JPS63128059A - Production of polyester resin composition - Google Patents
Production of polyester resin compositionInfo
- Publication number
- JPS63128059A JPS63128059A JP27415486A JP27415486A JPS63128059A JP S63128059 A JPS63128059 A JP S63128059A JP 27415486 A JP27415486 A JP 27415486A JP 27415486 A JP27415486 A JP 27415486A JP S63128059 A JPS63128059 A JP S63128059A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- weight
- copolymer
- acid
- parts
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 229920001225 polyester resin Polymers 0.000 title claims description 15
- 239000004645 polyester resin Substances 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920000098 polyolefin Polymers 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 238000004898 kneading Methods 0.000 claims abstract description 6
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 abstract description 26
- -1 polyethylene terephthalate Polymers 0.000 abstract description 23
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 12
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 12
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 abstract description 9
- 229920000728 polyester Polymers 0.000 abstract description 8
- 239000004014 plasticizer Substances 0.000 abstract description 7
- 239000002667 nucleating agent Substances 0.000 abstract description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 5
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 abstract description 4
- 159000000000 sodium salts Chemical class 0.000 abstract description 4
- 229920001169 thermoplastic Polymers 0.000 abstract description 3
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 15
- 239000000178 monomer Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 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
- DYJIIMFHSZKBDY-UHFFFAOYSA-N (3-benzoyloxy-2,2-dimethylpropyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(C)(C)COC(=O)C1=CC=CC=C1 DYJIIMFHSZKBDY-UHFFFAOYSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-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
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- LUVOGSNMSPGNFR-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)pent-2-enoic acid Chemical compound CCC=C(C(O)=O)C(=O)OCC1CO1 LUVOGSNMSPGNFR-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- NMSZFQAFWHFSPE-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxycarbonyl)but-3-enoic acid Chemical compound OC(=O)CC(=C)C(=O)OCC1CO1 NMSZFQAFWHFSPE-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-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
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JJUSZGHCZMBOEQ-UHFFFAOYSA-N [2-(benzoyloxymethyl)-3-hydroxy-2-(hydroxymethyl)propyl] benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(CO)(CO)COC(=O)C1=CC=CC=C1 JJUSZGHCZMBOEQ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- NJEWMASZLDQGBA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 2-propylidenepropanedioate Chemical compound C1OC1COC(=O)C(=CCC)C(=O)OCC1CO1 NJEWMASZLDQGBA-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 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
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 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
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229920006285 olefinic elastomer Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は良好な成形性および優れた外観を有し、かつ耐
衝撃性などの機械的性質が優れた成形品を与える熱可塑
性ポリエステル樹脂組成物の製法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a thermoplastic polyester resin composition that provides a molded article with good moldability, excellent appearance, and excellent mechanical properties such as impact resistance. It is related to the manufacturing method of things.
ポリエステル樹脂は機械的性質、電気的性質、耐熱性、
耐薬品性などに優れ数多くの工業製品に利用されている
。しかしながらポリエステル樹脂は耐衝撃性、特にノツ
チ付衝撃強度が劣り、また成形性が悪い等の欠点があり
、従来から多くの改善方法が提案されている。例えば、
特開昭６０−４０１５４号公報に開示されているエチレ
ン−α−オレフィン共重合体のエポキシ単量体グラフト
物をブレンドする方法、特開昭５８−１７１４８号公報
のα−オレフィンとα、β−不飽和酸のグリシジルエス
テルからなるグリシジル基含有共重合体およびエチレン
−α−オレフィン共重合体の両者をブレンドする方法、
特開昭５８−３８７４７号公報に開示される脂環式カル
ボン酸変性オレフィン系エラストマーをブレンドする等
の方法はポリエステル樹脂の耐衝撃性改良に関しては比
較的硬れている。しかしながら、これらの方法はポリエ
ステル樹脂の成形性改良については何ら解決策を与えて
いない。すなわち結晶化速度が遅いポリエチレンテレフ
