JPH03236931A - Blow hollow molded product - Google Patents
Blow hollow molded productInfo
- Publication number
- JPH03236931A JPH03236931A JP2033148A JP3314890A JPH03236931A JP H03236931 A JPH03236931 A JP H03236931A JP 2033148 A JP2033148 A JP 2033148A JP 3314890 A JP3314890 A JP 3314890A JP H03236931 A JPH03236931 A JP H03236931A
- Authority
- JP
- Japan
- Prior art keywords
- pps
- weight
- elastomer
- water
- hollow molded
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920001971 elastomer Polymers 0.000 claims abstract description 25
- 239000000806 elastomer Substances 0.000 claims abstract description 24
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000011342 resin composition Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 6
- 239000011347 resin Substances 0.000 claims abstract description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 54
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 54
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 10
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 9
- 238000002242 deionisation method Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 24
- 238000010306 acid treatment Methods 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 208000002387 Popliteal pterygium syndrome Diseases 0.000 description 52
- 239000000047 product Substances 0.000 description 30
- 238000000071 blow moulding Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 229920000098 polyolefin Polymers 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- -1 methyl ethyl Chemical group 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 229920002647 polyamide Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000012744 reinforcing agent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 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
- 238000007385 chemical modification Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 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
- 238000009835 boiling Methods 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 229920002379 silicone rubber Polymers 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- JITSWUFGPFIMFG-UHFFFAOYSA-N 1,1,2,2,4-pentachlorobutane Chemical compound ClCCC(Cl)(Cl)C(Cl)Cl JITSWUFGPFIMFG-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-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
- 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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-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
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
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- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 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
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- 239000000654 additive Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 150000004945 aromatic hydrocarbons Chemical class 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
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- 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
- 229920001400 block copolymer Polymers 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
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- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical class CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
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- 238000010103 injection stretch blow moulding Methods 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
- 239000005453 ketone based solvent Substances 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 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
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IWELDVXSEVIIGI-UHFFFAOYSA-N piperazin-2-one Chemical compound O=C1CNCCN1 IWELDVXSEVIIGI-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000005060 rubber Substances 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
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 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
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は耐熱性、耐薬品性および耐衝撃性のすぐれたブ
ロー中空成形品に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a blow hollow molded product having excellent heat resistance, chemical resistance and impact resistance.
〈従来の技術〉
ＰＰＳ樹脂（以下、ＰＰＳと略称する）は耐熱性、耐薬
品性、難燃性および電気特性がすぐれたエンジニアリン
グプラスチックであり１．電気・電子部品、自動車部品
および精密機械部品などの用途に対し、近年その需要が
ますます高まりつつある。しかし、ＰＰＳを成形加工す
る方法は、ＰＰＳの溶融流動性が非常に大きいことから
、はとんど射出成形に限られており、そのため成形品形
状は小型のものか大部分でたとえばブロー成形などによ
るボトルおよびタンクなどの大型部品への応用はあまり
なされていない。ブロー成形の例としてはたとえば特開
昭６１−２５５８３２号公報に記されたｐｐｓのブロー
成形容器およびその製造法が知られているが、これは著
しく高い重合度を有するＰＰＳを用い、なおかつ特殊な
射出延伸ブロー成形法を組合わせたものであり、汎用的
なＰＰＳのブロー成形技術が確立されたものとはいえな
い。<Prior Art> PPS resin (hereinafter abbreviated as PPS) is an engineering plastic with excellent heat resistance, chemical resistance, flame retardance, and electrical properties.1. Demand has been increasing in recent years for applications such as electrical/electronic parts, automobile parts, and precision mechanical parts. However, the method of molding PPS is mostly limited to injection molding due to the extremely high melt fluidity of PPS, so the shape of the molded product is mostly small or blow molding. However, it has not been widely applied to large parts such as bottles and tanks. As an example of blow molding, a pps blow molded container and its manufacturing method described in JP-A No. 61-255832 are known, but this uses PPS with a significantly high degree of polymerization and a special method. It is a combination of injection stretch blow molding, and it cannot be said that a general-purpose PPS blow molding technology has been established.
一方、自動車部品においてはエンジンルーム内のダクト
類をブロー成形によって製造する方法が普及してきてお
り、現在は主としてポリアミド系材料が使用されている
が、ポリアミド系材料では耐熱性が不十分であるために
耐熱性が高く、しかも耐薬品性、耐衝撃性も兼備したブ
ロー成形用材料が求められているのが実状である。On the other hand, in the field of automobile parts, the method of manufacturing ducts in the engine room by blow molding has become popular, and currently polyamide-based materials are mainly used, but polyamide-based materials have insufficient heat resistance. The current situation is that there is a need for blow molding materials that have high heat resistance, as well as chemical resistance and impact resistance.
〈発明が解決しようとする課題〉
そこで本発明者らは上記の諸要求を満足するブロー中空
成形品を特殊な成形法を適用することなく ｐｐｓ系ポ
リマを用いて得ることを課題として鋭意検討した結果、
脱イオン処理を施したＰＰＳ、エポキシ基含有オレフィ
ン系共重合体およびエラストマからなる樹脂組成物が通
常公知のブロー成形法を用いて良好な成形品を与えるこ
とができ、しかも得られた成形品は上記諸要求全てを満
足するものであることを見出し本発明に到達した。<Problem to be solved by the invention> Therefore, the present inventors have conducted intensive studies with the aim of obtaining a blown hollow molded product that satisfies the above requirements using a pps-based polymer without applying any special molding method. result,
A resin composition consisting of deionized PPS, an epoxy group-containing olefin copolymer, and an elastomer can be used to give a good molded product using a commonly known blow molding method, and the molded product obtained is The present invention was achieved by discovering that it satisfies all of the above requirements.
く課題を解決するための手段〉
すなわち本発明は、脱イオン処理を施したＰＰ３９８〜
６０重量％、エポキシ基含有オレフィン系共重合体２〜
４０重量％および前記オレフィン系共重合体以外のエラ
ストマ１〜３５重量％からなる樹脂成分１００重量部に
対し、無機充填材０〜２００重量部を添加してなるＰＰ
Ｓ組戒物を主たる構成成分とすることを特徴とするブロ
ー中空成形品を提供するものである。Means for Solving the Problems〉 That is, the present invention provides deionized PP398~
60% by weight, epoxy group-containing olefin copolymer 2~
PP made by adding 0 to 200 parts by weight of an inorganic filler to 100 parts by weight of a resin component consisting of 40% by weight and 1 to 35% by weight of an elastomer other than the olefin copolymer.
The present invention provides a blow-hollow molded product characterized by containing S group kaimono as a main component.
本発明で使用するＰＰＳとは、構造式
←Ｃチ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。The PPS used in the present invention is a polymer containing 70 mol% or more, more preferably 90 mol% or more of repeating units represented by the structural formula ←C-s+; It is not desirable because it impairs the sex.
