KR830000856B1 - Glass Fiber Reinforced Thermoplastic Polyester Composition - Google Patents
Glass Fiber Reinforced Thermoplastic Polyester Composition Download PDFInfo
- Publication number
- KR830000856B1 KR830000856B1 KR1019790003750A KR790003750A KR830000856B1 KR 830000856 B1 KR830000856 B1 KR 830000856B1 KR 1019790003750 A KR1019790003750 A KR 1019790003750A KR 790003750 A KR790003750 A KR 790003750A KR 830000856 B1 KR830000856 B1 KR 830000856B1
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- composition
- polyethylene terephthalate
- glass fiber
- parts
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 86
- 239000003365 glass fiber Substances 0.000 title claims description 70
- 229920000728 polyester Polymers 0.000 title claims description 52
- 229920001169 thermoplastic Polymers 0.000 title claims description 17
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 17
- -1 polyethylene terephthalate Polymers 0.000 claims description 70
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 45
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 37
- 239000004593 Epoxy Substances 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 29
- 239000012170 montan wax Substances 0.000 claims description 24
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 238000000465 moulding Methods 0.000 description 43
- 239000008188 pellet Substances 0.000 description 25
- 238000002156 mixing Methods 0.000 description 21
- 239000000835 fiber Substances 0.000 description 19
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 13
- 238000001746 injection moulding Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000002667 nucleating agent Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical group [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 235000019386 wax ester Nutrition 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 2
- 239000004164 Wax ester Substances 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 150000001334 alicyclic compounds Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012765 fibrous filler Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
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- UTOPWMOLSKOLTQ-UHFFFAOYSA-M octacosanoate Chemical class CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O UTOPWMOLSKOLTQ-UHFFFAOYSA-M 0.000 description 2
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
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- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
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- HRKAMJBPFPHCSD-UHFFFAOYSA-N Tri-isobutylphosphate Chemical compound CC(C)COP(=O)(OCC(C)C)OCC(C)C HRKAMJBPFPHCSD-UHFFFAOYSA-N 0.000 description 1
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- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229940067597 azelate Drugs 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
- 239000011324 bead Substances 0.000 description 1
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- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- BQSLMFSQEBXZHN-UHFFFAOYSA-N bis(8-methylnonyl) butanedioate Chemical compound CC(C)CCCCCCCOC(=O)CCC(=O)OCCCCCCCC(C)C BQSLMFSQEBXZHN-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
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- FIASKJZPIYCESA-UHFFFAOYSA-L calcium;octacosanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O FIASKJZPIYCESA-UHFFFAOYSA-L 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000010727 cylinder oil Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 description 1
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- UCEHPOGKWWZMHC-UHFFFAOYSA-N dioctyl cyclohex-3-ene-1,2-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1CCC=CC1C(=O)OCCCCCCCC UCEHPOGKWWZMHC-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- MSVORCUEJCHPKS-UHFFFAOYSA-N phenoxy(phenyl)phosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)OC1=CC=CC=C1 MSVORCUEJCHPKS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229940068917 polyethylene glycols Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 229940093635 tributyl phosphate Drugs 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
내용 없음.No content.
Description
본 발명은 열가소성 폴리에스테르 조성물, 특히 유리섬유 강화에 관련된 여러가지 결점을 제거하였으며 우수하고 균일한 품질을 갖는 성형품을 성형하기 위한 양호한 성형성을 갖고 또한, 표면 특성이 우수한 개량 유리섬유 강화열가소성 폴리에스테르 조성물에 관한 것이다.The present invention eliminates various drawbacks associated with thermoplastic polyester compositions, in particular glass fiber reinforcement, and has improved formability and excellent surface properties for forming molded articles having excellent and uniform quality. It is about.
더욱 구체적으로, 본 발명은More specifically, the present invention
(a) 35℃오르토-클로로페놀 중에서 책정했을때에 고유점도 0.4∼0.9를 갖는 폴리에틸렌 테레프탈 레이트 100중량부.(a) 100 weight part of polyethylene terephthalates which have intrinsic viscosity 0.4-0.9 when formulated in 35 degreeC ortho- chlorophenol.
(b) 몬탄왁스염 0.05∼3중량부.(b) 0.05 to 3 parts by weight of montan wax salt.
(c) 평균 길이 0.2mm이상을 갖는 유리섬유 5∼200중량부, 및(c) 5 to 200 parts by weight of glass fibers having an average length of at least 0.2 mm, and
(d) 분자내에 2개 이상의 에폭시기를 갖는 에폭시 화합물 0∼5중량부로 되는 유리섬유 강화열가소성 폴리에스테르 조성물에 관한 것이다. 필요에 따라 상기 조성물은 또한 착색억제제, 핵화제, 착색제, 안정제방화제, 자외선흡수제, 산화방지제, 윤활제, 충전제 및 대전방제 등으로 되는 군으로부터 선택된 1 이상의 첨가제를 포함할 수도 있다.(d) It is related with the glass fiber reinforced thermoplastic polyester composition which consists of 0-5 weight part of epoxy compounds which have two or more epoxy groups in a molecule | numerator. If desired, the composition may also include one or more additives selected from the group consisting of color inhibitors, nucleating agents, colorants, stabilizer preservatives, ultraviolet absorbers, antioxidants, lubricants, fillers, and antistatic agents.