タレートの様な樹脂は成形品の表面と内部との結晶化度
が不均一となり、外観、機械的性質、寸法安定性、形状
安定性が悪くなる。さらに結晶化が充分起こらないので
耐熱性の良好な製品が得られない。そこでポリエチレン
テレフタレートの成形性を改良するため核形成剤ならび
に可塑剤をブレンドする方法が提案されている。例えば
特開昭５８−２１７５４７号公報にはポリエチレンテレ
フタレート、無機充填剤と共に核形成剤としてオレフィ
ンとアクリル酸又はメタクリル酸との共重合体のナトリ
ウム又はカリウム塩を、可塑剤として脂肪族カルボン酸
とアルコールのエステルをブレンドする方法などが提案
されている。この方法によれば、確かに成形性の優れた
組成物が得られるものの無機充填剤を含むため表面が粗
くなるので、優れた外観を要求される用途には向かない
。また、この特許に開示されている核形成剤および可塑
剤を前記のポリエステルと変性オレフィン系エラストマ
ーの組成物に直接適用しても衝撃強度の低い組成物しか
得られない。以上の様な理由で成形品の外観および耐衝
撃性に優れ、成形性の良いポリエステル樹脂組成物は未
だ見い出されていない。Polyester resin has mechanical properties, electrical properties, heat resistance,
It has excellent chemical resistance and is used in many industrial products. However, polyester resins have drawbacks such as poor impact resistance, particularly notched impact strength, and poor moldability, and many methods for improving them have been proposed. for example,
A method of blending an epoxy monomer grafted product of an ethylene-α-olefin copolymer disclosed in JP-A No. 60-40154, a method of blending an epoxy monomer grafted product of an ethylene-α-olefin copolymer, and a method of blending an epoxy monomer graft product of an ethylene-α-olefin copolymer with an α-olefin and α, β- A method of blending both a glycidyl group-containing copolymer consisting of a glycidyl ester of an unsaturated acid and an ethylene-α-olefin copolymer,
The method of blending an alicyclic carboxylic acid-modified olefin elastomer disclosed in JP-A-58-38747 is relatively difficult to improve the impact resistance of polyester resins. However, these methods do not provide any solution for improving the moldability of polyester resins. That is, in the case of a resin such as polyethylene terephthalate, which has a slow crystallization rate, the degree of crystallinity between the surface and the inside of a molded article becomes uneven, resulting in poor appearance, mechanical properties, dimensional stability, and shape stability. Furthermore, since sufficient crystallization does not occur, a product with good heat resistance cannot be obtained. Therefore, in order to improve the moldability of polyethylene terephthalate, a method of blending a nucleating agent and a plasticizer has been proposed. For example, JP-A-58-217547 discloses polyethylene terephthalate, an inorganic filler, a sodium or potassium salt of a copolymer of olefin and acrylic acid or methacrylic acid as a nucleating agent, and an aliphatic carboxylic acid and alcohol as a plasticizer. A method of blending esters has been proposed. According to this method, although it is possible to obtain a composition with excellent moldability, the surface becomes rough due to the inclusion of an inorganic filler, so it is not suitable for applications that require an excellent appearance. Further, direct application of the nucleating agent and plasticizer disclosed in this patent to the above-mentioned composition of polyester and modified olefinic elastomer will only result in a composition with low impact strength. For the above-mentioned reasons, a polyester resin composition with excellent molded product appearance and impact resistance and good moldability has not yet been found.
そこで本発明者らは、成形品の表面特性が良好で、耐衝
撃性等の機械的性質、耐熱性等に優れ、しかも成形性の
良好な熱可塑性組成物を得るべく鋭意研究した結果、公
知のポリエステル樹脂改質成分の混練方法を工夫するこ
とが有効であることを見い出し、本発明に到達した。Therefore, the present inventors conducted extensive research to obtain a thermoplastic composition that has good surface properties for molded products, excellent mechanical properties such as impact resistance, heat resistance, etc., and also has good moldability. The inventors have discovered that it is effective to devise a method for kneading the polyester resin modifying components, and have arrived at the present invention.
すなわち本発明は熱可塑性ポリエステル樹脂（ａ）１０
０重量部に対し極性基含有ポリオレフィン（ｂｌを１な
いし１００重量部の範囲で溶融混練し、次いで有機酸金
属塩（ｃ１を０．０１ないし２０重量部の範囲で溶融混
練することを特徴とするポリエステル樹脂組成物の製法
を要旨とする。That is, the present invention uses thermoplastic polyester resin (a) 10
0 parts by weight of a polar group-containing polyolefin (BL) in a range of 1 to 100 parts by weight, and then melt-kneaded an organic acid metal salt (C1 in a range of 0.01 to 20 parts by weight). The gist is a method for producing a polyester resin composition.
