JPH0354989B2 - - Google Patents
Info
- Publication number
- JPH0354989B2 JPH0354989B2 JP29280185A JP29280185A JPH0354989B2 JP H0354989 B2 JPH0354989 B2 JP H0354989B2 JP 29280185 A JP29280185 A JP 29280185A JP 29280185 A JP29280185 A JP 29280185A JP H0354989 B2 JPH0354989 B2 JP H0354989B2
- Authority
- JP
- Japan
- Prior art keywords
- pps
- acid
- weight
- test piece
- polyphenylene sulfide
- 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.)
- Expired
Links
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 55
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 55
- 239000002253 acid Substances 0.000 claims description 21
- -1 glycidyl ester Chemical class 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 4
- 208000002387 Popliteal pterygium syndrome Diseases 0.000 description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 17
- 239000000843 powder Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000010306 acid treatment Methods 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 238000005453 pelletization Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012744 reinforcing agent Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000010425 asbestos Substances 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
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012784 inorganic fiber 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
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Description
<産業上の利用分野>
本発明は、衝撃特性の改良されたポリフエニレ
ンスルフイド樹脂組成物に関するものであり、更
に詳しくは、特定のポリフエニレンスルフイド樹
脂にオレフイン系共重合体を含有せしめることに
より衝撃特性の改良されたポリフエニレンスルフ
イド樹脂組成物に関するものである。
<従来の技術>
従来、衝撃特性の改善されたポリフエニレンス
ルフイド樹脂組成物としては、特開昭58−154757
号公報に、α−オレフインとα,β−不飽和酸の
グリシジルエステルからなるオレフイン系共重合
体を配合せしめてなる組成物が開示されている。
<発明が解決しようとする問題点>
しかしながら、前記公報記載の組成物において
も衝撃特性の改善効果は不充分である。更に詳述
すると、従来知られているように通常のポリフエ
ニレンスルフイド樹脂の分子鎖は反応性に乏しい
ため、前記公報記載のオレフイン系共重合体のよ
うなエポキシ基を含む反応性に富んだゴム成分を
配合しても、ポリフエニレンスルフイドとの界面
の付着が不充分であるため、充分な衝撃特性の改
善効果が得られていないのが現状である。そこで
本発明者らは、ゴム成分の衝撃特性改善効果の顕
著なポリフエニレンスルフイド樹脂組成物を得る
ことを目的として鋭意検討を行い、特定のポリフ
エニレンスルフイド樹脂に特定のゴム成分を配合
することによりこの目的が達せられることを見出
し、本発明に到達した。
<問題点を解決するための手段>
すなわち本発明は、酸処理を施されたのち洗浄
されたポリフエニレンスルフイド樹脂に、α−オ
レフイン60〜99.5重量%およびα,β−不飽和酸
のグリシジルエステル0.5〜40重量%を必須成分
とするオレイン系共重合体を含有せしめることを
特徴とするポリフエニレンスルフイド樹脂組成物
を提供するものである。
本発明で使用するポリフエニレンスルフイド
(以下PPSと称する)とは、構造式
<Field of Industrial Application> The present invention relates to a polyphenylene sulfide resin composition with improved impact properties, and more specifically, a polyphenylene sulfide resin composition containing an olefin copolymer in a specific polyphenylene sulfide resin. The present invention relates to a polyphenylene sulfide resin composition that has improved impact properties by increasing the impact properties. <Prior art> Conventionally, as a polyphenylene sulfide resin composition with improved impact properties, Japanese Patent Application Laid-Open No. 58-154757