ＰＰＳは一般に、特公昭４５−３３６８号公 ３−
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
量の重合体などがあり、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
物など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る。PPS is generally a polymer with a relatively small molecular weight obtained by the production method typified by Japanese Patent Publication No. 45-3368, and an essential polymer obtained by the production method typified by JP-B No. 52-12240. There are linear polymers with relatively high molecular weight, etc. In the polymer obtained by the method described in Japanese Patent Publication No. 45-3368, after polymerization, heating in an oxygen atmosphere or peroxide It is also possible to increase the degree of polymerization and use it by adding a crosslinking agent such as and heating it.
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、本質的に線状で比較的高分
子量の重合体がより好ましく使用される。Although it is possible to use PPS obtained by any method in the present invention, an essentially linear polymer having a relatively high molecular weight is 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など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.
本発明で用いるＰＰＳは上記重合工程を経て生成した後
酸処理、熱水処理または有機溶媒による洗浄により脱イ
オン処理を施されたものであることが必須である。It is essential that the PPS used in the present invention is produced through the above polymerization process and then subjected to deionization treatment by acid treatment, hot water treatment, or washing with an organic solvent.
脱イオン処理を胞されていないＰＰＳを用いた場合には
エポキシ基含有ポリオレフィン共重合体およびエラスト
マと混練した際の相溶性が悪く、得られる樹脂組成物の
外観不良や耐衝撃性の大幅な低下が起こり実用的な材料
を得ることができない。When PPS that has not been subjected to deionization treatment is used, it has poor compatibility when kneaded with epoxy group-containing polyolefin copolymers and elastomers, resulting in poor appearance and significant reduction in impact resistance of the resulting resin composition. occurs, making it impossible to obtain practical materials.
酸処理を行う場合は次のとおりである。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、プロピル酸などが挙げられ、なかで
も、酢酸、塩酸がより好ましく用いられ得るか、硝酸の
ようなＰＰＳを分解、劣化させるものは好ましくない。The case where acid treatment is performed is as follows. In the present invention, PPS
The acid used for the acid treatment is not particularly limited as long as it does not have the effect of decomposing PPS, and examples include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, propylic acid, etc. Among them, acetic acid, Hydrochloric acid is more preferably used, and nitric acid, which decomposes and degrades PPS, is not preferred.
酸処理の方法は、酸または酸の水溶液にＰＰＳを浸漬せ
しめるなどの方法があり、必要により適宜撹拌または加
熱することも可能である。The acid treatment may be carried out by immersing PPS in an acid or an aqueous solution of the acid, and stirring or heating may be carried out as necessary.
たとえは、酢酸を用いる場合、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
拌することにより十分な効果か得られる。ａ処理を施さ
れたＰＰＳは残留しているａまたは塩などを物理的に除
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。For example, when using acetic acid, an aqueous solution with a pH of 4.
A sufficient effect can be obtained by immersing the PPS powder in a solution heated to 90°C and stirring for 30 minutes. The a-treated PPS needs to be washed several times with water or warm water in order to physically remove residual a or salt.
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、蒸留水、脱イオン水で
あることが好ましい。The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the preferable effect of chemical modification of PPS by acid treatment.
熱水処理を行う場合は次のとおりである。When performing hot water treatment, the procedure is as follows.
本発明において使用する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°
Ｃ以上、さらに好ましくは１５０°Ｃ以上、特に好まし
くは１７０℃以上とすることが重要であり、１００℃未
満ではＰＰＳの好ましい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 to 100°C or higher, preferably 120°C.
It is important to keep the temperature at least C, more preferably at least 150°C, particularly preferably at least 170°C. If it is less than 100°C, the effect of the preferred chemical modification of PPS will be small, so it is not preferred.
本発明の熱水洗浄によるＰＰＳの好ましい化学的変性の
効果を発現するため、使用する水は蒸留水あるいは脱イ
オン水であることが好ましい。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ぶに対し、
ＰＰ３２００ｇ以下の浴比が選択される。The water used is preferably distilled water or deionized water in order to achieve the desired effect of chemical modification of PPS by hot water washing according to the present invention. The hydrothermal treatment is usually performed by adding a predetermined amount of PPS to a predetermined amount of water, and heating and stirring the mixture in a pressure vessel. As for the ratio of PPS to water, the more water the better, but usually,
A bath ratio of 3200 g PP or less 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。さらに、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, PPS that has undergone this hot water treatment operation is
It is preferable to wash with warm water several times to physically remove any remaining components.
有機溶媒で洗浄する場合は次のとおりである。When washing with an organic solvent, the procedure is as follows.
７
本発明でＰＰＳの洗浄に用いる有機溶媒は、ＰＰＳを分
解する作用などを有しないものであれば特に制限はなく
、たとえばＮ−メチルピロリドン、ジメチルホルムアミ
ド、ジメチルアセトアミド、１，３−ジメチルイミダゾ
リジノン、ヘキサメチルホスホラスアミド、ピペラジノ
ン類などの含窒素極性溶媒、ジメチルスルホキシド、ジ
メチルスルホン、スルホランなどのスルホキシド・スル
ホン系溶媒、アセトン、メチルエチルゲトン、ジヱチル
ケトン、アセトフェノンなどのケトン系溶媒、ジメチル
エーテル、ジプロピルエーテル、ジオキサン、テトラヒ
ドロフランなどのエーテル系溶媒、クロロホルム、塩化
メチレン、トリクロロエチレン、２塩化エチレン、パー
クロルエチレン、モノクロルエタン、ジクロルエタン、
テトラクロルヱクン、パークロルエタン、クロルベンゼ
ンなどのハロゲン系溶媒、メタノール、エタノール、プ
ロパツール、ブタノール、ペンタノール、エチレングリ
コール、プロピレングリコール、フェノール、クレゾー
ル、ポリエチレングリコール、ポリプロピレングリコー
ルなどのアルコール・フェノール系溶媒およびベンゼン
、トルエン、キシレンなどの芳香族炭化水素系溶媒など
が挙げられる。これらの有機溶媒のうちでも、Ｎ−メチ
ルピロリドン、アセトン、ジメチルホルムアミドおよび
クロロホルムなどの使用が特に好ましい。7 The organic solvent used for cleaning 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 N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and 1,3-dimethylimidazolid nitrogen-containing polar solvents such as hexamethylphosphorusamide, piperazinone, sulfoxide/sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone, and sulfolane, ketone solvents such as acetone, methyl ethyl getone, diethyl ketone, and acetophenone, dimethyl ether, dimethyl Ether solvents such as propyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane,
Halogenated solvents such as tetrachloroethane, perchlorethane, and chlorobenzene; alcohols and phenols such as methanol, ethanol, propatool, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, and polypropylene glycol; Examples include solvents and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform, and the like is particularly preferred.
また、これらの有機溶媒は、１種類または２種類以上の
混合で使用される。Further, these organic solvents may be used alone or in combination of two or more.