폴리에틸렌 테레프탈레이트 등의 직선형 포화폴리 에스테르는 2의 이화학적 성상들이 우수하기 때문에 섬유, 필름, 엔지니어링 플라스틱 등으로서 오랫동안 사용되어 왔으며, 근래 엔지니어링 플라스틱으로서 개발이 특히 주의를 끌고 있다. 그러나, 직선형 포화폴리에스테르의 본성은 엔지니어링플라스틱으로서 충분치 못하며, 따라서 이것을 엔지니어링플라스틱으로서 사용하기 위해 여러가지 개량이 있었다. 예를들면, 입자형 고상무기 또는 유기물질 등의 핵화제를 테레프탈산으로 부터 유도시킨 직선형 포화폴리에스테르와 혼합시켜 성형품 중에서 그의 결정화도를 증가시킴으로써 제조한 성형품의 밀도를 증가시키고, 고온에서 성형품의 치수안정성을 증대시키고, 성형회수를 단축시켜 생산성을 증대시키는 것은 공지이다. 이와같은 화학제로서 유용한 금속산화물,알칼리토금속염, 활석분말, 유리분말 및 5미크론 이하의 입경을 갖는 금속 분말과 같은 미세한 입자물질을 사용할 수 있다. 유기핵 화제로서는 장쇄 파라핀, 또는 스테아린산, 베헨산 및 몬탄산등의 고급 지방산 에스테르의 금속염을 사용할 수 있다.Straight saturated polyesters, such as polyethylene terephthalate, have been used for a long time as fibers, films, engineering plastics, etc. because of their excellent physicochemical properties, and development as an engineering plastic has attracted particular attention in recent years. However, the nature of linear saturated polyesters is not sufficient as engineering plastics, so there have been various improvements for using them as engineering plastics. For example, by mixing a nucleating agent such as a particulate solid or organic material with a linear saturated polyester derived from terephthalic acid to increase its crystallinity in the molded article, the density of the molded article is increased, and the dimensional stability of the molded article at a high temperature. It is known to increase the productivity, shorten the number of times of molding and increase productivity. Fine particles such as metal oxides, alkaline earth metal salts, talc powders, glass powders and metal powders having a particle diameter of 5 microns or less can be used as such chemical agents. As the nucleating agent, long-chain paraffins or metal salts of higher fatty acid esters such as stearic acid, behenic acid and montanic acid can be used.
폴리에스테르의 결정화도를 증가시키고 사출회수를 줄이기 위해 영국특허 제 1,249,252호(1971.10.13자 공고)에는 (a) 직설형 포화폴리에스테르, (b) 폴리에스테르의 중량에 기초해서 5미크론 이하의 입도를 갖는 불활성 고상유기물질 0∼3중량%, (c) 폴리에스테르의 중량에 기초해서 다기능성 에폭시화합물 0∼2중량%, (d) 폴리 에스테르의 중량에 기초해서 몬탁왁스 또는 몬탁왁스에스테르의 중성 또는 부분적으로 중화시킨 염 0∼1.5중량%로 되는 과립상 조성물이 기재되었는데, 이 입자는 0.01중량% 이하의 습기를 함유하고, 25℃에서 1.25dl/g 이상의 페놀 및 테트라클로로에탄 60 : 40 혼합물중 1% 용액으로 측정했을때에 저점도를 가지며, 이 입자는 폴리에스테르의 중량에 기초해서 몬탁왁스 또는 몬탁왁스에스테르의 중성 또는 부분적으로 중화시킨 염 0.01∼1중량%로 피북시킨다.In order to increase the crystallinity of the polyester and to reduce the number of injections, British Patent No. 1,249,252 (August 13, 1971) discloses a particle size of 5 microns or less based on the weight of (a) straight saturated polyester and (b) polyester. 0 to 3% by weight of inert solid organic material having, (c) 0 to 2% by weight of multifunctional epoxy compound based on the weight of polyester, (d) the neutrality of Montax wax or Montax wax ester based on the weight of polyester or Granular compositions of 0 to 1.5% by weight of partially neutralized salts have been described, which particles contain up to 0.01% by weight of moisture and are contained in a mixture of at least 1.25 dl / g phenol and tetrachloroethane 60:40 at 25 ° C. Low viscosity, as measured by 1% solution, based on the weight of the polyester and 0.01 to 1% by weight of neutral or partially neutralized salts of Montax wax or Montax wax ester Thereby it copybooks.
상기 영국특허 명세서에는 유리섬유와 기타 강화물질의 혼합물 전혀 기술하지 않았을 뿐만 아니라, 이들 물질을 혼합할때 생기는 기술상의 난제에 대해서도 전혀 기술하지 않고 있다.The British patent specification does not describe any mixtures of glass fibers and other reinforcing materials, nor does it describe any technical difficulties encountered when mixing these materials.
유리섬유의 혼합은 폴리에틸렌테레프탈레이트의 기계적 및 기타 물리적 성상들을 개량시키는 것으로 알려졌다. 이 방법은 폴리에스테르 조성물의 열적 성질들을 개량시키는 이점을 갖고 있다. 그러나, 유리섬유 강화열가소성 폴리에스테르 조성물은 유리섬유로 강화시키지 않은 폴리에틸렌 테레프탈레이트의 것과 다른 기술적 난제를 갖는다. 그중 대표적인 문제는 유리섬유로 강화시킨 결과 폴리에스테르조성물의 성형성이 크게 낮아진다는 것이다. 예를들면, 유리섬유 강화열가소성 폴리에스테르 조성물을 사출성형시킨 경우에, 사출성형기의 호퍼에 사입시킨 조성물은 사출성형기의 스크류채널에 부드럽고 균일하게 통과하지 않으므로 그의 미터링이 현저하게 불안정하게 된다. 이것은 짧은 간격으로 성형품을 만들어내게 되어 조성물은 약한 공급력을 갖는 성형품이 된다. 이 결점은 스크류 또는 호퍼의 형태나 또는 용융물의 크기나 형태를 변화시킴으로써 어느정도 치유할 수 있다. 그러나, 근본적으로 이 난제는 용이하게 해결되지 않는데, 그 이유는 조성물중 폴리에스테르와 유리섬유 사이에서 수축의 차이가 조성물의 표면을 현저하게 고르지 못하게 하며 조성물의 절단면에 유리섬유가 노출되어 성형물의 펠릿트 사이에서 활주가 감소되기 때문이다.Mixing of glass fibers is known to improve the mechanical and other physical properties of polyethylene terephthalate. This method has the advantage of improving the thermal properties of the polyester composition. However, glass fiber reinforced thermoplastic polyester compositions have other technical challenges than those of polyethylene terephthalate not reinforced with glass fibers. A representative problem among them is that the moldability of the polyester composition is greatly lowered as a result of reinforcement with glass fibers. For example, in the case of injection molding a glass fiber reinforced thermoplastic polyester composition, the composition injected into the hopper of the injection molding machine does not smoothly and uniformly pass through the screw channel of the injection molding machine, so that its metering becomes remarkably unstable. This results in molded articles at short intervals, so that the composition is a molded article with a weak supply. This defect can be cured to some extent by varying the shape of the screw or hopper or the size or shape of the melt. However, fundamentally this difficulty is not easily solved, because the difference in shrinkage between the polyester and the glass fibers in the composition makes the surface of the composition noticeably uneven and the glass fibers exposed on the cut surface of the composition result in pellets of the molding. This is because the slide is reduced between the two.