JP-A-2006-100001 discloses a composition comprising an olefin copolymer comprising an α-olefin and a glycidyl ester of an α,β-unsaturated acid. <Problems to be Solved by the Invention> However, even in the composition described in the above-mentioned publication, the effect of improving impact properties is insufficient. More specifically, as is conventionally known, the molecular chains of ordinary polyphenylene sulfide resins are poor in reactivity, so polyphenylene sulfide resins containing highly reactive epoxy groups, such as the olefin-based copolymers described in the above-mentioned publication, Even if a rubber component is blended, the adhesion at the interface with polyphenylene sulfide is insufficient, so the current situation is that a sufficient effect of improving impact properties cannot be obtained. Therefore, the present inventors conducted extensive studies with the aim of obtaining a polyphenylene sulfide resin composition that has a remarkable effect of improving the impact properties of the rubber component, and added a specific rubber component to a specific polyphenylene sulfide resin. It has been discovered that this objective can be achieved by blending, and the present invention has been achieved. <Means for solving the problem> That is, the present invention adds 60 to 99.5% by weight of α-olefin and α,β-unsaturated acid to polyphenylene sulfide resin that has been acid-treated and then washed. The present invention provides a polyphenylene sulfide resin composition containing an oleic copolymer containing 0.5 to 40% by weight of glycidyl ester as an essential component. The polyphenylene sulfide (hereinafter referred to as PPS) used in the present invention has the structural formula
【式】で示される繰返し単位を70
モル%以上、より好ましくは90モル%以上を含む
重合体であり、上記繰返し単位が70モル%未満で
は耐熱性が損われるため好ましくない。
PPSは一般に、特公昭45−3368号公報で代表さ
れる製造法により得られる比較的分子量の小さい
重合体と、特公昭52−12240号公報で代表される
製造法により得られる本質的に線状で比較的高分
子量の重合体等があり、前記特公昭45−3368号公
報記載の方法で得られた重合体においては、重合
後酸素雰囲気下において加熱することにより、あ
るいは過酸化物等の架橋剤を添加して加熱するこ
とにより高重合度化して用いることも可能であ
り、本発明においてはいかなる方法により得られ
たPPSを用いることも可能であるが、本発明の効
果が顕著であること、および、PPS自体の靭性が
すぐれるという理由で、前記特公昭52−12240号
公報で代表される製造法により得られる本質的に
線状で比較的高分子量の重合体が、より好ましく
用いられ得る。
また、PPSはその繰返し単位の30モル%未満を
下記の構造式を有する繰返し単位等で構成するこ