有機溶媒による洗浄の方法としては、有機溶媒中にＰＰ
Ｓを浸漬せしめるなどの方法があり、必要により適宜撹
拌または加熱することも可能である。As a method of cleaning with an organic solvent, PP is added in an organic solvent.
There are methods such as immersing S, and it is also possible to stir or heat as necessary.
有機溶媒でＰＰＳを洗浄する際の洗浄温度については特
に制限はなく、常温〜３００℃程度の任意の温度が選択
できる。洗浄温度が高くなる程洗浄効率か高くなる傾向
があるが、通常は常温〜１５０℃の洗浄温度で十分効果
が得られる。There is no particular restriction on the washing temperature when washing PPS with an organic solvent, and any temperature from room temperature to about 300°C can be selected. Although there is a tendency for the cleaning efficiency to increase as the cleaning temperature increases, a sufficient effect can usually be obtained at a cleaning temperature of room temperature to 150°C.
圧力容器中で、有機溶媒の沸点以上の温度で加圧下に洗
浄することも可能である。また、洗浄時間についても特
に制限はない。洗浄条件にもよるが、バッチ式洗浄の場
合、通常５分間以上洗浄することにより、十分な効果が
得られる。It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. Furthermore, there is no particular restriction on the cleaning time. Although it depends on the cleaning conditions, in the case of batch cleaning, sufficient effects can usually be obtained by cleaning for 5 minutes or more.
また連続式で洗浄することも可能である。It is also possible to wash continuously.
重合により生成したｐＰＳを有機溶媒で洗浄するのみで
十分であるが０本発明の効果をさらに発揮させるために
、水洗浄または温水洗浄と組合わせるのが好ましい。ま
た、Ｎ−メチルピロリドンなどの高沸点水溶性有機溶媒
を用いた場合は、有機溶媒洗浄後、水または温水で洗浄
することにより、残存有機溶媒の除去が容易に行えて好
ましい。これらの洗浄に用いる水は蒸留水、脱イオン水
であることが好ましい。Although it is sufficient to simply wash the pPS produced by polymerization with an organic solvent, in order to further exhibit the effects of the present invention, it is preferable to combine washing with water or hot water. Further, when a high-boiling water-soluble organic solvent such as N-methylpyrrolidone is used, residual organic solvent can be easily removed by washing with water or warm water after washing with the organic solvent. The water used for these washings is preferably distilled water or deionized water.
本発明で用いられるＰＰＳの溶融粘度は、特に制限なく
、ポリオレフィン類との混練が可能であればいかなる溶
融粘度のものでも用いることができるが、通常は３２０
℃、剪断速度１０Ｓ ｅ （−１における溶融粘度が１
００〜１０．０００ボイズのものが用いられる。The melt viscosity of PPS used in the present invention is not particularly limited, and any melt viscosity can be used as long as it can be kneaded with polyolefins, but usually 320
°C, shear rate 10S e (melt viscosity at -1 is 1
00 to 10,000 voise is used.
本発明で用いるエポキシ基含有オレフィン系重合体とは
、側鎖または主鎖にエポキシ基を有するオレフィン系重
合体であり、通常のエポキシ樹脂は含まれない。エポキ
シ基含有オレフィン系重合体として、側鎖にグリシジル
エステル、グリシジルエーテル、グリシジルアミンなど
のグリシジル基を有するオレフィン系重合体や二重結合
含有オレフィン系重合体の二重結合をエポキシ酸化した
ものなどが挙げられる。本発明ではこれらエポキシ基含
有オレフィン系重合体のうち、α−オレフィンとα、β
−不飽和酸のグリシジルエステルからなる共重合体が好
ましく用いられる。ここでいうα−オレフィンとしては
エチレン、プロピレンおよびブテン−１などが挙げられ
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）で示され
る化合物であり、具体的にはアクリル １１−
１２−
酸グリシジル、メタクリル酸グリシジルおよびエタクリ
ル酸グリシジルなどが挙げられる。エポキシ基含有オレ
フィン系重合体におけるエポキシ基の含有量は０．１〜
３０重量％、特に０．２〜２０重量％が好ましく、０．
１重量％未満では目的とする効果が得られず、３０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、成形性および機械特性が低下するため好まし
くない。The epoxy group-containing olefin polymer used in the present invention is an olefin polymer having an epoxy group in a side chain or main chain, and does not include a normal epoxy resin. Epoxy group-containing olefin polymers include olefin polymers with glycidyl groups in their side chains, such as glycidyl esters, glycidyl ethers, and glycidyl amines, and double bond-containing olefin polymers whose double bonds are oxidized with epoxy. Can be mentioned. In the present invention, among these epoxy group-containing olefin polymers, α-olefin and α, β
- Copolymers consisting of glycidyl esters of unsaturated acids are preferably used. The α-olefins mentioned here include ethylene, propylene, butene-1, and the like. Glycidyl esters of α,β-unsaturated acids are compounds represented by the general formula (R represents a hydrogen atom or a lower alkyl group), and specifically include glycidyl acrylic 11-12-acrylates and glycidyl methacrylates. and glycidyl ethacrylate. The content of epoxy groups in the epoxy group-containing olefin polymer is from 0.1 to
30% by weight, especially 0.2 to 20% by weight, preferably 0.2% to 20% by weight.
If it is less than 1% by weight, the desired effect will not be obtained, and if it exceeds 30% by weight, gelation will occur during melt-kneading with PPS, resulting in deterioration of extrusion stability, moldability and mechanical properties, which is not preferable.
エポキシ基含有オレフィン系重合体には、本発明の効果
を損なわない範囲で、他のオレフィン系モノマ、たとえ
ばアクリル酸メチル、メタクリル酸メチル、アクリロニ
トリル、スチレン、酢酸ビニルおよびビニルエーテルな
どを共重合せしめてもよい。The epoxy group-containing olefin polymer may be copolymerized with other olefin monomers, such as methyl acrylate, methyl methacrylate, acrylonitrile, styrene, vinyl acetate, and vinyl ether, as long as the effects of the present invention are not impaired. good.
本発明で第３成分として用いられるエラストマの例とし
ては、たとえば、ポリオレフィン系エラストマ、ジエン
系エラストマ、アクリル系エラストマ、ポリアミドエラ
ストマ、ポリエステルエラストマ、シリコーンエラスト
マ、フッ素エラストマおよび多硫化物エラストマなどが
挙げられる。ポリオレフィン系エラストマの具体例とし
ては、エチレン−プロピレン共重合体、エチレン−ブテ
ン共重合体、ポリブテン、エチレン−プロピレン−ジエ
ン共重合体およびエチレン−酢酸ビニル共重合体などが
挙げられる。Examples of the elastomer used as the third component in the present invention include polyolefin elastomer, diene elastomer, acrylic elastomer, polyamide elastomer, polyester elastomer, silicone elastomer, fluorine elastomer, and polysulfide elastomer. Specific examples of polyolefin elastomers include ethylene-propylene copolymers, ethylene-butene copolymers, polybutenes, ethylene-propylene-diene copolymers, and ethylene-vinyl acetate copolymers.