本発明をさらに詳細に説明するに本発明に使用される熱
可塑性ポリエステル樹脂は、ポリエチレンテレフタレー
トを主たる対象とするが、そのテレフタル酸成分又はグ
リコール成分の一部を他の共重合成分で置換しても良い
。共重合体成分としては、例えばイソフタル酸、ナフタ
レンジ−カルボン酸、４．４’−ジフェノキシエタンジ
カルボン酸、アジピン酸、セパチン酸及びシクロヘキサ
ンジカルボン酸等の２官能ジカルボン酸、ジオール成分
としてはエチレングリコール、トリメチレングリコール
、テトラメチレングリコール、ヘキサメチレングリコー
ル、ポリエチレングリコール、ポリプロピレングリコー
ル、ポリテトラメチレングリコール、ポリエチレングリ
コールとポリプロピレングリコールのコポリグリコール
等を挙げることが出来る。もちろん、これらのポリエス
テルは２種以上を混合しても良い。好ましいポリエステ
ルはポリエチレンテレフタレートもしくは８０モル％以
上のエチレンテレフタレート繰返し単位を有する結晶性
熱可塑性ポリエステルである。To explain the present invention in more detail, the thermoplastic polyester resin used in the present invention is mainly composed of polyethylene terephthalate, but some of the terephthalic acid components or glycol components are replaced with other copolymer components. Also good. Copolymer components include bifunctional dicarboxylic acids such as isophthalic acid, naphthalenedi-carboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, adipic acid, cepatic acid, and cyclohexanedicarboxylic acid, and diol components include ethylene glycol. , trimethylene glycol, tetramethylene glycol, hexamethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, copolyglycol of polyethylene glycol and polypropylene glycol, and the like. Of course, two or more types of these polyesters may be mixed. A preferred polyester is polyethylene terephthalate or a crystalline thermoplastic polyester having 80 mole percent or more of ethylene terephthalate repeating units.
本発明で用いる極性基含有ポリオレフィンは、分子内に
カルボキシル基もしくはその無水物を有するビニル単量
体、あるいは分子内にエポキシ基を有するビニル単量体
をオレフィン単量体存在下共重合するか、オレフィン系
重合体と上記ビニル単量体をグラフト重合する方法、ポ
リブタジェン、ポリイソプレンなどのポリジエン中に存
在する二重結合を公知の方法で酸化してエポキシ基を導
入する方法などによって得られたものを挙げることがで
きる。The polar group-containing polyolefin used in the present invention is obtained by copolymerizing a vinyl monomer having a carboxyl group or its anhydride in the molecule, or a vinyl monomer having an epoxy group in the molecule in the presence of an olefin monomer, or Those obtained by graft polymerization of an olefin polymer and the above vinyl monomer, or by oxidizing the double bonds present in polydienes such as polybutadiene and polyisoprene by a known method to introduce epoxy groups. can be mentioned.
ここでカルボキシル基含有ビニル単量体としては、アク
リル酸、メタクリル酸、マレイン酸、フマール酸、イタ
コン酸、シトラコン酸、テトラヒドロフタル酸、ビシク
ロ（２，２，１）ヘプト−２−ニンー５．６−ジカルボ
ン酸などの不飽和カルボン酸、無水マレイン酸、無水イ
タコン酸、無水シトラコン酸、テトラヒドロ無水フタル
酸、ビシクロ（２，２，１）ヘプト−２−エン−５，６
−ジカルボン酸無水物などの不飽和カルボン酸の無水物
などが挙げられるが、特に好ましくは無水マレイン酸で
ある。Here, the carboxyl group-containing vinyl monomers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo(2,2,1)hept-2-nin-5.6 -Unsaturated carboxylic acids such as dicarboxylic acids, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo(2,2,1)hept-2-ene-5,6
Examples include anhydrides of unsaturated carboxylic acids such as -dicarboxylic anhydrides, and maleic anhydride is particularly preferred.
分子内にエポキシ基を有するビニル単量体としてはアク
リル酸グリシジル、メタクリル酸グリシジル、イタコン
酸モノグリシジルエステル、ブテンジカルボン酸ジグリ
シジルエステル、ブテンジカルボン酸モノグリシジルエ
ステル、２−メチルアリルグリシジルエーテル、ビニル
−グリシジルエーテル、３，４−エポキシブテン、３．
４−エポキシ−３−メチル−１−ブテン、ビニルシクロ
ヘキセンモノオキシド、Ｐ−グリシジルスチレンなどが
挙げられ、中でもメタクリル酸グリシジルが好ましく使
用できる。Examples of vinyl monomers having an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, diglycidyl butene dicarboxylate, monoglycidyl butene dicarboxylate, 2-methylallyl glycidyl ether, vinyl- Glycidyl ether, 3,4-epoxybutene, 3.
Examples include 4-epoxy-3-methyl-1-butene, vinylcyclohexene monoxide, and P-glycidylstyrene, among which glycidyl methacrylate is preferably used.
またオレフィン単量体としては、エチレン、プロピレン
、ブテン−１，４−メチルペンテン−１、ヘキセン−１
、デセン−１などのα−オレフィン類およびブタジェン
、イソプレンなどのジオレフィン順を挙げることが出来
る。In addition, as olefin monomers, ethylene, propylene, butene-1,4-methylpentene-1, hexene-1
, α-olefins such as decene-1, and diolefins such as butadiene and isoprene.