とが可能である。It is a polymer containing 70 mol % or more, more preferably 90 mol % or more of the repeating unit represented by the formula. If the repeating unit is less than 70 mol %, heat resistance will be impaired, so it is not preferable. PPS is generally a polymer with relatively low molecular weight obtained by the production method typified by Japanese Patent Publication No. 45-3368, and an essentially linear polymer obtained by the production method typified by Japanese Patent Publication No. 52-12240. There are polymers with relatively high molecular weight, etc., and in the polymer obtained by the method described in the above-mentioned Japanese Patent Publication No. 45-3368, it is possible to cure the polymer by heating in an oxygen atmosphere after polymerization or by crosslinking with peroxide, etc. It is also possible to increase the degree of polymerization and use it by adding an agent and heating it, and in the present invention, it is possible to use PPS obtained by any method, but the effects of the present invention are remarkable. , and because PPS itself has excellent toughness, essentially linear and relatively high molecular weight polymers obtained by the production method typified by the above-mentioned Japanese Patent Publication No. 52-12240 are more preferably used. obtain. Furthermore, less than 30 mol% of the repeating units in PPS can be composed of repeating units having the following structural formula, etc.
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
本発明で用いられるPPSの溶融粘度は、成形品
を得ることが可能であれば特に制限はないが、
PPS自体の靭性の面では100ポアズ以上のものが、
成形性の面では10000ポアズ以下のものがより好
ましく用いられる。
本発明でPPSの酸処理に用いる酸は、PPSを分
解する作用を有しないものであれば特に制限はな
く、酢酸、塩酸、硫酸、リン酸、珪酸、炭酸、プ
ロピル酸等が挙げられ、なかでも、酢酸、塩酸が
より好ましく用いられ得るが、硝酸のようなPPS
を分解、劣化させるものは好ましくない。
本発明においては、PPSを酸で処理することが
必要であり、塩、アルカリ等では、PPSの好まし
い化学的変性が行われないので好ましくない。
酸処理の方法は、酸または酸の水溶液にPPSを
浸漬せしめる等の方法があり、必要により適宜撹
拌または加熱することも可能である。例えば、酢
酸で用いる場合、PH4の水溶液を80〜90℃に加熱
した中にPPS粉末を浸漬し、30分間撹拌すること
により充分な効果が得られる。酸処理を施された
PPSは残留している酸または塩等を物理的に除去
するため、水または温水で数回洗浄することが必
要である。
洗浄に用いる水は、酸処理によるPPSの好まし
い化学的変性の効果を損わない意味で、蒸溜水、
脱イオン水であることが好ましい。また、洗浄の
効率を改善する目的で、圧力容器中で100℃以上
の熱水で洗浄することも可能である。
本発明で酸処理に供するPPSは粉粒体であるこ
とが酸処理、洗浄の効率上好ましい。通常公知の
方法で製造されるPPSは粉粒体の形で得られるた
め、これらをペレタイズすることなく用いて酸処
理、洗浄するのが好ましく、必要によつては、分
級あるいは粉砕して用いることも可能である。
また、重合後の湿潤状態のPPSをそのまま酸処
理に供することも可能である。
また、本発明で用いるPPSには、本発明の効果
を損なわない範囲で、酸化防止剤、熱安定剤、滑
剤、結晶核剤、紫外線防止剤、着色剤などの通常
の添加剤および少量の多種ポリマを添加すること
ができ、更に、PPSの架橋度を制御する目的で、
通常の過酸化剤および、特開昭59−131650号公報
に記載されているチオホスフイン酸金属塩等の架
橋促進剤または特開昭58−204045号公報、特開昭
58−204046号公報等に記載されているジアルキル
錫ジカルボキシレート、アミノトリアゾール等の
架橋防止剤を配合することも可能である。
本発明で用いるオレフイン系共重合体とはα−
オレフインとα、β−不飽和酸のグリシジルエス
テルからなる共重合体であり、ここでいうα−オ
レフインとはエチレン、プロピレン、ブテン−1
などが挙げられるが、エチレンが好ましく用いら
れる。また、α、β−不飽和酸のグリシジルエス
テルとは、一般式
(Rは水素原子または低級アルキル基を示す)
デ示される化合物であり、具体的にはアクリル酸
グリシジル、メタクリル酸グリシジル、エタクリ
ル酸グリシジルなどが挙げられるが、なかでもメ
タクリル酸グリシジルが好ましく使用される。オ
レフイン系共重合体におけるα,β−不飽和酸の
グリシジルエステルの共重合量は0.5〜40重量%、
特に3〜30重量%が好ましく、0.5重量%未満で
は目的とする効果が得られず、40重量%を越える
とPPSとの溶融混練時にゲル化を生じ、押出安定
性、成形性および機械的特性が低下するため好ま
しくない。
また、オレフイン系共重合体には40重量%以下
で、かつ、本発明の目的を損なわない範囲で、更
に共重合可能な他の不飽和モノマ、例えば、ビニ
ルエーテル、酢酸ビニル、プロピオン酸ビニル、
アクリル酸メチル、メタクリル酸メチル、アクリ
ロニトリル、スチレンなどを共重合せしめてもよ
い。
PPSとオレフイン系共重合体を配合する割合に
