JPS62172056A - Polyphenylene sulfide composition - Google Patents
Polyphenylene sulfide compositionInfo
- Publication number
- JPS62172056A JPS62172056A JP1250586A JP1250586A JPS62172056A JP S62172056 A JPS62172056 A JP S62172056A JP 1250586 A JP1250586 A JP 1250586A JP 1250586 A JP1250586 A JP 1250586A JP S62172056 A JPS62172056 A JP S62172056A
- Authority
- JP
- Japan
- Prior art keywords
- pps
- weight
- olefin copolymer
- polyphenylene sulfide
- hot water
- 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
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 56
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000004711 α-olefin Substances 0.000 abstract description 30
- 229920000089 Cyclic olefin copolymer Polymers 0.000 abstract description 26
- 238000002156 mixing Methods 0.000 abstract description 9
- 239000000843 powder Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- -1 ethylene, propylene Chemical group 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 238000005453 pelletization Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000012744 reinforcing agent Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 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
- 238000007385 chemical modification Methods 0.000 description 2
- 238000007334 copolymerization reaction 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
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004519 manufacturing process 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
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 150000003839 salts Chemical class 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000010425 asbestos 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-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
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 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
- 239000004575 stone Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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、耐衝撃性の改良されたポリフェニレンスルフ
ィド組成物に関するものであり、更に詳しくは、特定の
ポリフェニレンスルフィド樹脂にα−オレフィン系共重
合体を含有せしめることにより耐衝撃性の改良されたポ
リフェニレンスルフィド組成物に関するものである。Detailed Description of the Invention <Industrial Application Field> The present invention relates to a polyphenylene sulfide composition with improved impact resistance. The present invention relates to a polyphenylene sulfide composition that has improved impact resistance by containing a polymer.
〈従来の技術〉
従来、耐衝撃性の改善されたボリフエニレンス従来、耐
衝撃性の改善されたポリフェニレンスルフィド樹脂組成
物としては、特開昭５９−２０７９２１＠公報に、ポリ
フェニレンスルフィド樹脂に不飽和カルボン酸またはそ
の無水物、またはそれらの誘導体をグラフト共重合した
α−オレフィンおよびエポキシ樹脂を配合せしめてなる
組成物が開示されている。<Prior art> Conventionally, polyphenylene sulfide resin compositions with improved impact resistance have been disclosed in Japanese Patent Application Laid-Open No. 59-207921, in which unsaturated carboxylic acid is added to polyphenylene sulfide resin. A composition comprising an epoxy resin and an α-olefin obtained by graft-copolymerizing α-olefin, anhydride thereof, or a derivative thereof is disclosed.
〈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耐衝撃
性の改善効果は不充分である。更に詳）ホすると、従来
知られているように通常のポリフェニレンスルフィド樹
脂の分子鎖は反応性に乏しいため、前記公報記載の共重
合体のような反応ｉ生に富んだゴム成分、あるいは、同
じく反応汁に富んだエポキシ樹脂を配合しても、ポリフ
ェニレンスルフィド樹脂との界面の付着か不充分である
ため、充分な耐＠撃性の改善効果が得られていないのか
現状である。<Problems to be Solved by the Invention> However, even in the composition described in the above-mentioned publication, the effect of improving impact resistance is insufficient. (More details) As is conventionally known, the molecular chains of ordinary polyphenylene sulfide resins have poor reactivity, so rubber components with high reactivity such as the copolymer described in the above-mentioned publication, or similar Even if an epoxy resin rich in reaction liquid is blended, the adhesion at the interface with the polyphenylene sulfide resin is insufficient, so the current situation is that a sufficient effect of improving impact resistance cannot be obtained.
そこで本発明者らは、ポリフェニレンスルフィド樹脂を
好ましく変性し、反応性を付与し、ゴムとを課題として
鋭意検討を行ない、特定の処理を行なったポリフェニレ
ンスルフィド樹脂に特定のゴム成分を配合することによ
りこの課題が解決されることを見出し、本発明に到達し
た。Therefore, the present inventors have conducted intensive studies on the problem of modifying polyphenylene sulfide resin in a preferable manner, imparting reactivity to it, and combining it with rubber. We have found that this problem can be solved and have arrived at the present invention.
く問題点を解決するための手段〉
すなわち本発明は、１００℃以上の熱水により処理され
たポリフェニレンスルフィド樹脂に、必須成分として、
不飽和カルボン酸またはその無水物、またはそれらの誘
導体０．０５〜１０．０重量％をグラフト共重合したα
−オレイン系共手合体を含有せしめてなる樹脂組成物を
提供するもので必る。Means for Solving Problems〉 That is, the present invention adds as an essential component to a polyphenylene sulfide resin treated with hot water of 100°C or higher.
α obtained by graft copolymerizing 0.05 to 10.0% by weight of an unsaturated carboxylic acid, its anhydride, or a derivative thereof.
- It is necessary to provide a resin composition containing an oleic covalent polymer.