また、前記極性基含有ビニル単量体をグラフトして極性
基含有ポリオレフィン（変性ポリオレフィンともいう）
とする際の出発物質として使用されるオレフィン系重合
体としては例えばポリエチレン、ポリプロピレン、ポリ
ブテン−１、ポリペンテン−１などのオレフィン類の単
独重合体またはエチレン−プロピレン共重合体、エチレ
ン−ブテン−１共重合体、プロピレン−ブテン−１共重
合体、エチレン−酢酸ビニル共重合体、プロピレン−酢
酸ビニル共重合体、エチレン−ブタジェン共重合体、エ
チレン−イソプレン共重合体、エチレン−クロロプレン
共重合体、プロピレン−ブタジェン共重合体、エチレン
−プロピレン−ブタジェン共重合体等の異種のオレフィ
ン類またはジオレフィン類との共重合体を挙げることが
でき、その共重合体の様式はランダム共重合体、ブロッ
ク共重合体、グラフト共重合体、交互共重合体のいずれ
のものでもよい。In addition, polar group-containing polyolefins (also referred to as modified polyolefins) can be produced by grafting the above-mentioned polar group-containing vinyl monomers.
Examples of olefinic polymers used as starting materials include homopolymers of olefins such as polyethylene, polypropylene, polybutene-1, and polypentene-1, ethylene-propylene copolymers, and ethylene-butene-1 copolymers. Polymer, propylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, propylene-vinyl acetate copolymer, ethylene-butadiene copolymer, ethylene-isoprene copolymer, ethylene-chloroprene copolymer, propylene -Copolymers with different types of olefins or diolefins such as butadiene copolymer and ethylene-propylene-butadiene copolymer can be mentioned, and the types of copolymers include random copolymers and block copolymers. It may be a polymer, a graft copolymer, or an alternating copolymer.
そして、特にエチレン−プロピレン共重合体、エチレン
−ブテン−１共重合体、エチレン−酢酸ビニル共重合体
、エチレン−プロピレン−ブタジェン共重合体、エチレ
ン−プロピレン−クロロプレン共重合体等が好ましい。Particularly preferred are ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-propylene-butadiene copolymer, ethylene-propylene-chloroprene copolymer, and the like.
そしてポリオレフィンないしオレフィン系エラストマー
は二種以上を混合して用いることもできる。なお上記の
オレフィン系重合体が極性基を有するものは、それ自体
でも使用できることは言うまでもない。Two or more types of polyolefins or olefin elastomers can also be used as a mixture. It goes without saying that the above-mentioned olefin polymers having polar groups can also be used as such.
変性ポリオレフィン１００重量部中の極性ビニル単量体
の含有量はモノマ一種にもよるが、−ｉに０．０１〜２
０重景％が好ましく 、０．０５〜１５重量％がより好
ましい。極性ビニル単量体含有ｉｏ、０１重量％以下で
は衝撃強度の改善効果は低り、２０重量％以上では核剤
添加後の衝撃強度が著しく低下する。The content of polar vinyl monomer in 100 parts by weight of modified polyolefin depends on the type of monomer, but -i is 0.01 to 2
0% by weight is preferable, and 0.05 to 15% by weight is more preferable. If the polar vinyl monomer content is less than 1% by weight, the effect of improving impact strength will be low, and if it is more than 20% by weight, the impact strength after addition of the nucleating agent will be significantly reduced.
極性基含有変性ポリオレフィンの添加量は、ポリエステ
ル樹脂１００重量部に対して１〜１００重量部であるこ
とが必要であり、２〜８０重量部であることがより好ま
しい。The amount of the polar group-containing modified polyolefin added needs to be 1 to 100 parts by weight, and more preferably 2 to 80 parts by weight, based on 100 parts by weight of the polyester resin.
添加１！！１重量部以下では耐衝撃性の改良効果に乏し
く１００重量部以上の場合機械的性質をかえって損なう
傾向がある。Addition 1! ! If it is less than 1 part by weight, the effect of improving impact resistance is poor, and if it is more than 100 parts by weight, the mechanical properties tend to be impaired.
本発明に使用する有機酸金属塩はポリエステルの結晶化
速度を促進するために添加される。すなわち、有機酸金
属塩は結晶核の形成に寄与するためである。The organic acid metal salt used in the present invention is added to accelerate the crystallization rate of the polyester. That is, this is because the organic acid metal salt contributes to the formation of crystal nuclei.