다른 결점은 비교적 높은 고유점도를 갖는 폴리에틸렌 테레프탈레이트가 사용하기에 어렵다는 것이다.Another drawback is that polyethylene terephthalate, which has a relatively high intrinsic viscosity, is difficult to use.
일반적으로, 유리섬유로 강화시키지 않은 폴리에틸렌 테레프탈레이트의 중합도는 가능한 증대시켜야 하는데, 그 이유는 그의 기계적 및 기타 물리적 성상들이 그의 중합도에 의해 현저하게 영향을 받기 때문이다. 그리하여, 이 기술계통에서 폴리에틸렌테레프탈레이트의 고유점도는 0.9이상, 특히 1이상이어야 되는 것으로 알려졌다. 그러나, 폴리에스테르의 고유점도가 유리섬유 강화열가소성 폴리에스테르 조성물중에서 극히 높을때에 조성물의 용융점도는 높아지게 되고, 그 결과 유리섬유중에서 폴리에스테르의 견고성은 약하게 된다. 그리하여, 폴리에스테르중 유리섬유의 분산성은 감소되어 균일하지 못한 성형품을 얻게된다. 그러므로, 이 성형물로 제조한 성형품의 기계적 및 열적 성상은 저하되게 되고, 경우에 따라서는 성형품이 소용가치가 없을 정도로 성형품의 제반 성상들이 변하게 된다.In general, the degree of polymerization of polyethylene terephthalate that is not reinforced with glass fibers should be increased as much as possible, because its mechanical and other physical properties are significantly affected by its degree of polymerization. Thus, it is known that the intrinsic viscosity of polyethylene terephthalate in this technical system should be at least 0.9, in particular at least 1. However, when the intrinsic viscosity of the polyester is extremely high in the glass fiber reinforced thermoplastic polyester composition, the melt viscosity of the composition becomes high, and as a result, the firmness of the polyester in the glass fiber becomes weak. Thus, the dispersibility of the glass fibers in the polyester is reduced to obtain a non-uniform molded article. Therefore, the mechanical and thermal properties of the molded article made from the molded article are lowered, and in some cases, the properties of the molded article are changed to such an extent that the molded article has no useful value.
또 다른 결점은, 성형품의 표면상에 윤탁현상이 발생하는 것이며, 이 결점은 유리섬유로 강화시키지 않은 폴리에틸렌테레프탈레이트보다 낮은 고유점도를 갖는 폴리에틸렌테레프탈레이트의 혼합유리섬유의 선택에 기인한 것이다. 이 현상을 유리섬유강화 폴리에틸렌테레프탈레이트 조성물이라고 하며, 이것은 폴리에스테르의 올리고머에 기인하는것 같다.Another drawback is that rusting occurs on the surface of the molded article, which is due to the selection of mixed glass fibers of polyethylene terephthalate having a lower intrinsic viscosity than polyethylene terephthalate not reinforced with glass fibers. This phenomenon is called glass fiber reinforced polyethylene terephthalate composition, and it seems to be due to the oligomer of polyester.
올리고머는 성형기 중에서 조성물을 응고해서 결정화시키는 도중에 성형물의 표면상에 유출되어 성형품과 성형기의 표면을 흐리게 한다.The oligomer flows out on the surface of the molding during the crystallization of the composition in the molding machine to cloud the surfaces of the molded article and the molding machine.
폴리에틸렌테레프탈레이트의 조성물을 성형할 경우에, 성형중 그의 결정화도를 촉진시키기 위해 성형기는 120°∼150℃로 예열시킨다. 그리하여, 혼탁현상은 특히 폴리에틸렌테레프탈레이트 조성물의 경우에 현저하게 된다. 이 현상은 성형품의 외관을 손상시키어 상품가치를 현저하게 저하시킨다.When molding the composition of polyethylene terephthalate, the molding machine is preheated to 120 ° to 150 ° C. to promote its crystallinity during molding. Thus, turbidity becomes particularly pronounced in the case of polyethylene terephthalate compositions. This phenomenon damages the appearance of the molded article and significantly lowers the value of the product.
혼탁도는 폴리에스테르의 중합도가 저하됨에 따라서 증가하게 된다. 충분히 높은 고유점도를 갖는 폴리에스테르는 상기한 바와 같이 유리섬유강화 폴리에스테르 조성물에 사용하기가 어려우므로 이 운탁현상은 유리섬유 강화열가소성 폴리에스테르를 사용했을 경우에 특히 증가하게 된다.Turbidity increases as the degree of polymerization of the polyester decreases. Polyesters having a sufficiently high intrinsic viscosity are difficult to use in glass fiber reinforced polyester compositions as described above, so this haze is particularly increased when glass fiber reinforced thermoplastic polyesters are used.
본 발명자들은 유리섬유로 강화시키지 않은 폴리에스테르에서 발견되지 않았던 새로운 결점들, 예를들면 성형성 감소, 충분히 높은 고유점도를 갖는 폴리에스테르 사용시의 제한조건 및 운탁현상의 발생등과 같은 결점을 유리하게 제거할 수 있는 유리섬유 강화열가소성 폴리에스테르 조성물을 제조하기 위해 예의 연구한 결과, 소량의 몬탁왁스염을 유리섬유 강화열가소성 폴리에스테르 조성물과 혼합함으로써 유리섬유를 혼합시킨으로써 생기는 조성물의 빈약한 성형성이 현저하게 개선되고, 저고유점도를 갖는 폴리에틸렌테레프탈레이트의 사용에 기인한 운탁현상의 결점을 편리하게 제거할 수 있음을 발견했다. 또한, 본 발명자등은 상기 조성물에 폴리에스테르 100중량부당 분자중에 2개 이상의 에폭시기를 갖는 에폭시 화합물 5중량부를 혼합시킴으로써 유리섬유 강화열가소성 폴리에스테르 조성물에서 흔히 발생하는 모울드 훌래쉬가 현저하게 감소되고, 이 조성물로 제조한 성형품의 강도가 또한 개량되었음을 발견했다.The inventors advantageously benefit from defects such as those not found in polyester not reinforced with glass fibers, such as reduced moldability, limitations in the use of polyesters with sufficiently high intrinsic viscosity, and the occurrence of haze. As a result of intensive studies to prepare a removable glass fiber reinforced thermoplastic polyester composition, the poor formability of the composition resulting from mixing glass fibers by mixing a small amount of Montax salt with a glass fiber reinforced thermoplastic polyester composition It has been found that the drawback of the phenomenon of haze due to the use of polyethylene terephthalate which is remarkably improved and has a low intrinsic viscosity can be conveniently eliminated. In addition, the present inventors, by mixing 5 parts by weight of the epoxy compound having two or more epoxy groups in the molecule per 100 parts by weight of polyester to the composition, the mold flakes commonly occurring in glass fiber reinforced thermoplastic polyester composition is significantly reduced, It has also been found that the strength of molded articles made from the composition has also been improved.