本発明で使用するポリフェニレンスルフィド（以下ＰＰ
Ｓと称する）とは、構造式ト♂トｓ ＋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
上を含む手合体であり、上記繰返し単位が７０モル％未
満では耐熱性がｎわれるため好ましくない。Polyphenylene sulfide (hereinafter referred to as PP) used in the present invention
(referred to as S) is a polymer containing 70 mol% or more, more preferably 90 mol% or more of repeating units represented by the structural formula ♂ s This is not preferable because it will result in n.
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ｊｑられる比較的分子量で代表される
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ＩＵられる本質的に線状で比較的高分子量の重合体等
がおり、前記特公昭４５−３３６８号公報記載の方法で
１ｑられた重合体においては、重合俊酸素雰囲気下にお
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めるが、本発明の
効果が顕著でおること、ａ３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
。PPS is generally a polymer with a relatively small molecular weight obtained by a manufacturing method represented by Japanese Patent Publication No. 45-3368, and a relatively low molecular weight represented by jq.
There are essentially linear and relatively high molecular weight polymers which can be produced by the production method typified by Japanese Patent Publication No. 52-12240, and polymers which can be produced by the method described in Japanese Patent Publication No. 45-3368. It is also possible to increase the degree of polymerization and use it by heating in a polymerization-prone oxygen atmosphere or by adding a crosslinking agent such as peroxide and heating. Although it is possible to use PPS produced by the above-mentioned method, it is possible to use PPS as represented by the above-mentioned Japanese Patent Publication No. 52-12240, because the effect of the present invention is remarkable and the toughness of PPS itself is excellent. Essentially linear, relatively high molecular weight polymers obtained by the process may be more preferably used.
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。Furthermore, less than 30 mol% of the repeating units of PPS can be composed of repeating units having the following structural formula, etc.
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ｔ１１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１０，０００ポアズ以下のものがより好ましく用い
られる。The melt viscosity of PPS used in the present invention is not particularly limited to t11 as long as it is possible to obtain a molded product, but in terms of toughness of PPS itself, it is 100 poise or more, and in terms of moldability, it is 10,000 poise or more. Poise or less is more preferably used.
本発明にあ、いて使用するＰＰＳを熱水処理するにあた
り、熱水の温度を１００℃以上、より好ましくは１２０
℃以上、さらに好ましくは１５０°Ｃ以上、特に好まし
くは’１７０’ｃ以上とすることが重要でおり、１００
°ｂ
化学的変性の効果が小さいため好ましくない。When treating the PPS used in the present invention with hot water, the temperature of the hot water is set at 100°C or higher, more preferably at 120°C.
It is important to keep the temperature above 150°C, more preferably above 150°C, particularly preferably above 170°C, and 100°C or above.
°b Not preferred because the effect of chemical modification is small.
本発明の熱水洗浄によるるＰＰＳの好ましい化学的変性
の効果を発現するため、使用する水は蒸溜水あるいは脱
イオン水であることが好ましい。In order to achieve the desired effect of chemical modification of PPS by hot water washing according to the present invention, the water used is preferably distilled water or deionized water.
熱水処理の操作は、通常、所定量の水に所定量のＰＰＳ
を投入し、圧力容器内で加熱、撹拌することにより行わ
れる。ＰＰＳと水との割合は、水の多い方が好ましいが
、通常、水１．ｆｌに対し、ＰＰ３２００ｇ以下の浴比
が選択される。Hydrothermal treatment operations typically involve adding a predetermined amount of PPS to a predetermined amount of water.
is heated and stirred in a pressure vessel. As for the ratio of PPS to water, the more water the better, but usually the ratio is 1. A bath ratio of less than 3200 g of PP to fl is selected.
また、処理の雰囲気は、末端基の分解は好ましくないの
で、これを回避するため不活性雰囲気下とすることが好
ましい。更に、この熱水処理操作を終えたＰＰＳは、残
留している成分を物理的に除去するため温水で数回洗浄
するのが好ましい。Furthermore, since decomposition of terminal groups is undesirable, the treatment atmosphere is preferably an inert atmosphere to avoid this. Furthermore, it is preferable to wash the PPS after this hot water treatment several times with hot water in order to physically remove any remaining components.
本発明で熱水処理に供するＰＰＳは粉粒体でおることが
好ましく、特に微細な粉粒体でおることが処理の効率上
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等することな
く用いて熱水迫埋供するのが好ましく、必要によっては
、分級必るいは扮砕して用いることも可能である。The PPS to be subjected to hot water treatment in the present invention is preferably in the form of powder or granules, and particularly preferably in the form of fine powder or granules from the viewpoint of treatment efficiency. Since PPS produced by a known method is usually obtained in the form of powder or granules, it is preferable to use them without pelletizing and burying them in hot water.If necessary, they may be classified or crushed. It is also possible to use
また、重合復の湿潤状態のＰＰＳをそのまま熱水処理に
供することも可能である。It is also possible to directly subject PPS in a wet state after polymerization to hot water treatment.