ジエン系エラストマとしてはスチレン−ブタジェン共重
合体、ポリブタジェン、ブタジェンアクリロニトリル共
重合体、ポリイソプレン、ブテン−イソプレン共重合体
、スチレン−ブタジェン−スチレン共重合体およびこれ
らの水添物などが挙げられる。Examples of the diene elastomer include styrene-butadiene copolymer, polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, styrene-butadiene-styrene copolymer, and hydrogenated products thereof.
アクリル系エラストマの具体例として、エチレン−（メ
タ〉アクリル酸メチル共重合体、エチレン−（メタ）ア
クリル酸エチル共重合体、エチレン−くメタ）アクリル
酸プロピル共重合体、エチレン−（メタ〉アクリル酸ブ
チル共重合体などのオレフィン−アクリル酸エステル共
重合体、（メタ）アクリル酸メチル−アクリロニトリル
共重合体、（メタ）アクリル酸プロピルーアクリロニト
リル共重合体、（メタ）アクリル酸ブチル−アクリロニ
トリル共重合体などの（メタ）アクリル酸ヱステルーア
クリロニトリル共重合体、エチレン−（メタ）アクリル
酸共重合体およびそれのＮａ、Ｚｎ、に、Ｃａ、Ｍｇな
どの金属塩、上述のブタジェン−アクリロニトリル共重
合体などが挙げられる。Specific examples of acrylic elastomers include ethylene-(meth)acrylic acid methyl copolymer, ethylene-(meth)ethyl acrylate copolymer, ethylene-(meth)acrylic acid propyl copolymer, and ethylene-(meth)acrylic acid copolymer. Olefin-acrylic acid ester copolymers such as butyl acid copolymers, methyl (meth)acrylate-acrylonitrile copolymers, propyl (meth)acrylate-acrylonitrile copolymers, butyl (meth)acrylate-acrylonitrile copolymers (meth)acrylic acid ester-acrylonitrile copolymer, ethylene-(meth)acrylic acid copolymer and its metal salts such as Na, Zn, Ca, Mg, etc., the above-mentioned butadiene-acrylonitrile copolymer Examples include merging.
ポリアミド系エラストマとは、ポリアミド成分のハード
セグメントとポリエーテル成分および／またはポリエス
テル成分のソフトセグメントを有するブロック共重合体
のエラストマである。ポリアミド成分の例としては
＋ＮＨ−ＲＩ−Ｃｏ−）−ｎまたは
−（−ＮＨ−Ｒ’−ＮＨＣＯ−Ｒ”−ＣＯ）ｎ （ここ
でＲＩ 、 Ｒ１およびＲ１は炭素数２〜１５のアルキ
レン基またはその置換体を示す〉が挙げられる。ポリエ
ーテル成分の例としては一＋０Ｒ１−ｎ （Ｒは炭素数
２〜１５のアルキレン基またはその置換体を示す〉か挙
げられ、ポリエステル成分の例としては＋ＯＲＩ−Ｃｏ
）ｎまたは＋Ｏ−Ｒ’−０ＣＯ−Ｒ”−〇〇−）−ｎ（
ここでＲＩ、Ｒ１およびＲ１は炭素数２〜１５のアルキ
レン基またはその置換体を示す）が挙げられる。またポ
リアミド系エラストマとしてはナイロン６、ナイロン６
６、ナイロン６１０、ナイロン１１およびナイロン１２
のランダム共重合体も含まれる。A polyamide elastomer is a block copolymer elastomer having a hard segment of a polyamide component and a soft segment of a polyether component and/or a polyester component. Examples of polyamide components include +NH-RI-Co-)-n or -(-NH-R'-NHCO-R''-CO)n (where RI, R1 and R1 are alkylene groups having 2 to 15 carbon atoms or Examples of polyether components include 1+0R1-n (R represents an alkylene group having 2 to 15 carbon atoms or a substituted product thereof), and examples of polyester components include +ORI -Co
)n or +O-R'-0CO-R”-〇〇-)-n(
Here, RI, R1 and R1 each represent an alkylene group having 2 to 15 carbon atoms or a substituted product thereof. In addition, polyamide elastomers include nylon 6 and nylon 6.
6, nylon 610, nylon 11 and nylon 12
Also included are random copolymers of
シリコーンエラストマは＋５Ｌ−０）ｎで表わされるポ
リシロキサンであり、Ｒとしてはメチル基の他、エチル
基、プロピル基、フェニル基、ビニル基、フッ素アルキ
ル基および＋ＣＨ２−）−ｍＣＮ基などが挙げられる。Silicone elastomer is a polysiloxane represented by +5L-0)n, and R includes, in addition to methyl, ethyl, propyl, phenyl, vinyl, fluoroalkyl, and +CH2-)-mCN groups. .
フッ素系エラストマとしてはたとえは、フッ化ビニリデ
ン−パーフルオロプロパン共重合体、フッ化ビニリデン
−三フッ化塩化エチレン共重合体、四フッ化エチレンー
プロピレン共重合体および四フッ化エチレンーＣ２Ｆ３
０ＣＦ３共重合体などの他、ジヒドロパーフルオロブチ
ルアクリ １５−
６
レート重合体、トリフルオロメトキシジヒドロパーフル
オロアクリレート共重合体などの含フＨ３
ッ素アクリレート重合体、＋５ｉ−０）ｎなどＣ２Ｈ４
ＣＦ３
のフルオロシリコーン系エラストマおよび０−ＣＨ２Ｃ
３Ｆ６Ｈ
系エラストマなどが挙げられる。Examples of fluorine-based elastomers include vinylidene fluoride-perfluoropropane copolymer, vinylidene fluoride-trifluorochloroethylene copolymer, tetrafluoroethylene-propylene copolymer, and tetrafluoroethylene-C2F3.
In addition to 0CF3 copolymers, fluorinated H3-containing acrylate polymers such as dihydroperfluorobutylacrylate polymers, trifluoromethoxydihydroperfluoroacrylate copolymers, and C2H4 such as +5i-0)n.
CF3 fluorosilicone elastomer and 0-CH2C
Examples include 3F6H elastomer.
多硫化物エラストマとは、式−＋ Ｒ−８ｍ ） ｎで
表わされるポリマであり、Ｒの例としてはＣＨ２−１−
Ｃ２Ｈ４−−−Ｃ３Ｈｅ
Ｃ４Ｈ６−−ＣａＨ＋ｚ−−ＣＩＯＨ２［１−Ｃ２Ｈ４
０Ｃ２Ｈ４−
−Ｃ２Ｈ４０ＣＨ２０Ｃ２Ｈ４−
−Ｃ２Ｈ４０Ｃ２Ｈ４０Ｃ２Ｈ４−
ＣＨ２ＣＨＣＨ２−、−ＣＨ２Ｃ３ＦＨ２ＯＨＯＲ′
＜Ｒ′は炭素数１〜４のアルキル基）およびｍは１〜４
である。A polysulfide elastomer is a polymer represented by the formula -+R-8m)n, where R is, for example, CH2-1-
C2H4--C3He C4H6--CaH+z--CIOH2[1-C2H4
0C2H4- -C2H40CH20C2H4- -C2H40C2H40C2H4- CH2CHCH2-, -CH2C3FH2OHOR'<R' is an alkyl group having 1 to 4 carbon atoms) and m is 1 to 4
It is.