본 발명자등은 또한 생성된 성형품의 강도를 유리섬유의 표면을 폴리에스테르 조성물과 혼합하기전에 상기 에폭시 화합물로 피봇시킴으로써 더욱 증대시킬 수 있고, 몬탁왁스염을 유리섬유, 핵화제등과 균일하게 혼합시킴으로써 펠릿트제조용 압출기의 호퍼에 삽입시키는 성형 조성물을 양호한 수율로 얻을수 있음을 발견했다.The present inventors can further increase the strength of the resulting molded article by pivoting the surface of the glass fiber with the epoxy compound before mixing it with the polyester composition, and by uniformly mixing the Montaxwax salt with the glass fiber, nucleating agent or the like. It has been found that a molding composition can be obtained in good yield which is inserted into the hopper of an extruder for pellet production.
본 발명의 목적은 상기한 여러가지 기술상의 결점들을 해결한 유리섬유 강화열가소성 폴리에스테르 조성물을 제조하는 것이다.It is an object of the present invention to produce a glass fiber reinforced thermoplastic polyester composition which solves the various technical drawbacks described above.
본 발명에서 사용하는 폴리에스테르는 35℃오르토-클로로 페놀 중에서 측정했을 때에 고유점도 0.4∼0.9를 갖는 폴리에틸렌 테레프탈레이트이다.The polyester used by this invention is polyethylene terephthalate which has intrinsic viscosity 0.4-0.9 when measured in 35 degreeC ortho- chloro phenol.
폴리에틸렌 테레프탈레이트는 공지이며, 테레프탈산 또는 그의 에스테르형성 유도체 및 에틸렌글리코올 또는 그의 에스테르형성 유도체로부터 유도될수 있다.Polyethylene terephthalate is known and can be derived from terephthalic acid or its esterifying derivatives and ethyleneglycool or its esterifying derivatives.
이것은, 폴리에틸렌 테레프탈레이트를 포함할 뿐만 아니라, 또한 90몰%이상의 테레프탈산 또는 그의 에스테트형성 유도체 및 에틸렌글리코올 또는 그의 에스테트형성 유도체와 잔여성분으로 프로필렌글리코올, 헥사메틸렌글리코올 또는 테트라메틸렌글리코올 등의 C3∼C6글리코올 및(또는) 이소프탈산 또는 나프탈렌-2.6-디카르복실산 등의 디카르복실산성분으로 되는 코폴리에스테르도 포함한다.This includes not only polyethylene terephthalate, but also propylene glycol, hexamethylene glycol or tetramethylene glycol as 90% or more of terephthalic acid or its esterifying derivative and ethylene glycol or its esterifying derivative and residual components. Ko is the like of the C 3 ~C 6 glycoside-ol and (or) such as isophthalic acid or naphthalene dicarboxylic acid -2.6- dicarboxylic acid component of the polyester also includes.
본 발명 조성물에서 사용하는 폴리에틸렌 테레프탈레이트(A) 35℃ 오르토-클로로페놀 중에서 측정했을때에 고유점도(η) 0.4∼0.9, 적합하기로는 0.45∼0.8을 갖는다. 고유점도 0.9는 상기 영국특허에서 명시한 약 1.17의 점도 감소치에 해당하며, 고유점도 0.8은 1.04의 점도 감소치에 해당한다.Polyethylene terephthalate (A) used in the composition of the present invention has an intrinsic viscosity (?) Of 0.4 to 0.9 and preferably 0.45 to 0.8 when measured in 35 ° C ortho-chlorophenol. Intrinsic viscosity 0.9 corresponds to a viscosity decrease of about 1.17 as specified in the British patent, and intrinsic viscosity 0.8 corresponds to a viscosity decrease of 1.04.
명시된 한계케 이하의 고유점도를 갖는 폴리에틸렌 테레프탈레이트를 사용하면 조성물의 기계적 강도와 열적 성상이 부족하게 되고, 한계치 이상의 고유점도를 갖는 폴리에틸렌 테레프탈레이트를 사용하면 생성 조성물의 용융점도를 증가시키고, 성형성 및 기타 성상들을 저하시키게 된다. 그리하여, 폴리에틸렌 테레프탈레이트의 고유점도는 특정범위내로 하여야 한다.The use of polyethylene terephthalate having an intrinsic viscosity below the specified limit results in a lack of mechanical strength and thermal properties of the composition, and the use of polyethylene terephthalate having an intrinsic viscosity above the limit increases the melt viscosity of the resulting composition, And other properties. Thus, the intrinsic viscosity of polyethylene terephthalate should be within a certain range.
폴리에틸렌 테레프탈레이트(A)100중량부당 몬탄왁스염 0.05∼3중량부는 본 발명 조성물중 중요한 성분이다.0.05-3 parts by weight of montan wax salt per 100 parts by weight of polyethylene terephthalate (A) is an important component in the composition of the present invention.
몬탁 왁스 염은 공지되었으며, 상기 영국특허 제 1,249,852호에 기재되었으며, 이것은 몬탁왁스 또는 몬탄왁스 에스테르 중성 또는 부분적으로 중화시킨 염이다. 몬탁왁스염은 사슬중에 주로 26∼32개의 탄소원자를 갖는 지방족 모노카르복실산으로 되는 산혼합물로부터 제조한 금속염(이하 몬탄산이라고함)이다.Montax wax salts are known and described in British Patent No. 1,249,852, which are either Montax wax or Montan wax ester neutral or partially neutralized salts. Montax salts are metal salts (hereinafter referred to as montanic acid) prepared from acid mixtures composed of aliphatic monocarboxylic acids with 26 to 32 carbon atoms mainly in the chain.