また本発明で用いるＰＰＳには、本発明の効果をｎ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受けの
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５
９−１３１６５０号公報に記載されているチオホスフィ
ン酸金属塩等の架橋促進剤または特開昭５８−２０４０
４５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おる
。In addition, the PPS used in the present invention may include antioxidants, heat stabilizers, lubricants, crystal nucleating agents,
Conventional additives such as UV inhibitors, colorants, and various polymers can be added, and in addition, for the purpose of controlling the degree of crosslinking of PPS, conventional peroxidants and JP-A-5
Crosslinking accelerators such as thiophosphinic acid metal salts described in JP-A No. 9-131650 or JP-A-58-2040
It is also possible to incorporate crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole described in JP-A No. 45, JP-A-58-204046, and the like.
本発明で用いるα−オレフィン系共重合体とは不飽和カ
ルボン酸またはその無水物、またはそれらの誘導体をグ
ラフト共重合したα−オレフィン系共重合体でおり、こ
こでいう幹成分のα−オレフィン系ポリマとしては、エ
チレン、プロピレン、ブテン−１、イソブチン、ペンテ
ン−１，４−メチルペンテン−１、ヘキセン−１等の重
合体めるいはこれらの共重合体が挙げられ、更に共重合
可能な他の七ツマを共重合せしめたものでもよい。The α-olefin copolymer used in the present invention is an α-olefin copolymer obtained by graft copolymerizing an unsaturated carboxylic acid, its anhydride, or a derivative thereof, and the α-olefin as the main component here is Examples of the system polymers include polymers such as ethylene, propylene, butene-1, isobutyne, pentene-1,4-methylpentene-1, and hexene-1, and copolymers thereof, and copolymers thereof. It may also be a copolymer of other nanatsuma.
この幹成分のα−オレフィン系ポリマにグラフト共重合
する不飽和カルボン酸またはその無水物の例を挙げると
、アクリル酸、メタクリル酸、マレイン酸、フマル酸、
イタコン酸、クロ（〜ン酸、メチルマレイン酸、メチル
フマル酸、メサコン酸、シ１〜ラコン酸、グルタコン酸
、マレイン酸水素メチル、マレイン酸水素エチル、フマ
ル酸水素メチル、フマル酸水素エチル、イタコン酸メチ
ル、無水マレイン酸、無水イタコン酸、無水メチルマレ
イン酸、無水シトラコン酸、エンドビシクロ−［２，２
，１］−５−へブテン−２，３−ジカルボン酸、エンド
ごシクロ−［２，２，１］−５−ヘプテン−２，３−無
水ジカルボン酸であり、これらの誘導体も用いられ得る
が、中でも無水マレイン酸がより好ましく用いられる。Examples of unsaturated carboxylic acids or their anhydrides that are graft copolymerized with the α-olefin polymer as the main component include acrylic acid, methacrylic acid, maleic acid, fumaric acid,
Itaconic acid, Chloroic acid, Methyl maleic acid, Methyl fumaric acid, Mesaconic acid, Laconic acid, Glutaconic acid, Methyl hydrogen maleate, Ethyl hydrogen maleate, Methyl hydrogen fumarate, Ethyl hydrogen fumarate, Itaconic acid Methyl, maleic anhydride, itaconic anhydride, methylmaleic anhydride, citraconic anhydride, endobicyclo-[2,2
, 1]-5-hebutene-2,3-dicarboxylic acid, endocyclo-[2,2,1]-5-heptene-2,3-dicarboxylic anhydride, although derivatives of these may also be used. Among them, maleic anhydride is more preferably used.
これらグラフト成分の共重合量は通常、０１Ｏ５〜１０
．０重量％、特に０．１〜５．０重量％が好ましく、０
．０５重１％未満では目的とする効果が得られず、１０
．０１璽％を越えるとＰＰＳとの溶融混練時にゲル化を
生じる、あるいは、得られる組成物が著しく８減し、外
観が損われる等の問題が生じるため好ましくない。The copolymerization amount of these graft components is usually 01O5 to 10
．． 0% by weight, particularly preferably 0.1 to 5.0% by weight, 0
．． If the weight of 05 weight is less than 1%, the desired effect cannot be obtained;
．． If the amount exceeds 0.01%, it is not preferable because gelation occurs during melt-kneading with PPS, or the resulting composition is significantly reduced by 8%, resulting in poor appearance.
ここでグラフト共重合とは、幹成分のα−オレフィン系
ポリマの一部または全部が不飽和カルボン酸またはその
無水物、またはそれらの誘導体と化学的に結合すること
を意味し、これらの反応は、溶液状態、懸濁状態、スラ
リー状態おるいは溶融状態で通常公知の方法で行うこと
ができる。Graft copolymerization here means that part or all of the α-olefin polymer as the backbone component is chemically bonded to an unsaturated carboxylic acid, its anhydride, or a derivative thereof, and these reactions are This can be carried out in a solution state, suspension state, slurry state or melt state by a commonly known method.