特に限定はない。
本発明において、繊維状および/または粒状の
強化剤は必須成分ではないが、必要に応じてPPS
とオレフイン系共重合体の合計100重量部に対し
て300重量部を越えない範囲で配合することが可
能であり、通常10〜300重量部の範囲で配合する
ことにより強度、剛性、耐熱性、寸法安定性等の
向上を図ることが可能である。
かかる繊維状強化剤としては、ガラス繊維、シ
ラスガラス繊維、アルミナ繊維、炭化珪素繊維、
セラミツク繊維、アスベスト繊維、石コウ繊維、
金属繊維等の無機繊維および炭素繊維等が挙げら
れる。
また粒状の強化剤としては、ワラステナイト、
セリサイト、カオリン、マイカ、クレー、ベント
ナイト、アスベスト、タルク、アルミナシリケー
トなどの珪酸塩、アルミナ、塩化珪素、酸化マグ
ネシウム、酸化ジルコニウム、酸化チタンなどの
金属酸化物、炭酸カウシウム、炭酸マグネシウ
ム、ドロマイトなどの炭酸塩、硫酸カルシウム、
硫酸バリウムなどの硫酸塩、ガラス・ビーズ、窒
化ホウ素、炭化珪素、サロヤン、シリカなどが挙
げられ、これらは中空であつてもよい。これら強
化剤は2種以上を併用することが可能であり、必
要によりシラン系およびチタン系などのカツプリ
ング剤で予備処理して使用することができる。
本発明の組成物の調製手段は特に制限はない
が、PPSとオレフイン系共重合体と強化剤とを
PPSの融点以上の温度で、押出機内で溶融混練
後、ペレタイズする方法が代表的である。
なお、溶融混練温度は280〜340℃が好ましく、
280℃未満ではPPSの溶融が不充分になることが
あり、340℃を越えるとオレフイン系共重合体の
熱劣化およびゲル化することがあるので注意を要
する。
以下に実施例を挙げて本発明をさらに詳細に説
明する。
<実施例>
参考例 1
(PPSの重合)
オートクレーブに硫化ナトリウム3.26Kg(25モ
ル、結晶水40%を含む)、水酸化ナトリウム4g、
酢酸ナトリウム三水和物1.36Kg(約10モル)およ
びN−メチル−2−ピロリドン(以下NMPと略
称する)7.9Kgを仕込み、撹拌しながら徐々に205
℃まで昇温し、水1.36Kgを含む留出水約1.5を
除去した。残留混合物に1,4−ジクロルベンゼ
ン3.75Kg(25.5モル)およいNMP2Kgを加え、
265℃で4時間加熱した。反応生成物を70℃の温
水で5回洗浄し、80℃で24時間減圧乾燥して、溶
融粘度約2500ポアズ(320℃、剪断速度1000秒-1)
の粉末状PPS約2Kgを得た。
同様の操作を繰返し、以下に記載の実施例に供
した。
実施例 1
参考例1で得られたPPS粉末約2Kgを90℃に加
熱されたPH4の酢酸水溶液20中に投入し、約30
分間撹拌し続けたのち、濾過し、濾液のPHが7に
なるまで約90℃の脱イオン水で洗浄し、120℃で
24時間減圧乾燥して粉末状とした。
この粉末と、エチレン−メタクリル酸グリシジ
ル(88/12重量比)共重合体(以下オレフイン系
共重合体と略称する)を80対20の重量比でドライ
ブレンドし、290〜310℃に設定したスクリユー押
出機により溶融混合し、ペレタイズした。次にペ
レツトを290〜300℃に設定したスクリユーインラ
イン型射出成形機に供給し、金型温度140〜150℃
の条件で機械特性評価用試験片を成形した。
得られた試験片について測定したアイゾツト衝
撃強度(ASTM D−256)、熱変形温度
(ASTM D−648)は第1表に記載の通りであ
り、衝撃強度が極めて大きく、かつ、オレフイン
系共重合体を配合しないものに比べ熱変形温度の
低下は小さかつた。
比較例 1〜2
参考例1で得られたPPS粉末をそのまま(比較
例1)および、実施例1と同様の方法で酢酸処理
し、洗浄、乾燥したもの(比較例2)を用い、オ
レフイン系共重合体を配合することなく、ペレタ
イズ、射出成形を行つた試験片について評価した
アイゾツト衝撃強度、熱変形温度は第1表に記載
のとおりであつた。
比較例 3
実施例1で参考例1で得られたPPS粉末を酢酸
処理して用いた代りに、参考例1で得られたPPS
粉末をそのまま用いたことのほかは実施例1と全
く同様の方法で、オレフイン系共重合体と溶融混
合、ペレタイズ、射出成形を行つた試験片につい
て評価したアイゾツト衝撃強度、熱変形温度は第
1表に記載のとおりであつた。
実施例 2
実施例1で、参考例1で得られたPPS粉末を酸
処理する際に酢酸を用いた代りに、PH4の塩酸を
用いたことのほかは、実施例1と全く同様の操作
を行い試験片を得た。
得られた試験片について評価した特性値は第1
表記載の通りであつた。
実施例 3
実施例1でエチレン−メタクリル酸グリシジル
(88/12重量比)共重合体を用いた代りに、共重
合比が94/6(重量比)の共重合体を用いたこと
のほかは、実施例1と全く同様の操作を行い、試
験片を得た。得られた試験片について評価した特
性値は第1表記載のとおりであつた。
実施例 4
実施例1でオレフイン系共重合体の配合割合を
20重量%とした代りに、10重量%としたことのほ
かは実施例1と全く同様の操作を行つた。得られ
た試験片について評価した特性値は第1表記載の
とおりであつた。
実施例 5〜6
実施例1と同様の方法で酸処理を行つたPPS粉
末と、オレフイン系共重合体とガラス繊維とを第
1表に記載の割合で実施例1と全く同様の方法で
溶融混合、ペレタイズ、射出成形を行い、得られ
た試験片について評価した特性値は第1表に記載
のとおりであつた。
比較例 4〜5
参考例1で得られたPPSとガラス繊維(比較例
4)、参考例1で得られたPPSとオレフイン系共
重合体とガラス繊維(比較例5)とをそれぞれ、
第1表に記載した割合で、実施例1と全く同様の
方法で溶融混合、ペレタイズ、射出成形し、得ら
れた試験片について評価した特性値は第1表に記
載の通りであつた。[Formula] The melt viscosity of PPS used in the present invention is not particularly limited as long as it is possible to obtain a molded article, but
In terms of toughness of PPS itself, it is over 100 poise.