몬탄왁스염은 주기율표 제 I∼III족에 해당하는 1이상의 금속, 예를들면 리튬, 나트륨, 칼륨, 바륨, 마그네숨, 칼슘 및 알루미늄 등의 양이온을 포함하는 것이 적합하며, 몬탄산의 나트륨염이 특히 적합하다.The montan wax salt preferably contains one or more metals corresponding to Groups I to III of the periodic table, for example, cations such as lithium, sodium, potassium, barium, magnesium, calcium, and aluminum. Especially suitable.
중성 또는 부분적으로 증화시킨 몬탁왁스염은 상기한 지방족 모노카르복실산 혼합물을 상기 금속의 수산화물 또는 산화물 0.2∼1 당량과 반응시켜 제조한다. 특히 수산화나트륨의 용액과 반응시켜 제조한 몬탄산나트륨이 적합하다.Neutral or partially thickened montaxaxes are prepared by reacting the aliphatic monocarboxylic acid mixtures described above with 0.2 to 1 equivalents of the hydroxides or oxides of the metals. Particularly suitable is sodium montanate prepared by reacting with a solution of sodium hydroxide.
몬탄왁스에스테르염은 몬탄산을 알킬렌기중 2∼4개의 탄소원자를 갖는 2가 알코올 0.9당량 이하, 특히 0.5∼0.8당량으로 에스테르화 시킨 다음에 에스테르화 생성물을 상기 금속의 산화물 또는 수산화물로 증화시켜 제조한다.Montan wax ester salts are prepared by esterifying montanic acid up to 0.9 equivalents, in particular 0.5 to 0.8 equivalents, of dihydric alcohols having 2 to 4 carbon atoms in the alkylene group, and then oxidizing the esterified product with an oxide or hydroxide of the metal. do.
에스테르화에 사용하는 2가 알콜올의 예로 에틸렌글리코올, 1,2-프로판디올, 1,3-프로판디올, 1,3-부탄디올 및 1,4-부탄디올을 들 수가 있다.Examples of the dihydric alcoholol used for esterification include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol and 1,4-butanediol.
본 발명에서, 몬탄왁스염은 몬탄왁스 및 몬탄왁스 에스테르의 염 모두를 포함한다.In the present invention, montan wax salts include both salts of montan wax and montan wax esters.
몬탄왁스염(B)은 폴리에틸렌테레프탈레이트(A) 100중량부 당 0.05∼3중량부, 적합하기로는 0.1∼2중량부, 더욱 적합하기로는 0.2∼1.5중량부의 양으로 사용한다. 몬탄왁스염의 양이 특정한계치 이하일 경우 유리섬유를 함유하는 폴리에틸렌 테레프탈레이트의 상기 결점을 제거하는 효과는 부족하며, 성형성과 표면 운탁현상에 관해 만족스런 개량을 얻을수 없다. 한편, 몬탄왁스 (B)의 양이 특정한계치 이상일 경우, 운탁현상은 특정한계치 내에서 몬탄왁스(B)양을 사용하는 경우와 동일한 정도로 감소시킬 수 있으나, 생성조성물의 성형성은 감소하게 된다.Montan wax salt (B) is used in an amount of 0.05 to 3 parts by weight, suitably 0.1 to 2 parts by weight, and more preferably 0.2 to 1.5 parts by weight per 100 parts by weight of polyethylene terephthalate (A). If the amount of the montan wax salt is below a certain threshold, the effect of eliminating the above defects of the polyethylene terephthalate containing glass fiber is insufficient, and satisfactory improvement in formability and surface haze is not obtained. On the other hand, when the amount of the montan wax (B) is more than a specific threshold, the haze phenomenon can be reduced to the same extent as when using the amount of montan wax (B) within a specific threshold, the formability of the resulting composition is reduced.
본 발명의 조성물중 또 다른 주요성분은 평균길이 0.2mm이상을 가지며, 폴리에틸렌 테레프탈레이트(A)100중량부 당 5∼200중량부를 사용하는 유리섬유(C)이다.Another main component in the composition of the present invention is glass fiber (C) having an average length of 0.2mm or more and using 5 to 200 parts by weight per 100 parts by weight of polyethylene terephthalate (A).
수지 강화용으로 시판되는 모든 유리섬유를 유리섬유(C)로서 사용할 수 있다. 이하에서 기술하는 방법으로 측정했을때에 평균길이는 0.2mm이상, 예를들면 약 0.2∼10mm이다. 평균길이가 0.2mm이고 미세한 유리섬유의 비율을 증가시킬 경우에, 생성 조성물로 제조한 성형품의 기계적 강도, 특히 충격 강도는 심하게 감소되며, 그의 열변형 온도는 또한 저하된다.Any glass fiber commercially available for resin reinforcement can be used as the glass fiber (C). When measured by the method described below, the average length is 0.2 mm or more, for example, about 0.2 to 10 mm. When the average length is 0.2 mm and the proportion of fine glass fibers is increased, the mechanical strength, in particular the impact strength, of the molded article made of the resulting composition is severely reduced, and its heat distortion temperature is also lowered.
이하에 기술하는 방법에 의해 측정된 유리섬유의 직경은 적당히 선택할 수 있는데, 예를들면 평균치로 약 8∼20미크론이다.The diameter of the glass fiber measured by the method described below can be appropriately selected, for example, about 8 to 20 microns in average value.
유리섬유(C)의 적당량은, 폴리에틸렌 테레프탈레이트(A) 100중량부당 5∼200중량부이다. 유리섬유의 양이 특정한계치 이하일 경우, 생성수지 조성물로 제조한 성형품의 열변형 온도및 표면경도는 감소된다.The appropriate amount of glass fiber (C) is 5-200 weight part per 100 weight part of polyethylene terephthalate (A). When the amount of glass fibers is below a certain threshold, the heat deformation temperature and the surface hardness of the molded article made of the resin composition are reduced.
유리섬유의 사용량이 특정한계치를 초과할 경우, 생성 조성물은 성형하기 어렵게 된다.When the amount of glass fiber used exceeds a certain threshold, the resulting composition becomes difficult to mold.