ＰＰＳとα−オレフィン系共重合体を配合する割合に特
に制限はないが、α−オレイン系共重合体が３重間％未
満では目的とする効果が１４にくく、また、３０重量％
を越えるとＰＰＳの強度、剛性、耐熱性が損なわれる恐
れが生ずるばかりでなく、溶融混練時にゲル化を生じ、
押出安定性、成形性が損われることがおるので、ＰＰ８
７０〜９７重量％に対し、α−オレフィン系共重合体３
０〜３重量％が好ましく、より好ましくはＰＰ３７５〜
９５重量％に対し、α−オレフィン系共小合体２５〜５
重量％、特にＰＰ５８０〜９０重量％に対し、α−オレ
フィン系共重合体２０〜１０１ｆｆｉ％の範囲を好まし
く選択することができる。There is no particular limit to the ratio of blending PPS and α-olefin copolymer, but if the α-olefin copolymer is less than 3% by weight, it will be difficult to achieve the desired effect, and if the content is less than 3% by weight,
Exceeding this may not only cause the strength, rigidity, and heat resistance of PPS to be impaired, but also cause gelation during melt-kneading.
PP8 may impair extrusion stability and moldability.
70 to 97% by weight of α-olefin copolymer 3
0 to 3% by weight is preferable, more preferably PP375 to
95% by weight, α-olefin copolymer 25-5
A range of 20 to 101 ffi% of the α-olefin copolymer can be preferably selected based on the weight% of the PP, particularly 580 to 90% by weight of the PP.
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α−オレフ
ィン系共重合体の合計１００重晟１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おり、通常１
０〜３００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。In the present invention, the fibrous and/or granular reinforcing agent is not an essential component, but may be used in an amount not exceeding 300 parts by weight per 100 kg/ml of PPS and α-olefin copolymer. It is possible to mix it, and usually 1
By blending in the range of 0 to 300 parts by weight, it is possible to improve strength, rigidity, heat resistance, dimensional stability, etc.
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、セラミック１繭
維、アスベス１〜繊維、石ロウ繊維、金属繊維等の無機
′ｍ維ａ３よび炭素繊維等が挙げられる。Such fibrous reinforcing agents include inorganic fibers such as glass fibers, shirasu glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbeth fibers, stone wax fibers, metal fibers, and carbon fibers. Can be mentioned.
また粒状の強化剤としては、ワラステナイト、セッサイ
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、アルミナシリヶ一トなどの珪酸塩、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、炭酸カルシウム、炭酸
マグネシウム、ドロマイ１〜などの炭酸塩、硫酸カルシ
ウム、硫酸バリウムなどの＠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
、これらは中空であってもよい。ごれら強化剤は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ップリング剤で予備処理して使用
することができる。In addition, granular reinforcing agents include wollastenite, sessite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as aluminasilicate, and metals such as alumina, silicon chloride, magnesium oxide, zirconium oxide, and titanium oxide. Examples include oxides, carbonates such as calcium carbonate, magnesium carbonate, and dolomites, @ acid salts such as calcium sulfate and barium sulfate, glass beads, boron nitride, silicon carbide, Saroyan, and silica. There may be. Two or more types of reinforcing agents can be used in combination, and if necessary, they can be pretreated with a coupling agent such as a silane type or titanium type before use.
本発明の組成物の調製手段は特に制限はないが、ＰＰＳ
とα−オレフィ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ｊ麦、ペレタイズす
る方法が代表的でおる。The means for preparing the composition of the present invention is not particularly limited, but PPS
A typical method is to melt-knead PPS, an α-olefin copolymer, and a reinforcing agent in an extruder at a temperature higher than the melting point of PPS, and then pelletize the mixture.
なＪ５、溶融混練温度は２８０〜３４０°Ｃが好ましく
、２８０ °Ｃ未満ではＰＰＳの溶融が不充分になるこ
とがおり、３４０℃を越えるとα−オレフィン系共重合
体の熱劣化およびゲル化することがおるので注意を要す
る。J5, the melt-kneading temperature is preferably 280 to 340°C. If it is less than 280°C, the melting of PPS may be insufficient, and if it exceeds 340°C, thermal deterioration and gelation of the α-olefin copolymer may occur. Please be careful as this may happen.
以下に実施例を挙げて本発明をざらに詳細に説明する。EXAMPLES The present invention will be explained in detail below by giving examples.
〈実施例〉
参考例１ （ＰＰＳの重合〉
オートクレーブに硫化ナトリ「クム３．２６Ｋｇ（２５
モル、結晶水４０％を含む）、水酸化す１〜リウム４３
、酢酸ナトリウム三水和物１．３６に！？（約１０モル
）およびＮ−メチル−２−ゴロリドン（以下ＮＭＰと略
称する＞７．９Ｋｇを仕込み、攪拌しながら徐々に２０
５℃まで昇温し、水１゜３６にぴを含む留出水約１．５
．ｆ！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）およびＮ Ｍ Ｐ
２ Ｋｇを加え、２６５°Ｃ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
減圧屹乾燥て、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。<Example> Reference Example 1 (Polymerization of PPS) Sodium sulfide cum 3.26 kg (25 kg) was placed in an autoclave.