本発明に使用される有機酸金属塩を形成する有機酸とし
ては、例えばギ酸、酢酸、ステアリン酸、モンタン酸、
オレイン酸、リノール酸、シュウ酸、フタル酸、イソフ
タル酸、テレフタル酸、酒石酸、サリチル酸、安息香酸
、炭酸などを挙げることができ、中でも安息香酸が好ま
しく、また塩を形成する金属としてはナトリウム、カリ
ウム、カルシウム、マグネシウム、バリウム、亜鉛を挙
げることができる。さらに本発明で用いる有機酸金属塩
にはオレフィンとアクリル酸又はメタクリル酸の共重合
体のナトリウム、カリウム、カルシウム、亜鉛塩等が含
まれる。両者の中では後者が好ましい。これらの有機酸
金属塩はもちろん、二種以上を混合して用いても良い。Examples of the organic acid forming the organic acid metal salt used in the present invention include formic acid, acetic acid, stearic acid, montanic acid,
Oleic acid, linoleic acid, oxalic acid, phthalic acid, isophthalic acid, terephthalic acid, tartaric acid, salicylic acid, benzoic acid, carbonic acid, etc. can be mentioned, among which benzoic acid is preferable, and metals forming salts include sodium and potassium. , calcium, magnesium, barium and zinc. Furthermore, the organic acid metal salts used in the present invention include sodium, potassium, calcium, zinc salts, etc. of copolymers of olefin and acrylic acid or methacrylic acid. Of the two, the latter is preferred. Of course, these organic acid metal salts may be used in combination of two or more kinds.
有機酸金属塩の配合量はポリエステル樹脂１００重量部
に対し０．０１〜２０重量部であり、好ましくは０．１
〜１０重量部の範囲である。The amount of the organic acid metal salt is 0.01 to 20 parts by weight, preferably 0.1 parts by weight, per 100 parts by weight of the polyester resin.
-10 parts by weight.
該配合量が０．０１重量部に満たない場合、結晶化速度
の促進効果は小さく、２０重量部を越えるとポリエステ
ルの機械的性質、耐熱性などに悪影舌を与える。If the amount is less than 0.01 part by weight, the effect of accelerating the crystallization rate is small, and if it exceeds 20 parts by weight, the mechanical properties, heat resistance, etc. of the polyester will be adversely affected.
本発明で得られる組成物には必須成分子ｂ）、（ｃ１の
ほかに、更に必要に応じて可塑剤、酸化防止剤、紫外線
吸収剤等の安定剤、滑剤、難燃剤、帯電防止剤、着色剤
、離型剤、ガラス繊維、タルクなどの充填剤等の各種無
機系ないし有機系化合物を配合することができる。In addition to essential components b) and (c1), the composition obtained in the present invention further includes stabilizers such as plasticizers, antioxidants, and ultraviolet absorbers, lubricants, flame retardants, antistatic agents, Various inorganic or organic compounds such as colorants, mold release agents, glass fibers, fillers such as talc, etc. can be blended.
可塑剤としては好ましくは脂肪族アルコールとカルボン
酸のエステルであって具体的には、アジピン酸−ジー（
２−エチルヘキシル）エステル、アジピン酸−ジ−ｎ−
ブチルエステル、ポリ−（ブタン１．３−ジオールアジ
ペート）、ポリ（ヘキサン−１，６−ジオールアジペー
ト）、ポリ−（ブタン−１，４−ジオールアジペート）
、モンクン酸エステル、アルキルスルホン酸−Ｐ−フェ
ニルエステル、ジエチレングリコール−ジ−ベンゾエー
ト、ネオペンチルグリコール−ジ−ベンゾエート、ペン
タエリトリトールジベンゾエート、チオ−ジ−エタノー
ル−ジ−ベンゾエートなどが挙げられる。これらは、も
ちろん混合して用いても良い。配合量は通常ポリエステ
ル樹脂１００重量部に対し０．０１〜２０重量部であり
、好ましくは０．１〜１０重量部である。The plasticizer is preferably an ester of aliphatic alcohol and carboxylic acid, specifically adipic acid-di(
2-ethylhexyl) ester, adipic acid di-n-
Butyl ester, poly(butane 1,3-diol adipate), poly(hexane-1,6-diol adipate), poly(butane-1,4-diol adipate)
, moncitric acid ester, alkylsulfonic acid-P-phenyl ester, diethylene glycol di-benzoate, neopentyl glycol di-benzoate, pentaerythritol dibenzoate, thio-di-ethanol di-benzoate, and the like. Of course, these may be used in combination. The blending amount is usually 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the polyester resin.
本発明においては、核剤たる有機酸金属塩（ｃ）を添加
する前にポリエステル樹脂（ａ）と掻性基含有ポリオレ
フィンＴｂ）とを充分溶融混練しておくことが必要であ
る。In the present invention, it is necessary to sufficiently melt and knead the polyester resin (a) and the scratchable group-containing polyolefin Tb) before adding the organic acid metal salt (c) as a nucleating agent.
すなわちポリエステル樹脂と極性基含有ポリオレフィン
とを充分溶融混練した後、有機酸金属塩を添加し、溶融
混練する。That is, after sufficiently melt-kneading the polyester resin and the polar group-containing polyolefin, the organic acid metal salt is added and the mixture is melt-kneaded.
一括して必須三成分を溶融混練しても、（ａ）成分と（
ｃ）成分とを溶融混練後（ｂ）成分を溶融混練してもポ
リエステル樹脂の衝撃強度は改良されない。Even if the three essential components are melted and kneaded all at once, component (a) and (
Even if component (b) is melt-kneaded after component (c) is melt-kneaded, the impact strength of the polyester resin will not be improved.