유리섬유(C)는 분자중에 2개 이상의 예폭시기를 갖는 에폭시 화합물로 표면 코우팅해도 좋으며, 이것은 본 발명 조성물의 기계적 강도를 증가시키기 위해 또한 적합하다.The glass fibers (C) may be surface coated with an epoxy compound having two or more preliminary groups in the molecule, which is also suitable for increasing the mechanical strength of the composition of the present invention.
표면 코우팅 에폭시 화합물의 예로 비스페놀 A를 에피클로로 하이드린으로 반응시켜 제조한 비스페놀 A형 에폭시 화합물(평균 중합도 20이하, 적합하기로는 15이하) 4,4-디하이드록시 디페닐메탄올 에피클로로 히드린과 반응시켜 얻은 비스페놀 F형 에폭시 화합물(평균중합도 20이하, 적합하기로는 15이하), 폴리(알킬렌 에테르 글리코올디글리시딜 에테르류), 예로 폴리에틸렌 글리코올 디글리시딜 에테르 또는 폴리프로필렌글리코올 디글리시딜 에테르, 알킬렌 글리코올 디글리시딜 에테르류, 예로 에틸렌글리코올 디글리시딜 에테르 또는 부탄디올-1,4-디글리시딜에테르, 솔비톨 폴리글리시딜에테르, 글리세롤 폴리글리시딜에테르디글리세롤 폴리글리시딜에테르, 비닐 사이클로헥산 디옥사이드, 디사이클로펜타디엔 디옥사이드, 3,4-에폭시-6-메틸 사이클로헥실메틸-3,4-에폭시-6-메틸사이클로헥산카아보네이트와 노볼락수지 및 에피클로로히드린으로부터 유도한 노볼락형 에폭시 화합물을 사용할수 있다. 이들 에폭시 화합물을 단독으로 또는 서로 혼합시킨 형태로 사용할 수 있다.As an example of the surface coating epoxy compound, a bisphenol A type epoxy compound prepared by reacting bisphenol A with epichlorohydrin (average degree of polymerization of 20 or less, preferably 15 or less) 4,4-dihydroxy diphenylmethanol epichlorohydrin Bisphenol F-type epoxy compound (average degree of polymerization 20 or less, suitably 15 or less), poly (alkylene ether glycodiglycidyl ethers) obtained by reaction with, for example, polyethylene glycol diglycidyl ether or polypropylene glycol Diglycidyl ether, alkylene glyco diglycidyl ethers, such as ethyleneglycool diglycidyl ether or butanediol-1,4-diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycid Diethyl ether diglycerol polyglycidyl ether, vinyl cyclohexane dioxide, dicyclopentadiene dioxide, between 3,4-epoxy-6-methyl As may be used hexyl-3,4-epoxy-6-methylcyclohexane carbonate and carbon - a novolac-type epoxy compounds derived from a novolac resin and epichlorohydrin. These epoxy compounds can be used individually or in the form which mixed with each other.
표면 코우팅 에폭시 화합물의 양은 필요에 따라 선택할 수 있다. 이것은 유리섬유(C)의 중량에 기초해서 0.1∼10중량%, 더욱 적합하기로는 0.1∼5중량%로 사용하는 것이 적합하다.The amount of surface coating epoxy compound can be selected as needed. It is suitable to use this at 0.1 to 10 weight% based on the weight of glass fiber (C), More preferably, to 0.1 to 5 weight%.
표면 코우팅수단은 적당히 선택할 수 있다. 가장 적합한 수단은 유리섬유제조시에 상기 에폭시 화합물을 커플링제 일부 또는 전부와 함께 사용하는 것이다. 이때에, 폴리비닐 클로라이드와 같이 양호한 필름 성형력을 갖는 다른 수지를 함께 사용하는 것이 적합하다.The surface coating means can be suitably selected. The most suitable means is to use the epoxy compound with some or all of the coupling agent in the manufacture of glass fibers. At this time, it is suitable to use together other resins having good film forming power, such as polyvinyl chloride.
유리섬유의 코우팅 표면이 에폭시 화합물액을 비교적 다량으로 사용하기 때문에 끈적끈적하게 되면, 유리의 취급이 용이하게 되는데, 예를들면 에폭시 화합물과 산무수물 또는 아민형의 경화제로 코우팅한 다음에 코우팅한 유리섬유를 중간 열처리하여 끈적끈적하게 되는것을 방지한다.If the coating surface of the glass fiber is sticky because it uses a relatively large amount of epoxy compound liquid, it becomes easy to handle the glass, for example, after coating with an epoxy compound and an acid anhydride or an amine type curing agent Intermediate heat treatment of the coated glass fibers prevents them from becoming sticky.
여러가지의 커플링제를 물론 이들 다기능 에폭시 화합물과 함께 사용할 수도 있다.Various coupling agents can of course also be used with these multifunctional epoxy compounds.
본 발명의 유리섬유 강화열가소성 폴리에스테르 조성물은 또한 분자중에 2개 이상의 에폭시기를 가지며 폴리에틸렌 테레프탈레이트(A) 100중량부당 5중량부까지 이 에폭시화합물(D)을 포함할수 있으며, 이것은 양호한 결과를 가져온다.The glass fiber reinforced thermoplastic polyester composition of the present invention also has two or more epoxy groups in the molecule and may contain up to 5 parts by weight of this epoxy compound (D) per 100 parts by weight of polyethylene terephthalate (A), which results in good results.
에폭시 화합물 (D)과 결합시키면 생성조성물의 성형중 성형기의 분리선을 따라 형성되는 훌래쉬를 방지해 주며, 또한 성형품의 기계적 강도를 증가시키게 된다.The combination with the epoxy compound (D) prevents the flash formed along the separation line of the molding machine during molding of the resultant composition, and also increases the mechanical strength of the molded article.