mole, including 40% water of crystallization), 1 to 43 lithium hydroxide
, sodium acetate trihydrate to 1.36! ? (approximately 10 moles) and N-methyl-2-gorolidone (hereinafter abbreviated as NMP) >7.9 kg were added, and while stirring, gradually
The temperature is raised to 5℃, distilled water containing 1.36 liters of water is approximately 1.5
．． f! was removed. Add 1,4-dichlorobenzene to the residual mixture3. '75Kg (25,5 mol) and N M P
2 Kg was added and heated at 265°C for 4 hours. The reaction product was washed 5 times with hot water at 70°C, dried under reduced pressure at 80°C for 24 hours, and had a melt viscosity of about 2500 poise (320°C,
Approximately 2 kg of powdered PPS with a shear rate of 1000 sec-1) was obtained.
同様の操作を繰返し、以下に記載の実施例に供した。The same operation was repeated and used in the examples described below.
参考例２ （α−オレイン系共重合体の調製）９０モル
％のエチレンと１０モル％のブテン−１からなるエチレ
ン・ブテン−１共重合体１００張最部に対し、少量のア
セ１ヘンに溶解したジーを一ブチルパーオキサイド０．
１重量部および無水マレイン酸１．５宙吊部を添加した
のち、２００°Ｃに設定したスクリュー押出機に供給し
、混練し、ベレン］〜化した。Reference Example 2 (Preparation of α-oleic copolymer) A small amount of acetic acid was added to the 100% ethylene-butene-1 copolymer consisting of 90 mol% ethylene and 10 mol% butene-1. Add 0.0% of the dissolved zeolite to monobutyl peroxide.
After adding 1 part by weight and 1.5 suspended parts of maleic anhydride, the mixture was fed to a screw extruder set at 200°C, kneaded, and converted into belene.
このペレットを粉砕後、アセトンにより未反応の無水マ
レイン酸を抽出し、次いでプレス・シートの核外吸収ス
ペクトルでグラフト重合した無水マレイン酸を定量した
ところ０．８８重１％の無水マレイン酸を含有している
ことがわかった。After crushing the pellets, unreacted maleic anhydride was extracted with acetone, and the graft-polymerized maleic anhydride was quantified using the extranuclear absorption spectrum of the press sheet, and found to contain 0.88% by weight of maleic anhydride. I found out that it is.
参考例３ （α−オレイン系共重合体の調製）参考例２
でエチ１ノン・ブテン−１共用合体を用いＬこ代りに、
８０モル％のエチレン−プロピレン共重合体を用いたこ
との他は参考例２と全く同様の方法でペレットを（９だ
。Reference example 3 (Preparation of α-oleic copolymer) Reference example 2
In place of L, using ethyl-1-non-butene-1 co-combined,
Pellets (9) were prepared in exactly the same manner as in Reference Example 2, except that 80 mol% ethylene-propylene copolymer was used.
参考例２と全く同様の方法でグラフ１〜重合した無水マ
レイン竣を定量したところ０．９２Φ１ｉ％の無水マレ
イン酸を含有し−（いた。When the final maleic anhydride polymerized in Graph 1 was quantified in exactly the same manner as in Reference Example 2, it was found to contain 0.92Φ1i% of maleic anhydride.
参考例４ （α−オレイン系共重合体の調製）参考例２
で用いたエチレン・ブテン−１共重合体１００重量部を
１−ルエン５００重量部に９０℃にて加熱攪拌して溶解
（変、無水マレイン酸を４部を添加し溶解した。次に、
溶液を１０５°Ｃまで昇温し、トルエン３０重量部にジ
−ｔ−ブチルパーオキサイド０．１重は部を溶解した溶
液を３０ぷんかんかけて滴下した後、１０５°Ｃで５時
間保持し重合を行った。得られたグラフト共重合体溶液
にトルエン５００重量部を７ＪＩ］え希釈した後、等量
の５０℃のメタノール中に少量ずつ滴下し、グラフト重
合されたα−オレフィン系共重合体を析出させ、洗浄、
乾燥した。このα−オレフィン系共重合体について、参
考例２と全く同様の方法で評価した無水マレイン酸含有
量は２．５７重量％であった。Reference example 4 (Preparation of α-oleic copolymer) Reference example 2
100 parts by weight of the ethylene-butene-1 copolymer used in 1-toluene was dissolved in 500 parts by weight of 1-toluene by heating and stirring at 90°C (4 parts of maleic anhydride was added and dissolved. Next,
The temperature of the solution was raised to 105°C, and a solution of 0.1 part by weight of di-t-butyl peroxide dissolved in 30 parts by weight of toluene was added dropwise over 30 drops, followed by holding at 105°C for 5 hours. Polymerization was performed. The obtained graft copolymer solution was diluted with 500 parts by weight of toluene (7JI), and then added dropwise little by little into an equal amount of methanol at 50°C to precipitate the graft-polymerized α-olefin copolymer, Washing,
Dry. The maleic anhydride content of this α-olefin copolymer was evaluated in exactly the same manner as in Reference Example 2 and was found to be 2.57% by weight.