本発明の組成物の製法における混練は公知の方法で行う
ことができる。例えば、押出機、ニーダ−、バンバリー
ミキサ−中で混練すればよい。この際、極性基含有変性
ポリオレフィンの平均分散粒径が３μ以下となる様混練
することが好ましい。Kneading in the method for producing the composition of the present invention can be performed by a known method. For example, the mixture may be kneaded in an extruder, kneader, or Banbury mixer. At this time, it is preferable to knead so that the average dispersed particle size of the polar group-containing modified polyolefin is 3 μm or less.
本発明によって得られる組成物は射出成形、押出成形な
どの通常の方法で容易に成形でき、特に射出成形時に１
３０℃以下の温度の金型を使用しても、外観良好で機械
的性質の優れた成形品を得ることができる。本発明の組
成物は種々の形態で種々の用途に使用できるが、特に耐
衝撃性、高剛性、高耐熱性の要求される分野、例えば自
動車外板用材料などに好適である。The composition obtained according to the present invention can be easily molded by a conventional method such as injection molding or extrusion molding.
Even if a mold with a temperature of 30° C. or lower is used, a molded product with good appearance and excellent mechanical properties can be obtained. Although the composition of the present invention can be used in various forms for various purposes, it is particularly suitable for fields requiring impact resistance, high rigidity, and high heat resistance, such as materials for automobile outer panels.
以下に実施例を挙げて本発明の効果を詳述する。EXAMPLES The effects of the present invention will be explained in detail with reference to Examples below.
実施例１
１９０℃におけるメルトインデックスが３．６０ｇ／１
０ｍ１ｎであるエチレン含量８５モル％のエチレン−ブ
テン共重合体１００重量部と無水マレイン酸１重量部、
２．５−ジメチル−２，５−ジ（ターシャリ−ブチルパ
ーオキシ）ヘキシン−３０，０６重量部を混合した後、
２５鶴φ、Ｌ／Ｄ ＝２８の単軸押出機に供給して２５
０℃で押出して無水マレイン酸変性エチレン−ブテン共
重合体（以下変性ＢＢＲと略す。）を得た。この変性Ｅ
ＢＲをキシレンに溶解しアセトンで再沈でん後乾燥し、
滴定法により無水マレイン酸のグラフト量を測定したと
ころ０．４５重量％であった。次に固有粘度０．６５ｄ
！／ｇのポリエチレンテレフタレートのベレ′ント８０
重量部と上に示した変性ＥＢＲのペレツ１−２０重量部
を混合し押出機に供給して２５０℃で溶融混練／再ペレ
タイズした。Example 1 Melt index at 190°C is 3.60g/1
100 parts by weight of an ethylene-butene copolymer with an ethylene content of 85 mol% and 1 part by weight of maleic anhydride,
After mixing 30.06 parts by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne,
25 Tsuru φ, L/D = 28 by feeding into a single screw extruder 25
Extrusion was performed at 0°C to obtain a maleic anhydride-modified ethylene-butene copolymer (hereinafter abbreviated as modified BBR). This degeneration E
Dissolve BR in xylene, reprecipitate with acetone and dry.
The amount of maleic anhydride grafted was measured by titration and found to be 0.45% by weight. Next, the intrinsic viscosity is 0.65d
! /g polyethylene terephthalate berent 80
Parts by weight and 1 to 20 parts by weight of the modified EBR pellets shown above were mixed and fed to an extruder and melt-kneaded/re-pelletized at 250°C.
（ＰＥＴ／変性ＥＢＲ予備混練品）このベレットを減圧
乾燥機で乾燥した後、核形成剤として中和度６０％のエ
チレン−メタクリル酸共重合体のナトリウム塩（エチレ
ン／メタクリル酸の重量比＝８５／１５）３重量部、可
塑剤としてジエチレングリコールジベンゾエート４重量
部を加えて再び押出機にて２５０℃で押出して得られる
ペレットをシリンダ一温度２６０℃、金型温度１２０℃
の条件で射出成形した。(PET/modified EBR pre-kneaded product) After drying this pellet in a vacuum dryer, the sodium salt of an ethylene-methacrylic acid copolymer with a degree of neutralization of 60% (weight ratio of ethylene/methacrylic acid = 85 /15) 3 parts by weight and 4 parts by weight of diethylene glycol dibenzoate as a plasticizer were added and extruded again in an extruder at 250°C, resulting in a pellet with a cylinder temperature of 260°C and a mold temperature of 120°C.
Injection molding was carried out under the following conditions.
つづいて下記の方法により物性測定を行った。Subsequently, physical properties were measured by the following method.
Ｍ Ｆ Ｒ： ＡＳＴＭ Ｄ−１２３８に従って測定し
た。MFR: Measured according to ASTM D-1238.