In terms of moldability, those having a diameter of 10,000 poise or less are more preferably used. The acid used in the acid treatment of PPS in the present invention is not particularly limited as long as it does not have the effect of decomposing PPS, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, propylic acid, etc. Even acetic acid, hydrochloric acid may be used more preferably, but PPS such as nitric acid
Anything that decomposes or deteriorates is undesirable. In the present invention, it is necessary to treat PPS with an acid, and salts, alkalis, etc. are not preferred because they do not achieve the desired chemical modification of PPS. The acid treatment includes methods such as immersing PPS in an acid or an aqueous solution of an acid, and it is also possible to stir or heat as appropriate, if necessary. For example, when using acetic acid, a sufficient effect can be obtained by immersing PPS powder in an aqueous solution of PH4 heated to 80 to 90°C and stirring for 30 minutes. acid treated
PPS needs to be washed several times with water or hot water to physically remove residual acids or salts. The water used for washing may be distilled water,
Preferably it is deionized water. Additionally, in order to improve cleaning efficiency, it is also possible to wash with hot water of 100°C or higher in a pressure vessel. The PPS to be subjected to acid treatment in the present invention is preferably in the form of powder or granules in terms of efficiency of acid treatment and cleaning. PPS, which is usually produced by known methods, is obtained in the form of powder or granules, so it is preferable to use them without pelletizing and then acid treatment and washing.If necessary, they can be used after being classified or pulverized. is also possible. Furthermore, it is also possible to directly subject PPS in a wet state after polymerization to acid treatment. In addition, the PPS used in the present invention may contain ordinary additives such as antioxidants, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet inhibitors, colorants, and small amounts of various other additives, to the extent that they do not impair the effects of the present invention. Polymers can be added and further, for the purpose of controlling the degree of crosslinking of PPS,
Common peroxidants and crosslinking accelerators such as thiophosphinic acid metal salts described in JP-A-59-131650, or JP-A-58-204045, JP-A-Sho.
It is also possible to incorporate crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole described in JP 58-204046 and the like. The olefin copolymer used in the present invention is α-
It is a copolymer consisting of olefin and glycidyl ester of α,β-unsaturated acid, and α-olefin here refers to ethylene, propylene, butene-1
etc., but ethylene is preferably used. In addition, glycidyl ester of α,β-unsaturated acid has the general formula (R represents a hydrogen atom or a lower alkyl group) Specific examples include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, among which glycidyl methacrylate is preferably used. . The amount of copolymerized glycidyl ester of α,β-unsaturated acid in the olefin copolymer is 0.5 to 40% by weight,
Particularly preferred is 3 to 30% by weight; if it is less than 0.5% by weight, the desired effect cannot be obtained, and if it exceeds 40% by weight, gelation occurs during melt-kneading with PPS, resulting in poor extrusion stability, moldability, and mechanical properties. This is not preferable because it reduces the In addition, the olefinic copolymer may contain other copolymerizable unsaturated monomers, such as vinyl ether, vinyl acetate, vinyl propionate, etc., in an amount of 40% by weight or less and within a range that does not impair the purpose of the present invention.
Methyl acrylate, methyl methacrylate, acrylonitrile, styrene, etc. may be copolymerized. There is no particular limitation on the proportion of PPS and olefin copolymer to be blended. In the present invention, fibrous and/or granular reinforcing agents are not essential components, but PPS may be used as needed.
It is possible to blend in an amount not exceeding 300 parts by weight with respect to a total of 100 parts by weight of the olefin copolymer and the olefin copolymer.Usually, by blending in the range of 10 to 300 parts by weight, strength, rigidity, heat resistance, It is possible to improve dimensional stability and the like. Such fibrous reinforcing agents include glass fiber, shirasu glass fiber, alumina fiber, silicon carbide fiber,
Ceramic fiber, asbestos fiber, gypsum fiber,
Examples include inorganic fibers such as metal fibers and carbon fibers. In addition, as particulate reinforcing agents, wollastenite,
Silicates such as sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, metal oxides such as alumina, silicon chloride, magnesium oxide, zirconium oxide, titanium oxide, cowsium carbonate, magnesium carbonate, dolomite, etc. carbonate, calcium sulfate,
Examples include sulfates such as barium sulfate, glass beads, boron nitride, silicon carbide, Saroyan, silica, etc., and these may be hollow. Two or more of these reinforcing agents can be used in combination, and if necessary, they can be pretreated with coupling agents such as silane and titanium before use. There are no particular limitations on the means for preparing the composition of the present invention, but PPS, an olefinic copolymer, and a reinforcing agent are used.