実施例１
参考例１で得られたＰＰＳ粉末約２Ｋｇと］悦イオン水
１０．ｆ！とをオートクレーブに仕込み、常圧で密閉し
たのち、１８０℃まで胃温し、攪拌しながら約３０分間
保温したのち冷却した。内容物を取りだし濾過し、更に
、７０℃の脱イ剖ン水約１０９の中にＰＰＳを浸漬、撹
拌し、濾過する操作を５回繰返したのち、１２０℃で２
４時間減圧乾燥し、粉末状とした。Example 1 Approximately 2 kg of PPS powder obtained in Reference Example 1 and 10. f! The mixture was placed in an autoclave, sealed at normal pressure, heated to 180°C, kept warm for about 30 minutes with stirring, and then cooled. The contents were taken out and filtered, and the operation of immersing PPS in deionized water at 70°C, stirring, and filtering was repeated 5 times.
It was dried under reduced pressure for 4 hours to form a powder.
この粉末と、参考例２で１得られたα−オレフィン系共
重合体とを８０対２０の重量化でトライブレンドし、２
９０〜３１０℃に設定したスクリュー押出機により溶融
混合し、ペレタイズした。次にペレットを２９０〜３０
０ ℃に設定したスクリューインライン型射出成形機に
供給し、金型温度１５０℃の条件で機械特性評価用試験
片を成形した。This powder and the α-olefin copolymer obtained in Reference Example 2 were triblended at a weight ratio of 80:20, and 2
The mixture was melt-mixed and pelletized using a screw extruder set at 90 to 310°C. Next, add pellets to 290-30
The sample was supplied to a screw in-line injection molding machine set at 0°C, and a test piece for mechanical property evaluation was molded at a mold temperature of 150°C.
た。Ta.
ｊｑ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＞、引張伸度（ＡＳＴＭ
Ｄ−６３８）および熱変形温度（ＡＳＴＭ Ｄ−６４
８＞は第１表に記載の通りであり、衝撃強度が極めて大
きく、靭性が付与されており、かつ、α−オレフィン系
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
さかった。Izot impact strength (ASTM D-256>, tensile elongation (ASTM
D-638) and heat distortion temperature (ASTM D-64)
8> is as shown in Table 1, and the impact strength was extremely high and toughness was imparted, and the decrease in heat distortion temperature was smaller than that of those without blending the α-olefin copolymer.
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と同様の方法で熱水処理し、洗浄、乾
燥したもの（比較例２）を用い、α−オレフィン系共重
合体を配合することなく、ペレタイズ、射出成形を行っ
た試験片について評価したアイゾツト衝撃強度、引張伸
度、熱変形温度（よ第１表に記載のとおりでめった。Comparative Examples 1-2 The PPS powder obtained in Reference Example 1 was used as it was (Comparative Example 1)
And a test piece that was treated with hot water in the same manner as in Example 1, washed and dried (Comparative Example 2), and pelletized and injection molded without blending the α-olefin copolymer. The Izot impact strength, tensile elongation, and heat distortion temperature were evaluated as shown in Table 1.
比較例３
実施例１で参考例１で得られたＰＰＳ粉末を熱水処理し
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、
α−オレフィン系共重合体と？８融混合、ペレタイズ、
射出成形を行った試験片について評価したアイゾツト衝
撃強度、引張伸度、熱変形温度は第１表に記載のとおり
であった。Comparative Example 3 Completely the same as Example 1 except that instead of using the PPS powder obtained in Reference Example 1 after hot water treatment, the PPS powder obtained in Reference Example 1 was used as it was. In the method of
α-olefin copolymer? 8 melt mixing, pelletizing,
The Izot impact strength, tensile elongation, and heat distortion temperature evaluated for the injection molded test pieces were as shown in Table 1.
比較例４
実施例１で参考例１で得られたＰＰＳ粉末を熱水処理し
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、ＰＰＳとα−オレフィン系共重合体の合計１
００重量部に対し、２重量部のビスフェノールＡ型エポ
キシ樹脂（油化シェル・エポキシ（株）製゛′エピコー
ト”１００７）を配合したことのほかは実施例１と全く
同様の方法でペレタイズ、射出成形を行った。Comparative Example 4 Instead of using the PPS powder obtained in Reference Example 1 after hot water treatment, the PPS powder obtained in Reference Example 1 was used as it was, and a mixture of PPS and α-olefin copolymer was used. Total 1
Pelletizing and injection were carried out in the same manner as in Example 1, except that 2 parts by weight of bisphenol A type epoxy resin ("Epicote" 1007 manufactured by Yuka Shell Epoxy Co., Ltd.) was added to 00 parts by weight. I did the molding.
ＩＪられた試験片について評価した特性値は第１表記載
の通りであった。The characteristic values evaluated for the IJ test pieces were as listed in Table 1.