曲げ弾性率（ＦＭ）および曲げ強度（ＦＳ） ：１／８
’厚の試験片を用いＡＳＴＭ Ｄ７９０−８０により
測定した。Flexural modulus (FM) and bending strength (FS): 1/8
It was measured according to ASTM D790-80 using a test piece with a thickness of 1.
アイゾツト衝撃強度（１２） ： １／８“厚のノツチ
付試験片を用いＡＳＴＭ Ｄ−２５６により測定した。Izot impact strength (12): Measured according to ASTM D-256 using a 1/8" thick notched test piece.
留棒試験（ＦＤ） ： ２ ｍ厚の試験片を１６０℃で
１時間アニール後ＡＳＴＭ Ｄ−１７０９に従って一３
０℃で測定した。Fastening rod test (FD): 2 m thick specimen was annealed at 160°C for 1 hour and then tested according to ASTM D-1709.
Measured at 0°C.
熱変形温度（ＨＤＴ） ：荷重６６ＰＳ Ｉの条件で
ＡＳＴＭ Ｄ−２５６により測定した。Heat distortion temperature (HDT): Measured according to ASTM D-256 under a load of 66 PS I.
結晶化速度（ΔＨイ／ΔＨ６）；示差熱分析計（Ｄ Ｓ
Ｃ）を用いて測定した。サンプルをｌｌ４の型枠内に
入れ２９０℃、６０ ｋｇ ／ ｃａｌの条件でプレス
しその後水冷してプレスシートを得た。Crystallization rate (ΔHi/ΔH6); Differential thermal analyzer (DS
C). The sample was placed in a 114-sized mold and pressed at 290°C and 60 kg/cal, and then cooled with water to obtain a pressed sheet.
このプレスシートの中心部より約１０ｍｇのサンプルを
秤りとり１０℃／ｗｉｎで昇温２９０℃で１０ｍ１ｎ保
持した後１０℃／ｍｉｎで降温するという条件でＤＳＣ
測定を行った。得られた熱量曲線より昇温時の結晶化温
度におけるピーク面積から求めた熱量ΔＨ。Approximately 10 mg of sample was weighed from the center of this press sheet and subjected to DSC under the conditions that the temperature was raised at a rate of 10°C/win, held at 290°C for 10 ml, and then cooled at a rate of 10°C/min.
Measurements were taken. The amount of heat ΔH was determined from the peak area at the crystallization temperature during heating from the obtained heat amount curve.
降温時の結晶化時におけるピーク面積より求めた熱量Δ
Ｈｃを測定した。この様にして得られたΔＨ，Ｉ／ΔＨ
ｃは結晶化し易さの指標であり、この値が小さい程ポリ
エステルが結晶化し易いことを示している。Heat amount Δ determined from the peak area during crystallization when the temperature is lowered
Hc was measured. ΔH, I/ΔH obtained in this way
c is an index of ease of crystallization, and the smaller this value is, the easier it is for the polyester to crystallize.
実施例２
実施例１で使用した変性ＥＢＲをエチレン−グリシジル
メタクリレート共重合体（グリシジルメタクリレート含
量１０重量％）と未変性ＥＢＲのｌ：１混合物（重量比
）に代える以外はすべて実施例１と同じ方法で行った結
果を表に示す。Example 2 Everything is the same as Example 1 except that the modified EBR used in Example 1 is replaced with a 1:1 mixture (weight ratio) of ethylene-glycidyl methacrylate copolymer (glycidyl methacrylate content 10% by weight) and unmodified EBR. The results obtained using the method are shown in the table.
比較例１
実施例１で使用したポリエチレンテレフタレート８０重
量部と変性ＥＢＲ２０重量部、実施例１で使用したエチ
レン−メタクリル酸共重合体のナトリウム塩３重量部ジ
エチレングリコールジベンゾエート４重量部を一括して
押出機に供給し２５０″Ｃで溶融混練／再ペレタイズし
た。次いでこのベレットを用いて射出成形を行い物性を
測定した。結果を表に示す。Comparative Example 1 80 parts by weight of polyethylene terephthalate used in Example 1, 20 parts by weight of modified EBR, 3 parts by weight of the sodium salt of the ethylene-methacrylic acid copolymer used in Example 1, and 4 parts by weight of diethylene glycol dibenzoate were extruded all at once. The pellets were fed into a machine and melt-kneaded/re-pelletized at 250''C. Next, injection molding was performed using this pellet, and the physical properties were measured. The results are shown in the table.
比較例２
比較例１の変性ＥＢＲをエチレン−グリシジルメタクリ
レート共重合体（グリシジルメタクリレート含量１０重
量％）に代える以外はすべて比較例１と同様の方法で行
った。Comparative Example 2 Comparative Example 1 was carried out in the same manner as in Comparative Example 1 except that the modified EBR in Comparative Example 1 was replaced with an ethylene-glycidyl methacrylate copolymer (glycidyl methacrylate content: 10% by weight).