A typical method is to melt and knead PPS in an extruder at a temperature higher than the melting point of PPS and then pelletize it. In addition, the melt-kneading temperature is preferably 280 to 340°C,
If the temperature is lower than 280°C, the melting of PPS may become insufficient, and if the temperature exceeds 340°C, the olefin copolymer may undergo thermal deterioration and gelation, so care must be taken. The present invention will be explained in more detail with reference to Examples below. <Example> Reference example 1 (Polymerization of PPS) In an autoclave, 3.26 kg of sodium sulfide (25 mol, containing 40% crystal water), 4 g of sodium hydroxide,
1.36 kg (approximately 10 mol) of sodium acetate trihydrate and 7.9 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were charged, and the mixture was gradually heated to 205 kg while stirring.
The temperature was raised to ℃, and about 1.5 kg of distilled water containing 1.36 kg of water was removed. Add 3.75 Kg (25.5 mol) of 1,4-dichlorobenzene and 2 Kg of NMP to the remaining mixture.
Heated at 265°C for 4 hours. The reaction product was washed 5 times with hot water at 70°C and dried under reduced pressure at 80°C for 24 hours to obtain a melt viscosity of approximately 2500 poise (320°C, shear rate 1000 s -1 ).
Approximately 2 kg of powdered PPS was obtained. The same operation was repeated and used in the examples described below. Example 1 Approximately 2 kg of PPS powder obtained in Reference Example 1 was poured into a PH4 acetic acid aqueous solution heated to 90°C, and the mixture was heated to approximately 30°C.
After stirring for a minute, filter, wash with deionized water at about 90°C until the pH of the filtrate is 7, and heat at 120°C.
It was dried under reduced pressure for 24 hours to form a powder. This powder was dry blended with ethylene-glycidyl methacrylate (88/12 weight ratio) copolymer (hereinafter referred to as olefin copolymer) at a weight ratio of 80:20, and then The mixture was melt-mixed using an extruder and pelletized. Next, the pellets are fed to a screw in-line injection molding machine set at 290-300℃, and the mold temperature is 140-150℃.
A test piece for mechanical property evaluation was molded under the following conditions. The Izot impact strength (ASTM D-256) and heat distortion temperature (ASTM D-648) measured for the obtained test piece are as shown in Table 1, and the impact strength is extremely high and the olefin copolymer The decrease in heat deformation temperature was smaller than in the case where no coalescence was added. Comparative Examples 1 to 2 Olefin-based The Izod impact strength and heat distortion temperature evaluated for test pieces pelletized and injection molded without blending the copolymer were as shown in Table 1. Comparative Example 3 In Example 1, instead of using the PPS powder obtained in Reference Example 1 after treating it with acetic acid, the PPS powder obtained in Reference Example 1 was used.
The Izod impact strength and heat distortion temperature of the test pieces evaluated by melt-mixing with the olefin copolymer, pelletizing, and injection molding were performed in exactly the same manner as in Example 1 except that the powder was used as it was. It was as described in the table. Example 2 The procedure was exactly the same as in Example 1, except that hydrochloric acid with a pH of 4 was used instead of acetic acid when the PPS powder obtained in Reference Example 1 was acid-treated. A test piece was obtained. The characteristic values evaluated for the obtained test piece were the first
It was as described in the table. Example 3 Except that instead of using the ethylene-glycidyl methacrylate (88/12 weight ratio) copolymer in Example 1, a copolymer with a copolymerization ratio of 94/6 (weight ratio) was used. A test piece was obtained by performing exactly the same operation as in Example 1. The characteristic values evaluated for the obtained test piece were as listed in Table 1. Example 4 The blending ratio of the olefin copolymer in Example 1 was
The same operation as in Example 1 was carried out except that the concentration was changed to 10% by weight instead of 20% by weight. The characteristic values evaluated for the obtained test piece were as listed in Table 1. Examples 5 to 6 PPS powder treated with acid in the same manner as in Example 1, olefin copolymer, and glass fiber were melted in exactly the same manner as in Example 1 in the proportions listed in Table 1. The characteristic values evaluated for the test pieces obtained by mixing, pelletizing, and injection molding were as shown in Table 1. Comparative Examples 4 to 5 PPS obtained in Reference Example 1 and glass fiber (Comparative Example 4), PPS obtained in Reference Example 1, olefin copolymer, and glass fiber (Comparative Example 5),
The test pieces were melt-mixed, pelletized, and injection molded in exactly the same manner as in Example 1 at the ratios listed in Table 1, and the characteristic values evaluated for the obtained test pieces were as listed in Table 1.