これらのエラストマは１種または２種以上の混合物で使
用される。These elastomers may be used alone or in a mixture of two or more.
本発明で用いる樹脂組成物におけるＰＰＳの配合割合は
６０〜９８重量％、好ましくは６５〜９５重合％の範囲
内である。配合割合が６０重量％に満たないと、成形し
た中空成形品の耐熱性、耐薬品性か不足するため好まし
くなく、−左記合量が９８重量％を越えると、中空成形
品の成形性、耐衝撃性が不足するため好ましくない。第
２成分のエポキシ基含有オレフィン系共重合体の配合割
合は２〜４０重量％、好ましくは５〜３０重量％の範囲
内である。また第３成分のエラストマの配合割合は１〜
３５重量％である。エラストマの添加は特に表面外観の
向上に有効であるが、配合量が３５重量％を越えると中
空成形品の耐熱性が損なわれるため好ましくない。The blending ratio of PPS in the resin composition used in the present invention is in the range of 60 to 98% by weight, preferably 65 to 95% by weight. If the blending ratio is less than 60% by weight, the heat resistance and chemical resistance of the hollow molded product will be insufficient, which is undesirable. If the combined amount exceeds 98% by weight, the moldability and resistance of the blow molded product will deteriorate. Unfavorable because of lack of impact resistance. The blending ratio of the epoxy group-containing olefin copolymer as the second component is in the range of 2 to 40% by weight, preferably 5 to 30% by weight. In addition, the blending ratio of the third component, elastomer, is 1 to 1.
It is 35% by weight. Addition of an elastomer is particularly effective in improving the surface appearance, but if the amount exceeds 35% by weight, it is not preferred because the heat resistance of the blow molded product will be impaired.
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とエポキシ基
含有オレフィン系共重合体およびエラストマの合計１０
０重量部に対して２００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１０〜１５０重量部の範囲で
配合することにより強度、剛性、耐熱性、寸法安定性な
ど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 if necessary, the total amount of PPS, epoxy group-containing olefin copolymer, and elastomer
It is possible to blend in an amount not exceeding 200 parts by weight to 0 parts by weight, and it is usually blended in a range of 10 to 150 parts by weight to improve strength, rigidity, heat resistance, dimensional stability, etc. Is possible.
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、セラミック繊維
、アスベスト繊維、石コウ繊維、金属繊維および炭素繊
維などが挙げられる。Examples of such fibrous reinforcing agents include glass fibers, glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers, and carbon fibers.
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、炭酸カルシウム、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、炭化珪素およびシリカなどが挙げられ、これら
は中空であってもよい。Granular reinforcing agents include wollastenite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, and metal oxides such as alumina, silicon chloride, magnesium oxide, zirconium oxide, and titanium oxide. carbonates such as calcium carbonate, magnesium carbonate, dolomite, sulfates such as calcium sulfate, barium sulfate, glass beads, boron nitride, silicon carbide, and silica, which may be hollow.
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ップリング
剤で予備処理して使用することができる。These reinforcing agents can be used in combination of two or more,
If necessary, it can be used after being pretreated with a silane-based or titanium-based coupling agent.
また本発明で用いるＰＰＳとエポキシ基含有オレフィン
系共重合体およびエラストマからなる樹脂組成物には、
本発明の効果を損わない範囲で、酸化防止剤、熱安定剤
、滑剤、結晶核剤、紫外線防止剤、着色剤、難燃剤など
の通常の添加剤および少量の他種ポリマを添加すること
ができ、さらに、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ィン酸金属塩などの架橋促進
剤または特開昭５８−１９−
２０−
２０４０４５号公報、特開昭５８−２０４０４６号公報
など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などの架橋防止剤を配合すること
も可能である。In addition, the resin composition comprising PPS, an epoxy group-containing olefin copolymer, and an elastomer used in the present invention includes:
Conventional additives such as antioxidants, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet inhibitors, colorants, flame retardants, and small amounts of other polymers may be added to the extent that the effects of the present invention are not impaired. Furthermore, for the purpose of controlling the degree of crosslinking of PPS, ordinary peroxidants and crosslinking accelerators such as thiophosphinic acid metal salts described in JP-A-59-131650 or JP-A-58-1989 can be used. It is also possible to incorporate crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole described in JP-A No. 19-20-204045 and JP-A-58-204046.
本発明で用いる樹脂組成物の調製方法は特に制限はなく
、ＰＰＳ、エポキシ基含有オレフィン系共重合体、エラ
ストマの粉末、ペレット細片および必要に応じて強化剤
をリボンブレンダー、ヘンシェルミキサー、■ブレンダ
ーなどを用いてトライブレンドした後、バンバリーミキ
サ−、ミキシングロール、単軸または２軸の押出機およ
びニーダ−などを用いて溶融混練する方法などが挙げら
れる。なかでも十分な混練力を有する単軸または２軸の
押出機を用いて溶融混練する方法が代表的である。The method for preparing the resin composition used in the present invention is not particularly limited, and PPS, epoxy group-containing olefin copolymer, elastomer powder, pellet pieces, and optionally a reinforcing agent are mixed in a ribbon blender, a Henschel mixer, or a blender. Examples include a method in which the mixture is tri-blended using a Banbury mixer, mixing roll, single-screw or twin-screw extruder, kneader, etc. Among these, a method of melt-kneading using a single-screw or twin-screw extruder having sufficient kneading power is typical.
本発明のブロー中空成形品は、上記のようにして得られ
た樹脂組成物を通常公知のブロー成形法、すなわち基本
的には樹脂組成物を押出機に供給し、溶融押出しをして
パリソンを形成せしめ、その後目的とする２〜３次元的
中空成形体とすることによって得られる。通常公知のブ
ロー成形法の代表例としてはダイレクトブロー法、アキ
ュームレーターブロー法および多次元ブロー法などを挙
げることができ、また他材料との組合せにおいて用いら
れる多層ブロー成形法、エクスチェンジブロー成形法な
どを適用することも勿論可能である。The blow-hollow molded product of the present invention can be produced by using the normally known blow molding method using the resin composition obtained as described above, that is, basically, the resin composition is fed to an extruder and melt-extruded to form a parison. It is obtained by forming the desired two- to three-dimensional hollow molded body. Typical examples of commonly known blow molding methods include direct blow molding, accumulator blow molding, and multidimensional blow molding, as well as multilayer blow molding and exchange blow molding, which are used in combination with other materials. Of course, it is also possible to apply.
