor skin roughness [Effects of the invention] As described above, the filler combination consisting of engineering plastic, rubber-reinforced styrene resin, and non-fibrous inorganic filler By employing the production method of the present invention when producing a resin composition, a resin composition having superior physical properties can be obtained as compared to the conventional batch melt-mixing method.
Claims (1)
リフェニレンエーテル、ポリアリレートから選ばれた１
種又は２種以上のエンジニアリングプラスチック（Ａ）
５〜６０重量部、ゴム強化スチレン系樹脂（Ｂ）１０〜
９４重量部および非繊維状無機充填剤（Ｃ）１〜５０重
量部（ただし、（Ａ）＋（Ｂ）＋（Ｃ）の合計量を１０
０重量部とする。）からなる充填剤配合樹脂組成物を製
造するにあたり、まず、上記（Ｂ）成分と（Ｃ）成分を
溶融混合し、次いで、得られた混合物と上記（Ａ）成分
とを溶融混合することを特徴とする充填剤配合樹脂組成
物の製造方法。1 selected from polycarbonate, polyamide, saturated polyester, polyphenylene ether, polyarylate
Species or two or more types of engineering plastics (A)
5 to 60 parts by weight, rubber reinforced styrene resin (B) 10 to
94 parts by weight and 1 to 50 parts by weight of non-fibrous inorganic filler (C) (however, the total amount of (A) + (B) + (C) is 10 parts by weight)
0 parts by weight. ) In producing the filler-containing resin composition, first, the above (B) component and (C) component are melt-mixed, and then the obtained mixture and the above (A) component are melt-mixed. A method for producing a characteristic filler-containing resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19533490A JP2917049B2 (en) | 1990-07-23 | 1990-07-23 | Method for producing filler-containing resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19533490A JP2917049B2 (en) | 1990-07-23 | 1990-07-23 | Method for producing filler-containing resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0480249A true JPH0480249A (en) | 1992-03-13 |
| JP2917049B2 JP2917049B2 (en) | 1999-07-12 |
Family
ID=16339448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19533490A Expired - Fee Related JP2917049B2 (en) | 1990-07-23 | 1990-07-23 | Method for producing filler-containing resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2917049B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001009241A1 (en) * | 1999-07-29 | 2001-02-08 | Shanghai Genius Advanced Material Co. Ltd. | High fluidible, impact resistant conductive acrylonitrile-butadiene-styrene terpolymer material and preparing method thereof |
| CN103059550A (en) * | 2011-10-18 | 2013-04-24 | 上海杰事杰新材料(集团)股份有限公司 | Polyphenylene oxide/polystyrene blend alloy material, its preparation method and application |
-
1990
- 1990-07-23 JP JP19533490A patent/JP2917049B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001009241A1 (en) * | 1999-07-29 | 2001-02-08 | Shanghai Genius Advanced Material Co. Ltd. | High fluidible, impact resistant conductive acrylonitrile-butadiene-styrene terpolymer material and preparing method thereof |
| JP2003529626A (en) * | 1999-07-29 | 2003-10-07 | 上海▲傑▼事▲傑▼新材料股▲分▼有限公司 | High fluidity impact resistant conductive acrylonitrile-butadiene-styrene three-dimensional copolymer composition and method for producing the same |
| CN103059550A (en) * | 2011-10-18 | 2013-04-24 | 上海杰事杰新材料(集团)股份有限公司 | Polyphenylene oxide/polystyrene blend alloy material, its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2917049B2 (en) | 1999-07-12 |
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