【表】
実施例 7
実施例1と同様の方法で酸処理を行つたPPS粉
末と、オレフイン系共重合体とポリエチレンとを
80対10対10の重量比でドライブレンドし、以下、
実施例1と全く同様の方法で溶融混合、ペレタイ
ズ、射出成形を行い試験片を得た。得られた試験
片について評価したカツト・ノツチ付アイゾツト
衝撃強度は38Kg・cm/cm・ノツチであり、熱変形
温度(高荷重)は103℃である。
実施例 8
実施例7でポリエチレンを用いた代りに、無水
マレイン酸をグラフトしたポリエチレン−ポリプ
ロピレン共重合体(三井石油化学工業(株)製”N−
タフマー”MP−0610”)を用いたことのほかは、
実施例7と全く同様の方法で試験片を得た。得ら
れた試験片について評価したカツト・ノツチ付ア
イゾツト衝撃強度は、42Kg・cm/cm・ノツチであ
り、熱変形温度(高荷重)は104℃であつた。
実施例 9
実施例1と同様の方法で酸処理を行つたPPS粉
末と、オレフイン系共重合体とを60対40の比でド
ライブレンドし、以下、実施例1と全く同様の方
法で溶融混合ペレタイズおよび射出成形を行い試
験片を得た。得られた試験片について評価したカ
ツト・ノツチ付アイゾツト衝撃強度は76Kg・cm/
cm・ノツチ、ノツチなしアイゾツト衝撃強度は
120Kg・cm/cm2以上であり、熱変形温度は98℃で
あつた。
実施例 10
実施例1と同様の方法で酸処理を行つたPPS粉
末/オレフイン系共重合体/ガラス繊維=65/
35/70の比で実施例5と同様に溶融混合ペレタイ
ズおよび射出成形を行い試験片を得た。得られた
試験片について評価したカツト・ノツチ付アイゾ
ツト衝撃強度は20Kg・cm/cm・ノツチであり、熱
変形温度は251℃であつた。
実施例 11
実施例2と同様の方法で酸処理を行つた。PPS
粉末およびエチレン−メタクリル酸グリシジル
(94/6重量比)共重合体とを55対45の比でドラ
イブレンドし、以下、実施例1と全く同様の方法
で溶融混合ペレタイズおよび射出成形を行い試験
片を得た。得られた試験片について評価したカツ
ト・ノツチ付アイゾツト衝撃強度は77Kg・cm/
cm・ノツチ、ノツチなしアイゾツト衝撃強度は
120Kg・cm/cm2以上であり、熱変形温度は97℃で
あつた。
<発明の効果>
本発明により、耐衝撃性が極めて優れたポリフ
エニレンスルフイド樹脂組成物が得られるように
なつた。[Table] Example 7 PPS powder treated with acid in the same manner as in Example 1, olefin copolymer, and polyethylene were combined.
Dry blend at a weight ratio of 80:10:10, and the following:
A test piece was obtained by performing melt mixing, pelletizing, and injection molding in exactly the same manner as in Example 1. The cut/notch Izo impact strength evaluated for the obtained test piece was 38 Kg·cm/cm·notch, and the heat distortion temperature (high load) was 103°C. Example 8 Instead of using polyethylene in Example 7, a polyethylene-polypropylene copolymer grafted with maleic anhydride (manufactured by Mitsui Petrochemical Industries, Ltd. "N-") was used.