このようにして成形された本発明のブロー中空成形品の
具体例としては、ボトル、タンクおよびダクトなどが挙
げられ、これらは耐熱性、耐薬品性および耐衝撃性にす
ぐれた中空成形品として、薬液用容器、空調ダクト類、
自動車エンジンルーム内のダクトおよびパイプなどに有
用である。Specific examples of blow molded products of the present invention formed in this way include bottles, tanks, ducts, etc., and these are blow molded products with excellent heat resistance, chemical resistance, and impact resistance. Containers for chemical solutions, air conditioning ducts,
Useful for ducts and pipes in automobile engine compartments.
〈実施例〉 以下に実施例を挙げて本発明をさらに詳しく説明する。<Example> The present invention will be explained in more detail with reference to Examples below.
なお実施例および比較例に記された諸特性は下記の方法
で測定した。Note that the various properties described in the Examples and Comparative Examples were measured by the following methods.
（１）成形性：樹脂組成物ベレットを５０ｍｍφ押出機
を具備するブロー成形機
に供給し、シリンター温度３２
０℃で押出しを行い、外径１０
０＋ｎｍ、肉厚４ｒａｍのパリソンを形成した後金型内
で空気を吹き込
み、１辺１５０ｍｍ、高さ５００
關の正四角柱型容器を成形した。(1) Moldability: The resin composition pellet is supplied to a blow molding machine equipped with a 50 mmφ extruder, and extrusion is performed at a cylinder temperature of 320°C to form a parison with an outer diameter of 100+ nm and a wall thickness of 4 rams, and then molded. Air was blown into the container to form a square prism-shaped container with sides of 150 mm and height of 500 mm.
この成形品胴部の上部および下 部各５カ所の厚みを測定し、上 部平均厚みと下部平均厚みの差 が１面以内のものを成形性良好、 厚みの差が１面を越えるものを 不良と判定した。The top and bottom of this molded body Measure the thickness at 5 places on each part, and Difference between average thickness of part and average thickness of bottom part Good moldability for those with less than one surface. Items with a difference in thickness of more than one side It was determined to be defective.
（２）耐熱性二上記容器胴部に２．５ ｋｇの荷重をか
けて所定の温度で１時間処理
した際に、変形量が２ｍｍ以内と
なる最高温度を測定し、耐熱性
の目安とした。(2) Heat resistance 2 When a load of 2.5 kg was applied to the body of the above container and the container was treated at a specified temperature for 1 hour, the highest temperature at which the amount of deformation was within 2 mm was measured, and this was used as a guideline for heat resistance. .
（３）耐衝撃性二上記容器を１ｍの高さからコンクリー
ト床上に落下せしめ、容
器の破損、クラックの有無を目
視判定した。ｎ＝２０で試験を
行い、破壊しなかったものの個
数を数え、非破壊率として１０
０分率で表示し、耐衝撃性の目
安とした。(3) Impact resistance 2 The above container was dropped from a height of 1 m onto a concrete floor, and the presence or absence of damage and cracks in the container was visually determined. The test was conducted with n=20, and the number of samples that did not break was counted, and the non-destructive rate was expressed as a percentage of 100, which was used as a measure of impact resistance.
参考例１ （ＰＰＳの重合）
オートクレーブに硫化ナトリウム３．２６ ｋｇ（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） ７．９ ｋｇを仕込み、撹拌しながら徐々に２
０５℃まで昇温し、水１．３６ｂｇを含む留出水約１．
５ｊ！を除去した。Reference Example 1 (Polymerization of PPS) 3.26 kg (25 kg) of sodium sulfide was placed in an autoclave.
mol, containing 40% water of crystallization), 4 g of sodium hydroxide,
Sodium acetate trihydrate 1.36 kg (approximately 10 moles)
and 7.9 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), and gradually added 2
Distilled water containing about 1.36 bg of water was heated to 0.05°C.
5j! was removed.
残留混合物に１，４−ジクロルベンゼン３．７５ ｋｇ
（２５，５モル）およびＮＭＰ２ｋｇ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°Ｃで２４時間減圧乾燥して、溶融粘度約
２５００ポアズ（３２０℃、剪断速度１０秒−１）の粉
末状ＰＰＳ （Ｐ’−１）約２ｋｇを得た。3.75 kg of 1,4-dichlorobenzene in the residual mixture
(25,5 mol) and 2 kg of NMP, 265°
The mixture was heated at 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 powdered PPS (P'-1) with a melt viscosity of about 2500 poise (320°C, shear rate 10 s-1). ) Approximately 2 kg was obtained.
３− ＝ ２４ 同様の操作を繰返し、以下に記載の実施例に供した。3- = 24 The same operation was repeated and used in the examples described below.
参考例２ （ＰＰＳの酸処理）
参考例１で得られたＰＰＳ粉末約２ｂｇを、９０℃に加
熱されたｐＨ４の酢酸水溶液２０４２中に投入し、約３
０分間撹拌し続けたのち濾過し、炉液の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、酸処理ＰＰＳ （Ｐ−２）
を得た。Reference Example 2 (Acid treatment of PPS) Approximately 2 bg of the PPS powder obtained in Reference Example 1 was put into an acetic acid aqueous solution 2042 with a pH of 4 heated to 90°C.
After continuing to stir for 0 minutes, it was filtered, washed with deionized water at about 90°C until the pH of the furnace solution reached 7, dried under reduced pressure at 120°C for 24 hours to form a powder, and acid-treated PPS (P-2 )
I got it.
参考例３ （ＰＰＳの熱水処理）
参考例１で得られたＰＰＳ粉末約２ｂｇと脱イオン水１
０℃とをオートクレーブに仕込み、常圧で密閉したのち
、１７５°Ｃまで昇温し、撹拌しながら約３０分間保温
したのち冷却した。内容物を取出し濾過し、さらに、７
０℃の脱イオン水約１０１の中にＰＰＳを浸漬、撹拌し
、濾過する操作を５回繰返した。その後１２０℃で２４
時間減圧乾燥して熱水洗浄ＰＰＳ （Ｐ’−３）を得た
。Reference Example 3 (Hot water treatment of PPS) Approximately 2 bg of PPS powder obtained in Reference Example 1 and 1 gram of deionized water
0°C was placed in an autoclave, the autoclave was sealed at normal pressure, the temperature was raised to 175°C, the temperature was kept for about 30 minutes with stirring, and then the autoclave was cooled. Remove the contents, filter, and add 7
The procedure of immersing PPS in about 10 ml of deionized water at 0°C, stirring, and filtering was repeated five times. Then at 120℃ for 24
The product was dried under reduced pressure for hours to obtain hot water-washed PPS (P'-3).