実施例２〜４、比較例５
実施例１で、参考例１で得られたＰＰＳ粉末を熱水処理
する際に温度を１８０℃とした代りに第１表に記載の温
度としたことのほかは、実施例１と全く同様の操作を行
い試験片を得た。Examples 2 to 4, Comparative Example 5 In Example 1, when the PPS powder obtained in Reference Example 1 was treated with hot water, the temperature was set to 180°C instead of the temperature listed in Table 1. A test piece was obtained by performing exactly the same operation as in Example 1.
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
通りであった。The characteristic values evaluated for the obtained test piece were as shown in Table 1.
実施例５〜６
実施例］で参考例２で得られたα−オレフィン系共重合
体を用いた代りに、それぞれ参考例３（実施例５）、参
考例４（実施例６）で（ｑられたα−オレフィン系共重
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。Examples 5 to 6 Instead of using the α-olefin copolymer obtained in Reference Example 2, in Reference Example 3 (Example 5) and Reference Example 4 (Example 6), (q A test piece was obtained by carrying out exactly the same operation as in Example 1, except for using the α-olefin copolymer prepared in Example 1.
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
通りであった。The characteristic values evaluated for the obtained test piece were as shown in Table 1.
実施例７
実施例１でα−オレフィン系共重合体の配合割合を２０
重量％とじた代りに、１０手ｆｆｉ％としたことのほか
は実施例１と全く同様の操作を行った。Example 7 In Example 1, the blending ratio of the α-olefin copolymer was changed to 20
The same operation as in Example 1 was carried out, except that instead of binding by weight, 10 ffi% was used.
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
とおりでめった。The characteristic values evaluated for the obtained test piece were as shown in Table 1.
実施例８〜９
実施例１と同様の方法で熱水処理を行ったＰＰＳ粉末と
、参考例２で得られたα−オレフィン系共重合体とガラ
ス繊維とを第１表に記載の３１１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、１
ｑられた試験片について評価した特性値は第１表に記載
のとおりでめった。Examples 8 to 9 PPS powder treated with hot water in the same manner as in Example 1, the α-olefin copolymer obtained in Reference Example 2, and glass fiber were combined in the 311 polymerization shown in Table 1. Melt mixing, pelletizing, and injection molding were carried out in exactly the same manner as in Example 1.
The characteristic values evaluated for the tested test pieces were as shown in Table 1.
比較例６〜７
参考例１で得られたＰＰＳとガラス繊維（比較例６）、
参考例１で得られたＰＰＳと参考例２で得られたα−オ
レフィン系共重合体とガラス繊維（比較例７）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、ｊｑられた
試論片について評価した特性値は第１表に記載の通りで
あった。Comparative Examples 6-7 PPS and glass fiber obtained in Reference Example 1 (Comparative Example 6),
The PPS obtained in Reference Example 1, the α-olefin copolymer obtained in Reference Example 2, and glass fiber (Comparative Example 7) were mixed in the same proportions as in Example 1, respectively, as shown in Table 1. The characteristic values evaluated for the sample pieces melt-blended, pelletized, injection molded and jqed using the method described above were as shown in Table 1.
第１表の結果から、熱水処理を施したＰＰＳを使用した
樹脂組成物は、熱水処理をしないものに比べて耐衝撃性
および引張破断伸度に代表される靭性が特に優れたもの
でおることがわかった。From the results in Table 1, the resin compositions using PPS treated with hot water have particularly excellent impact resistance and toughness represented by tensile elongation at break compared to those without hot water treatment. I found out that there is.
実施例１０
実施例１で、ＰＰＳとα−オレフィン系共重合体の合計
１００重量部に対し、比較例４で用いたエポキシ樹脂２
重量部を配合したことのほかは実施例１と全く同様の方
法で試験片を得た。Example 10 In Example 1, the epoxy resin 2 used in Comparative Example 4 was added to a total of 100 parts by weight of PPS and α-olefin copolymer.
A test piece was obtained in exactly the same manner as in Example 1 except that the parts by weight were blended.
得られた試験片について評価したカット・ノツチ付アイ
ゾツト衝撃強度は２４に！Ｊ・Ｃｍ／Ｃｍ・ノツチで必
り、熱変形温度（高荷重）は１０３℃であり、熱変形温
度（高荷重）は１００℃であった。The cut and notched Izot impact strength evaluated for the obtained test piece was 24! For J・Cm/Cm・notch, the heat distortion temperature (high load) was 103°C, and the heat distortion temperature (high load) was 100°C.
実施例１１
実施例１と同様の方法で熱水処理を行ったＰＰＳ粉末と
、参考例２で得られたα−オレフィン系共重合体とポリ
エチレンとを８０対１０対１０の重量比でトライブレン
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）けた。得られた試
験片について評価したカット・ノツチ付アイゾツ１〜衝
撃強度は１４ Ｋｇ・ｃｍ／ｃｍ・ノツチであり、熱変
形温度（高荷重）は１０２°Ｃであった。Example 11 Tri-blend of PPS powder treated with hot water in the same manner as in Example 1, the α-olefin copolymer obtained in Reference Example 2, and polyethylene at a weight ratio of 80:10:10. Then, melt mixing, pelletizing, and injection molding were performed in exactly the same manner as in Example 1 to obtain test pieces. The cut/notched Izotsu 1 impact strength evaluated for the obtained test piece was 14 Kg·cm/cm·notch, and the heat distortion temperature (high load) was 102°C.