In addition to using Tafmar “MP-0610”),
A test piece was obtained in exactly the same manner as in Example 7. The cut/notch Izo impact strength evaluated for the obtained test piece was 42 kg·cm/cm·notch, and the heat distortion temperature (high load) was 104°C. Example 9 PPS powder treated with an acid in the same manner as in Example 1 and an olefin copolymer were dry blended at a ratio of 60:40, and then melt-mixed in the same manner as in Example 1. A test piece was obtained by pelletizing and injection molding. The cut/notch impact strength evaluated for the obtained test piece was 76 kg・cm/
cm・Notch, Izotsu impact strength without notch
It was 120Kg·cm/cm 2 or more, and the heat distortion temperature was 98°C. Example 10 PPS powder/olefin copolymer/glass fiber treated with acid in the same manner as in Example 1 = 65/
A test piece was obtained by melt mixing pelletizing and injection molding in the same manner as in Example 5 at a ratio of 35/70. The cut/notch Izo impact strength evaluated for the obtained test piece was 20 kg·cm/cm·notch, and the heat distortion temperature was 251°C. Example 11 Acid treatment was carried out in the same manner as in Example 2. PPS
The powder and ethylene-glycidyl methacrylate (94/6 weight ratio) copolymer were dry blended at a ratio of 55:45, and then melt-mixed pelletizing and injection molding were performed in exactly the same manner as in Example 1 to obtain test pieces. I got it. The cut/notch impact strength evaluated for the obtained test piece was 77Kg・cm/
cm・Notch, Izotsu impact strength without notch
It was 120Kg·cm/cm 2 or more, and the heat distortion temperature was 97°C. <Effects of the Invention> According to the present invention, a polyphenylene sulfide resin composition having extremely excellent impact resistance can now be obtained.
Claims (1)
レンスルフイド樹脂に、α−オレフイン60〜99.5
重量%およびα,β−不飽和酸のグリシジルエス
テル0.5〜40重量%を必須成分とするオレフイン
系共重合体を含有せしめることを特徴とする樹脂
組成物。1. α-olefin 60 to 99.5 is added to polyphenylene sulfide resin that has been acid-treated and washed.
1. A resin composition comprising an olefinic copolymer containing 0.5 to 40% by weight of a glycidyl ester of an α,β-unsaturated acid as an essential component.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29280185A JPS62153343A (en) | 1985-12-27 | 1985-12-27 | Resin composition |
DE8686309991T DE3671458D1 (en) | 1985-12-27 | 1986-12-22 | POLYPHENYLENE SULFIDE RESIN COMPOSITION AND METHOD FOR THE PRODUCTION THEREOF. |
EP86309991A EP0228268B1 (en) | 1985-12-27 | 1986-12-22 | A polyphenylene sulfide resin composition and a process for producing it |
US07/142,669 US4889893A (en) | 1985-12-27 | 1988-01-07 | Polyphenylene sulfide resin composition and a process for producing it |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29280185A JPS62153343A (en) | 1985-12-27 | 1985-12-27 | Resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62153343A JPS62153343A (en) | 1987-07-08 |
JPH0354989B2 true JPH0354989B2 (en) | 1991-08-21 |
Family
ID=17786520
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP29280185A Granted JPS62153343A (en) | 1985-12-27 | 1985-12-27 | Resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62153343A (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63179963A (en) * | 1987-01-20 | 1988-07-23 | Dainippon Ink & Chem Inc | Thermoplastic resin composition |
JPH06104773B2 (en) * | 1987-09-08 | 1994-12-21 | 東レ株式会社 | Polyphenylene sulfide resin composition |
JPH0662849B2 (en) * | 1988-02-03 | 1994-08-17 | ポリプラスチックス株式会社 | Polyarylene sulfide resin composition |
JP2590250B2 (en) * | 1989-01-30 | 1997-03-12 | 東レ株式会社 | Plastic tubular body |
JPH0698673B2 (en) * | 1990-02-13 | 1994-12-07 | 東レ株式会社 | Blow hollow molded products |
JP2879804B2 (en) * | 1992-11-30 | 1999-04-05 | 東レ株式会社 | Method for producing polyphenylene sulfide resin composition |
JP2002226604A (en) | 2001-01-31 | 2002-08-14 | Toyoda Gosei Co Ltd | Resin molding |
JP3811012B2 (en) | 2001-01-31 | 2006-08-16 | 豊田合成株式会社 | Fuel system parts |
US7173090B2 (en) | 2001-10-25 | 2007-02-06 | Asahi Kasei Chemicals Corporation | Polyphenylene sulfide resin composition |
JP4974265B2 (en) * | 2002-12-27 | 2012-07-11 | 東レ株式会社 | Polyphenylene sulfide resin composition |
JP2012177015A (en) * | 2011-02-25 | 2012-09-13 | Polyplastics Co | Polyarylene sulfide resin composition |
KR101944898B1 (en) * | 2012-06-11 | 2019-02-01 | 에스케이케미칼 주식회사 | Polyarylene sulfide resin composition and a preparation method thereof |
-
1985
- 1985-12-27 JP JP29280185A patent/JPS62153343A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS62153343A (en) | 1987-07-08 |
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