参考例４ （ＰＰＳの溶媒洗浄〉
参考例１で得られた粉末的２ｋｇを１００℃に加熱した
ＮＭＰ２０ｉ中に投入し、約３０分間撹拌した後、濾過
し、続いて約９０℃のイオン交換水で洗浄した。このも
のを１２０℃で２４時間減圧乾燥してＮＭＰ洗浄ＰＰＳ
（Ｐ−４＞を得た。Reference Example 4 (Solvent washing of PPS) 2 kg of the powder obtained in Reference Example 1 was poured into NMP20i heated to 100°C, stirred for about 30 minutes, filtered, and then washed with ion-exchanged water at about 90°C. This product was dried under reduced pressure at 120°C for 24 hours and washed with NMP-washed PPS.
(P-4> was obtained.
実施例１
参考例２で得られたＰＰＳ （Ｐ−２）６５重量％、エ
チレン／グリシジルメタクリレート共重合体（８８／１
２重量比）１０重量％、三井石油化学■製エチレン／プ
ロピレンゴム（゛′タフマ”ＰＯ６８０）１０重量％お
よびガラス繊維１５重量％をヘンシェルミキサーでトラ
イブレンドした後、６５開φ単軸押出機のホッパーに投
入し、シリンダー温度３２０℃、スクリエー回転数４０
ｒＤＴｎの条件で溶融混練を行いベレット化した。この
ペレットを１３０’Ｃで３時間熱風乾燥した後、前記の
ブロー成形機を用いて１辺１５０叩、高さ５００■の正
四角柱型容器を成形した。この結果、パリソンのドロー
ダウンも小さく、表面外観良好な中空成形品が得られた
。この中空成形品の物性は第１表に示すとおりであり、
成形品中の肉厚の偏りもなく、耐熱性および耐衝撃性も
良好な極めて実用価値の高い成形品であることが判明し
た。Example 1 65% by weight of PPS (P-2) obtained in Reference Example 2, ethylene/glycidyl methacrylate copolymer (88/1
After tri-blending 10% by weight of ethylene/propylene rubber ('Tafuma' PO680) manufactured by Mitsui Petrochemicals and 15% by weight of glass fiber in a Henschel mixer, Pour into hopper, cylinder temperature 320℃, Scrier rotation speed 40
Melt kneading was performed under rDTn conditions to form pellets. The pellets were dried with hot air at 130'C for 3 hours, and then molded into a square prism-shaped container with a side of 150 strokes and a height of 500 cm using the blow molding machine described above. As a result, a hollow molded product with a small parison drawdown and a good surface appearance was obtained. The physical properties of this blow molded product are shown in Table 1.
It was found that the molded product has no uneven wall thickness, has good heat resistance and impact resistance, and has extremely high practical value.
比較例１
エチレン／グリシジルメタクリレート共重合体およびエ
チレン／プロピレンゴムを使用せず、ＰＰＳ （Ｐ−２
＞８５重量％、ガラス繊維１５重量％の組成とした以外
は実施例１と同様の手順で溶融混線を行い、得られたベ
レットを乾燥後ブロー成形機に供して成形を試みたが、
このものはパリソンのドローダウンが大きく、均一な肉
厚の成形品を得ることができなかった。また、成形品の
耐熱性および耐衝撃性も劣るものであった。Comparative Example 1 PPS (P-2
>85% by weight and glass fiber 15% by weight, melt mixing was performed in the same manner as in Example 1, and the resulting pellet was dried and then subjected to a blow molding machine to attempt molding.
This product had a large parison drawdown, making it impossible to obtain a molded product with uniform wall thickness. Furthermore, the heat resistance and impact resistance of the molded product were also poor.
実施例２
参考例３で得られたＰＰＳ （Ｐ−３）６０重量％、実
施例１で用いたエチレン／グリシジルメタクリレート共
重合体１０１ｉ量％およびエチレン／ブテン−１共重合
体（三井石油化学■製“タフマ″Ａ４０８５）１０重量
％およびガラス繊維２０重量％を実施例１と同様の手順
で溶融混練、ブロー成形を行った。ここでもパリソンの
ドローダウンは小さく、表面外観良好なブロー中空成形
品が得られ、しかもこのものの物性は第１表に示すとお
り、均一性、耐熱性、耐衝撃性いずれも良好であった。Example 2 60% by weight of PPS (P-3) obtained in Reference Example 3, 101i% by weight of the ethylene/glycidyl methacrylate copolymer used in Example 1, and ethylene/butene-1 copolymer (Mitsui Petrochemical ■ In the same manner as in Example 1, 10% by weight of Tafuma A4085) and 20% by weight of glass fibers were melt-kneaded and blow-molded. Again, the drawdown of the parison was small and a blown hollow molded product with good surface appearance was obtained, and as shown in Table 1, the physical properties of this product were good in terms of uniformity, heat resistance, and impact resistance.
比較例２
参考例１で得られたＰＰＳ （Ｐ−１）をＰ２の代わり
に使用した以外は実施例１と全く同様に溶融混練、ブロ
ー成形を実施したが、このものは、表面外観の悪い成形
品しか得ることができず、しかもその耐衝撃性は第１表
に示すとおり著しく劣ったものであり、実用に耐えるも
のではなかった。Comparative Example 2 Melt-kneading and blow molding were carried out in exactly the same manner as in Example 1 except that PPS (P-1) obtained in Reference Example 1 was used instead of P2, but this product had a poor surface appearance. Only molded products could be obtained, and the impact resistance thereof was extremely poor as shown in Table 1, and was not suitable for practical use.
実施例３〜９
ＰＰＳ樹脂、エポキシ基含有オレフィン系重合体、エラ
ストマおよび充填材の種類と配合量を第１表に示したよ
うに変更し、実施例１と同 ２７−
２８−
様の手順で溶融混練、次いでブロー成形を実施した。い
ずれの場合も表面外観良好な中空成形品が得られた。こ
れらの諸物性は第１表に示すとおりであり、成形品の均
一性、耐熱性および耐衝撃性ともにすぐれたものであっ
た。Examples 3 to 9 The same procedure as in Example 1 was followed except that the types and amounts of the PPS resin, epoxy group-containing olefin polymer, elastomer, and filler were changed as shown in Table 1. Melt kneading and then blow molding were performed. In all cases, hollow molded products with good surface appearance were obtained. These physical properties are shown in Table 1, and the molded product was excellent in uniformity, heat resistance, and impact resistance.
〈発明の効果〉
本発明のブロー中空成形品は、すぐれたブロー成形性、
耐衝撃性および耐熱性を有しており、耐薬品性タンク、
ボトルおよび自動車のダクト類などの用途に対し有益に
使用することができる。<Effects of the Invention> The blow hollow molded product of the present invention has excellent blow moldability,
Has impact resistance and heat resistance, chemical resistant tank,
It can be advantageously used for applications such as bottles and automotive ductwork.