比較例３
実施例１のＰＥＴ／変性ＥＢＲ予備混練品を射出成形し
物性を測定した。結果を表に示す。Comparative Example 3 The PET/modified EBR pre-kneaded product of Example 1 was injection molded and its physical properties were measured. The results are shown in the table.
比較例４．５
比較例４としてポリエチレンテレフタレート単味の射出
成形の結果を、比較例５としてポリエチレンテレフタレ
ート８０重量部に実施例１で使用したエチレン−メタク
リル酸共重合体のナトリウム塩３重量部、ジエチレング
リコールジベンゾエート４重量部を配合したサンプルの
射出成形結果を表に示す。Comparative Example 4.5 Comparative Example 4 shows the results of injection molding of single polyethylene terephthalate, Comparative Example 5 shows 80 parts by weight of polyethylene terephthalate, 3 parts by weight of the sodium salt of the ethylene-methacrylic acid copolymer used in Example 1, The injection molding results of a sample containing 4 parts by weight of diethylene glycol dibenzoate are shown in the table.
Claims (1)
対し極性基含有ポリオレフィン（ｂ）を１ないし１００
重量部の範囲で溶融混練し、次いで有機酸金属塩（ｃ）
を０．０１ないし２０重量部の範囲で溶融混練すること
を特徴とするポリエステル樹脂組成物の製法。(1) 1 to 100 parts of polar group-containing polyolefin (b) per 100 parts by weight of thermoplastic polyester resin (a)
Melt and knead in a range of parts by weight, and then add organic acid metal salt (c)
1. A method for producing a polyester resin composition, which comprises melt-kneading in a range of 0.01 to 20 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27415486A JPH0726007B2 (en) | 1986-11-19 | 1986-11-19 | Method for producing polyester resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27415486A JPH0726007B2 (en) | 1986-11-19 | 1986-11-19 | Method for producing polyester resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63128059A true JPS63128059A (en) | 1988-05-31 |
| JPH0726007B2 JPH0726007B2 (en) | 1995-03-22 |
Family
ID=17537780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27415486A Expired - Fee Related JPH0726007B2 (en) | 1986-11-19 | 1986-11-19 | Method for producing polyester resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0726007B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63248845A (en) * | 1987-04-03 | 1988-10-17 | Mitsubishi Kasei Corp | Polyethylene terephthalate resin composition |
| JPS6475558A (en) * | 1987-09-17 | 1989-03-22 | Kanegafuchi Chemical Ind | Polyethylene terephthalate-based polymer composition |
| JPH02127437A (en) * | 1988-11-08 | 1990-05-16 | Teijin Ltd | Sheet comprising polyester resin composition and hot-molded material thereof |
| WO1996034057A1 (en) * | 1995-04-26 | 1996-10-31 | Alliedsignal Inc. | Polyester molding compositions |
| US6864318B2 (en) * | 1998-08-27 | 2005-03-08 | Atofina | Thermoplastic compositions comprising a crosslinked phase |
| WO2006068193A1 (en) * | 2004-12-24 | 2006-06-29 | Toagosei Co., Ltd. | Thermoplastic resin composition and molded article |
-
1986
- 1986-11-19 JP JP27415486A patent/JPH0726007B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63248845A (en) * | 1987-04-03 | 1988-10-17 | Mitsubishi Kasei Corp | Polyethylene terephthalate resin composition |
| JPS6475558A (en) * | 1987-09-17 | 1989-03-22 | Kanegafuchi Chemical Ind | Polyethylene terephthalate-based polymer composition |
| JPH02127437A (en) * | 1988-11-08 | 1990-05-16 | Teijin Ltd | Sheet comprising polyester resin composition and hot-molded material thereof |
| WO1996034057A1 (en) * | 1995-04-26 | 1996-10-31 | Alliedsignal Inc. | Polyester molding compositions |
| US5723520A (en) * | 1995-04-26 | 1998-03-03 | Alliedsignal Inc. | Polyester molding compositions and articles exhibiting good impact, heat and solvent resistance |
| US6864318B2 (en) * | 1998-08-27 | 2005-03-08 | Atofina | Thermoplastic compositions comprising a crosslinked phase |
| WO2006068193A1 (en) * | 2004-12-24 | 2006-06-29 | Toagosei Co., Ltd. | Thermoplastic resin composition and molded article |
| JP2006176711A (en) * | 2004-12-24 | 2006-07-06 | Toagosei Co Ltd | Thermoplastic resin composition |
| JP4645809B2 (en) * | 2004-12-24 | 2011-03-09 | 東亞合成株式会社 | Thermoplastic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0726007B2 (en) | 1995-03-22 |
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