〈発明の効果〉
本発明により、耐衝撃性が極めて優れたボ１ノフ工二し
ンスルーノイド樹脂組成物が得られるようになった。<Effects of the Invention> According to the present invention, it has become possible to obtain a synthetic resin composition having extremely excellent impact resistance.
Claims (1)
ルフィド樹脂に、必須成分として、不飽和カルボン酸ま
たはその無水物、またはそれらの誘導体０．０５〜１０
．０重量％をグラフト共重合したα−オレイン系共重合
体を含有せしめてなるポリフェニレンスルフィド組成物
。The polyphenylene sulfide resin treated with hot water of 100°C or higher contains an unsaturated carboxylic acid, anhydride thereof, or a derivative thereof as an essential component from 0.05 to 10%.
．． A polyphenylene sulfide composition containing 0% by weight of a graft copolymerized α-olein copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61012505A JPH0653848B2 (en) | 1986-01-23 | 1986-01-23 | Polyphenylene sulfide composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61012505A JPH0653848B2 (en) | 1986-01-23 | 1986-01-23 | Polyphenylene sulfide composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62172056A true JPS62172056A (en) | 1987-07-29 |
| JPH0653848B2 JPH0653848B2 (en) | 1994-07-20 |
Family
ID=11807208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61012505A Expired - Lifetime JPH0653848B2 (en) | 1986-01-23 | 1986-01-23 | Polyphenylene sulfide composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0653848B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01217091A (en) * | 1988-02-25 | 1989-08-30 | Nisshin Steel Co Ltd | Resin composition having excellent adhesion to metal |
| JPH02308855A (en) * | 1989-05-25 | 1990-12-21 | Dainippon Ink & Chem Inc | Resin composition for sealing electronic part |
| US5087666A (en) * | 1990-07-10 | 1992-02-11 | Phillips Petroleum Company | Modified poly(arylene sulfide) composition with improved impact strength and reduced shrinkage |
| US5786422A (en) * | 1991-02-13 | 1998-07-28 | Tosoh Corporation | Polyphenylene sulfide resin composition |
| US7173090B2 (en) | 2001-10-25 | 2007-02-06 | Asahi Kasei Chemicals Corporation | Polyphenylene sulfide resin composition |
| JP2007517968A (en) * | 2004-01-12 | 2007-07-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Thermally conductive thermoplastic resin composition |
| US7910655B2 (en) | 2003-11-21 | 2011-03-22 | Cheil Industrial Inc. | Polyarylene sulfide thermoplastic resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56136847A (en) * | 1980-03-31 | 1981-10-26 | Dainippon Ink & Chem Inc | Polyarylenesulfide composition |
| JPS57108135A (en) * | 1980-12-26 | 1982-07-06 | Asahi Glass Co Ltd | Method for removing common salt from polyphenylene sulfide resin |
| JPS62151460A (en) * | 1985-12-26 | 1987-07-06 | Sumitomo Chem Co Ltd | Polyarylene sulfide resin composition |
-
1986
- 1986-01-23 JP JP61012505A patent/JPH0653848B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56136847A (en) * | 1980-03-31 | 1981-10-26 | Dainippon Ink & Chem Inc | Polyarylenesulfide composition |
| JPS57108135A (en) * | 1980-12-26 | 1982-07-06 | Asahi Glass Co Ltd | Method for removing common salt from polyphenylene sulfide resin |
| JPS62151460A (en) * | 1985-12-26 | 1987-07-06 | Sumitomo Chem Co Ltd | Polyarylene sulfide resin composition |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01217091A (en) * | 1988-02-25 | 1989-08-30 | Nisshin Steel Co Ltd | Resin composition having excellent adhesion to metal |
| JPH02308855A (en) * | 1989-05-25 | 1990-12-21 | Dainippon Ink & Chem Inc | Resin composition for sealing electronic part |
| US5087666A (en) * | 1990-07-10 | 1992-02-11 | Phillips Petroleum Company | Modified poly(arylene sulfide) composition with improved impact strength and reduced shrinkage |
| US5786422A (en) * | 1991-02-13 | 1998-07-28 | Tosoh Corporation | Polyphenylene sulfide resin composition |
| US7173090B2 (en) | 2001-10-25 | 2007-02-06 | Asahi Kasei Chemicals Corporation | Polyphenylene sulfide resin composition |
| US7910655B2 (en) | 2003-11-21 | 2011-03-22 | Cheil Industrial Inc. | Polyarylene sulfide thermoplastic resin composition |
| JP2007517968A (en) * | 2004-01-12 | 2007-07-05 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Thermally conductive thermoplastic resin composition |
| JP4764351B2 (en) * | 2004-01-12 | 2011-08-31 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Thermally conductive thermoplastic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0653848B2 (en) | 1994-07-20 |
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