Claims (4)
樹脂９８〜６０重量％、エポキシ基含有オレフィン系共
重合体２〜４０重量％および前記オレフィン系共重合体
以外のエラストマ１〜３５重量％からなる樹脂成分１０
０重量部に対し、無機充填材０〜２００重量部を添加し
てなるポリフェニレンスルフィド樹脂組成物を主たる構
成成分とすることを特徴とするブロー中空成形品。(1) A resin component consisting of 98-60% by weight of a deionized polyphenylene sulfide resin, 2-40% by weight of an epoxy group-containing olefin copolymer, and 1-35% by weight of an elastomer other than the olefin copolymer. 10
A blow hollow molded article characterized in that the main component thereof is a polyphenylene sulfide resin composition in which 0 to 200 parts by weight of an inorganic filler is added to 0 parts by weight.
することからなる請求項（１）記載のブロー中空成形品
。(2) The blow hollow molded article according to claim (1), wherein the deionization treatment comprises treatment with an acid aqueous solution and then washing with water.
ことからなる請求項（１）記載のブロー中空成形品。(3) The blow hollow molded article according to claim (1), wherein the deionization treatment comprises treatment with hot water and then washing with water.
することからなる請求項（１）記載のブロー中空成形品
。(4) The blow hollow molded product according to claim (1), wherein the deionization treatment comprises washing with an organic solvent and then washing with water.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3314890A JP2932567B2 (en) | 1990-02-13 | 1990-02-13 | Blow blow molding |
| US08/410,938 US5625002A (en) | 1988-06-02 | 1995-03-27 | Polyphenylene sulfide composition and shaped articles made therefrom |
| US08/475,793 US5654358A (en) | 1988-06-02 | 1995-06-07 | Polyphenylene sulfide composition and shaped articles made therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3314890A JP2932567B2 (en) | 1990-02-13 | 1990-02-13 | Blow blow molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03236931A true JPH03236931A (en) | 1991-10-22 |
| JP2932567B2 JP2932567B2 (en) | 1999-08-09 |
Family
ID=12378498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3314890A Expired - Fee Related JP2932567B2 (en) | 1988-06-02 | 1990-02-13 | Blow blow molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2932567B2 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0697442A1 (en) | 1994-08-09 | 1996-02-21 | General Electric Company | Epoxy modified blends of poly(arylenesulfide) and polyetherimide resins |
| JP2001247767A (en) * | 2000-03-07 | 2001-09-11 | Toray Ind Inc | Resin composition |
| JP2004339478A (en) * | 2003-04-25 | 2004-12-02 | Toyoda Gosei Co Ltd | Resin molded product, especially fuel tank |
| JP2006012649A (en) * | 2004-06-28 | 2006-01-12 | Toray Ind Inc | Resin coated wire |
| JP2008111063A (en) * | 2006-10-31 | 2008-05-15 | Toray Ind Inc | Extruded hollow molded article and method for producing the same |
| JP2010006858A (en) * | 2008-06-24 | 2010-01-14 | Toray Ind Inc | Polyphenylene sulfide resin composition |
| JP2011132336A (en) * | 2009-12-24 | 2011-07-07 | Toray Ind Inc | Fuel tank |
| WO2013049098A1 (en) | 2011-09-27 | 2013-04-04 | Sabic Innovative Plastics Ip B.V. | Blends of polysiloxane/polyimide block copolymer and poly(arylene sulfide) |
| WO2013049100A1 (en) | 2011-09-27 | 2013-04-04 | Sabic Innovative Plastics Ip B.V. | Blends of polyetherimide sulfone and poly(arylene sulfide) |
| WO2013049099A1 (en) | 2011-09-27 | 2013-04-04 | Sabic Innovative Plastics Ip B.V. | Blends of polyetherimide sulfone and poly(arylene sulfide) and methods of making |
| WO2013148943A2 (en) | 2012-03-30 | 2013-10-03 | Sabic Innovative Plastics Ip B.V. | Compressors including polymeric components |
| EP2578637A4 (en) * | 2010-05-26 | 2015-09-23 | Dainippon Ink & Chemicals | Resin composition for blow-molded hollow article, blow-molded hollow article, and production processes |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6645623B2 (en) | 2000-07-20 | 2003-11-11 | E. I. Du Pont De Nemours And Company | Polyphenylene sulfide alloy coated wire |
-
1990
- 1990-02-13 JP JP3314890A patent/JP2932567B2/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0697442A1 (en) | 1994-08-09 | 1996-02-21 | General Electric Company | Epoxy modified blends of poly(arylenesulfide) and polyetherimide resins |
| JP2001247767A (en) * | 2000-03-07 | 2001-09-11 | Toray Ind Inc | Resin composition |
| JP2004339478A (en) * | 2003-04-25 | 2004-12-02 | Toyoda Gosei Co Ltd | Resin molded product, especially fuel tank |
| JP4596787B2 (en) * | 2003-04-25 | 2010-12-15 | 豊田合成株式会社 | Fuel tank |
| JP2006012649A (en) * | 2004-06-28 | 2006-01-12 | Toray Ind Inc | Resin coated wire |
| JP2008111063A (en) * | 2006-10-31 | 2008-05-15 | Toray Ind Inc | Extruded hollow molded article and method for producing the same |
| JP2010006858A (en) * | 2008-06-24 | 2010-01-14 | Toray Ind Inc | Polyphenylene sulfide resin composition |
| JP2011132336A (en) * | 2009-12-24 | 2011-07-07 | Toray Ind Inc | Fuel tank |
| EP2578637A4 (en) * | 2010-05-26 | 2015-09-23 | Dainippon Ink & Chemicals | Resin composition for blow-molded hollow article, blow-molded hollow article, and production processes |
| WO2013049098A1 (en) | 2011-09-27 | 2013-04-04 | Sabic Innovative Plastics Ip B.V. | Blends of polysiloxane/polyimide block copolymer and poly(arylene sulfide) |
| WO2013049099A1 (en) | 2011-09-27 | 2013-04-04 | Sabic Innovative Plastics Ip B.V. | Blends of polyetherimide sulfone and poly(arylene sulfide) and methods of making |
| US8618218B2 (en) | 2011-09-27 | 2013-12-31 | Sabic Innovative Plastics Ip B.V. | Blends of polysiloxane/polyimide block copolymer and poly(arylene sulfide) |
| WO2013049100A1 (en) | 2011-09-27 | 2013-04-04 | Sabic Innovative Plastics Ip B.V. | Blends of polyetherimide sulfone and poly(arylene sulfide) |
| US9909006B2 (en) | 2011-09-27 | 2018-03-06 | Sabic Global Technologies B.V. | Blends of polyetherimide sulfone and poly(arylene sulfide) |
| WO2013148943A2 (en) | 2012-03-30 | 2013-10-03 | Sabic Innovative Plastics Ip B.V. | Compressors including polymeric components |
| EP3255279A1 (en) | 2012-03-30 | 2017-12-13 | SABIC Global Technologies B.V. | Compressors including polymeric components |
| WO2021059218A2 (en) | 2019-09-27 | 2021-04-01 | Shpp Global Technologies B.V. | Semi-crystalline polymer-ceramic core-shell particle powders, and processes for making and articles comprising such powders |
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