에폭시 화합물(D)의 예로, 비스페놀 A를 에피클로로히드린과 반응시켜 얻은 비스페놀 A형 에폭시화합물(평균 중합도 20이하, 적합하기로는 15이하), 노볼락수지와 에피클로로히드린으로부터 얻은 노볼락형 에폭시 화합물(평균중합도 20이하, 적합하기로는 15이하), 방향족 카아복실산과 에피클로로히드린으로부터 얻은 방향족 카르복실산형 에폭시 화합물(평균중합도 20이하, 적합하기로는 15이하), 사이클로헥센, 이사이클로 펜타디엔 및 사이클로펜타디엔등의 지환족화합물로부터 얻은 지환족 화합물형 에폭시 화합물, 저분자량 폴리에틸렌 글리코올의 글리시딜에테르 등을 사용할 수 있다. 이중에서, 디에폭시 화합물이 적합하다Examples of the epoxy compound (D) include bisphenol A type epoxy compounds obtained by reacting bisphenol A with epichlorohydrin (average degree of polymerization of 20 or less, preferably 15 or less), novolak type obtained from novolac resin and epichlorohydrin. Epoxy compounds (average degree of polymerization of 20 or less, suitably 15 or less), aromatic carboxylic acid type epoxy compounds obtained from aromatic carboxylic acids and epichlorohydrin (average degree of polymerization of 20 or less, suitably 15 or less), cyclohexene, dicyclo penta Alicyclic compound type epoxy compounds obtained from alicyclic compounds, such as diene and cyclopentadiene, glycidyl ether of low molecular weight polyethylene glycol, etc. can be used. Of these, diepoxy compounds are suitable.
특히, 적합한 화합물은 비스페놀 A형 화함물과 저분자량(174)의 폴리에틸렌글리코올의 디글리시딜에테르이다.In particular, suitable compounds are diglycidyl ethers of bisphenol A compounds and low molecular weight 174 polyethyleneglycols.
에폭시 화합물(D)의 사용량이 특정한계치 이하일 경우, 용융상태에서 조성물의 유동성은 감소되며, 생성되는 조성물은 제조한 성형품의 외관 및 물성들은 또한 역효과를 미치는 경항이 있다. 그리하여, 에폭시 화합물은 폴리에틸렌테레프탈레이트(A) 100중량부당 5중량%이하의 양으로 사용하는 것이 좋다.If the amount of the epoxy compound (D) is below a certain threshold, the flowability of the composition in the molten state is reduced, the resulting composition has a tendency to adversely affect the appearance and properties of the molded article produced. Thus, the epoxy compound is preferably used in an amount of 5% by weight or less per 100 parts by weight of polyethylene terephthalate (A).
본 발명의 유리섬유 강화열가소성 폴리에스테르 조성물은 핵화제, 착색제, 방염제, 자외선흡수제, 산화방지제, 윤활제, 증색억제제, 충전제 및 대전방지제로 되는 군중에서 선택된 1이상의 첨가제를 또한 함유해도 좋다. 핵화제의 예로, 활석, 점토, SiO2, Al2O3, TiO2, 석묵, CaCO3, MgCO3, ZnO 및 규산알루미늄 등의 무기물질과 옥살산, 스테아린산 및 안식향산등의 유기물질의 분말을 사용할 수있다. 핵화제의 사용량은 적당량으로 선택하는데, 예를들면 폴리에틸렌 테레프탈레이트의 중량에 기초해서 약 0.01∼약5중량%로 사용한다. 핵화제는 20미크론, 적합하기로는 5미크론 이하의 평균입경을 갖는것이 적합하다.The glass fiber reinforced thermoplastic polyester composition of the present invention may also contain at least one additive selected from the group consisting of nucleating agents, colorants, flame retardants, ultraviolet absorbers, antioxidants, lubricants, color inhibitors, fillers and antistatic agents. Examples of nucleating agents include powders of inorganic substances such as talc, clay, SiO 2 , Al 2 O 3 , TiO 2 , quartz, CaCO 3 , MgCO 3 , ZnO and aluminum silicates, and powders of organic substances such as oxalic acid, stearic acid and benzoic acid. Can be. The amount of nucleating agent to be used is selected in an appropriate amount, for example, from about 0.01 to about 5% by weight based on the weight of polyethylene terephthalate. Nucleating agents are suitably those having an average particle diameter of 20 microns, suitably 5 microns or less.
착색제의 예로서, 아조계 및 안트라퀴논계 등의 염료, 아조안료, 프탈로시아닌안료 및 퀴나크리돈 안료 등의 유기안료 및 산화티탄, 카아본블랙, 적철산화물 및 황화카드뮴 등의 무기안료등을 사용할 수 있다.Examples of the colorant may include dyes such as azo and anthraquinones, organic pigments such as azo pigments, phthalocyanine pigments and quinacridone pigments, and inorganic pigments such as titanium oxide, carbon black, hematite oxide, and cadmium sulfide. have.
착색제의 사용량은 적당하게 선택해야 되는데, 예를들면 폴리에틸렌테레프탈레이트의 중량에 기초해서 약 0.01∼약5중량%, 적합하기로는 약 0.05∼약2중량%로서 사용한다.The amount of the colorant to be used must be appropriately selected, for example, about 0.01 to about 5% by weight, suitably about 0.05 to about 2% by weight, based on the weight of the polyethylene terephthalate.
방염제의 예로서, 브롬화 비페닐에테르, 비스페놀 A의 고리를 브롬화시킨 생성물로 제조한 폴리카아보네이트 등의 할로겐함유 화합물, 원소인, 트리페닐모스페이트 등의 인화합물과 포스포로아미드 등의 인 질소 결합을 갖는 화합물을 들 수가 있다. 방염제는 예를들면, 폴리에틸렌 테레프탈레이트의 중량에 기초해서 약 0.5∼약 50중량%, 적합하기로는 약 3∼약25중량%이다.Examples of the flame retardant include phosphorus compounds such as halogenated compounds such as polycarbonate produced from brominated biphenyl ether and a product of brominated bisphenol A, phosphorus nitrogen such as triphenyl phosphate, phosphorus nitrogen such as phosphoramide, and the like. The compound which has a bond is mentioned. The flame retardant is, for example, about 0.5 to about 50% by weight, suitably about 3 to about 25% by weight, based on the weight of the polyethylene terephthalate.
자외선 흡수제의 예로서 2-하이드록시-4-메톡시벤조페논 등의 벤조페논 화합물, (2-하이드록시-5-메틸페닐) 벤조트리아졸등의 벤조트리아졸 화합물 및 살리실산페닐등의 살리실레이트 화합물을 사용할 수 있다. 자외선 흡수제는 예를들면, 폴리에틸렌테레프탈레이트의 중량에 기초해서 약 0.01∼약2중량%, 적합하기로는 약 0.05∼약1중량%로 사용한다.Examples of ultraviolet absorbers include benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone, benzotriazole compounds such as (2-hydroxy-5-methylphenyl) benzotriazole, and salicylate compounds such as phenyl salicylate. Can be used. For example, the ultraviolet absorber is used in an amount of about 0.01 wt% to about 2 wt%, suitably about 0.05 wt% to about 1 wt%, based on the weight of the polyethylene terephthalate.
산화방지제의 예로서, 2,4,6-트리-삼급부틸페놀 등의 방해된 페놀화합물, 디라우릴 티오디프로피오네이트등의 유황함유 화합물 및 페닐-α-나프틸아민등의 아민 화합물을 들 수가 있으며, 이 산화방지제는 폴리에틸렌테레프탈레이트의 중량에 기초해서 약 0.01∼약2중량%, 적합하기로는 약 0.05∼1중량%로 사용한다.Examples of the antioxidant include hindered phenol compounds such as 2,4,6-tri-tert-butylphenol, sulfur-containing compounds such as dilauryl thiodipropionate, and amine compounds such as phenyl-α-naphthylamine. This antioxidant is used in an amount of about 0.01 to about 2% by weight, suitably about 0.05 to 1% by weight, based on the weight of the polyethylene terephthalate.
윤활제로서는, 액체파라핀등의 파라핀계왁스, 팔미틴산등의 지방산, 부틸스테아레이트등의 지방산에스테르 및 스테아린산 나트륨등의 지방산 금속염등을 사용할 수 있으며, 이 윤활제는 폴리에스테르의 중량에 기초해서 약 0.01∼약2중량%, 적합하기로는 약 0.05∼약1중량%으로 사용한다.As the lubricant, paraffin waxes such as liquid paraffin, fatty acids such as palmitic acid, fatty acid esters such as butyl stearate and fatty acid metal salts such as sodium stearate can be used, and the lubricants are about 0.01 to about based on the weight of the polyester. 2 wt%, suitably about 0.05 to about 1 wt%.
본 발명의 조성물에 있어서, 몬탄왁스(B)염의 사용은 중요하다. 그러나, 이 화합물은 성형품 중에서 착색을 일으키기 쉬우므로 이 착색을 억제시키는데 유리한 증색억제제를 사용하는 것이 특히 유리하다. 이목적에 특히 적합한 증색억제제로서 (i) 구조식In the composition of the present invention, the use of the montan wax (B) salt is important. However, since this compound is liable to cause coloring in the molded article, it is particularly advantageous to use a color inhibitor which is advantageous for suppressing this coloring. Particularly suitable thickening inhibitors for this purpose are (i) structural formulas
(식중, R은 서로 동일하거나 또는 상이한 것으로서 각각 수소원자, 1가의 탄화수소기 및 -OR'기(여기에서 R'은 수소원자 또는 1가의 탄화수소기임)이다)으로 표시되는 화합물.Wherein R is the same or different from each other and is represented by a hydrogen atom, a monovalent hydrocarbon group and a -OR 'group, wherein R' is a hydrogen atom or a monovalent hydrocarbon group.
(ii) 구조식(ii) structural formula
(식중, R는 상기한 바와 같다)(Wherein R is as defined above)
으로 표시되는 화합물 및Compound represented by
(iii) 방해된 페놀 화합물등을 사용할 수 있다. 증색억제제는 폴리에틸렌 테레프탈레이트 100중량부당 0.01∼2중량부로 사용한다.(iii) A hindered phenol compound or the like can be used. The color inhibitor is used in 0.01 to 2 parts by weight per 100 parts by weight of polyethylene terephthalate.
상기 구조식에서, R기의 1가 탄화수소기는 12개이하의 탄소원자를 갖는 알킬, 아랄킬 및 아릴기가 적합하다. 알킬기의 예로는 메틸, 에틸, 프로필, 이소프로필, 부틸, 펜틸, 헥실, 사이클로헥실, 옥틸, 데실등이 적합하며, 아릴기로는 페닐, 나프틸, 메틸페닐, 페닐페닐 및 브롬화페닐이 적합하며, 아랄킬기로서는 벤질기가 적합하다. 증색 억제제로서 특히 적합한 인화합물로서는 인산, 인산에스테르, 예로 트리메틸포스페이트 메틸디에틸 포스페이트, 트리에틸포스테이트, 트리이소부틸 포스페이트, 트리부틸포스페이트 및 트리페닐포스페이트, 아인산, 아인산에스테르, 예로트리메틸 포스파이트, 트리에틸포스파이트 및 트리페닐포스파이트, 포스폰산, 포스폰산 유도체, 예로 페닐포스폰산 및 페닐페닐포스포네이트, 포스핀산 및 포스핀산 유도체, 예로 디메틸포스핀산등을 사용할 수 있으나, 이중에서 트리메틸 또는 트리페닐 포스페이트 등의 인산염이 특히 적합하다.In the above structural formula, the monovalent hydrocarbon groups of the R groups are suitable alkyl, aralkyl and aryl groups having up to 12 carbon atoms. Examples of the alkyl group are methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, octyl, decyl, and the like. Suitable aryl groups include phenyl, naphthyl, methylphenyl, phenylphenyl and phenyl bromide. As the kill group, benzyl group is suitable. Particularly suitable phosphorus compounds as coloration inhibitors include phosphoric acid, phosphate esters such as trimethylphosphate methyldiethyl phosphate, triethylphosphate, triisobutyl phosphate, tributylphosphate and triphenylphosphate, phosphorous acid, phosphite esters such as trimethyl phosphite, tri Ethyl phosphite and triphenyl phosphite, phosphonic acid, phosphonic acid derivatives such as phenylphosphonic acid and phenylphenylphosphonate, phosphinic acid and phosphinic acid derivatives such as dimethylphosphinic acid, etc. can be used, but among these, trimethyl or triphenyl Phosphates such as phosphate are particularly suitable.
방해된 페놀 화합물로서 2,6-디-삼급 부틸-p-크레졸, 2,4,6-트리-삼급. 부틸페놀. 1,3,5-트리메틸-2,4,6-트리스(3,5-디-삼급. 부틸-4-하이드록시 벤질), 벤젠, n-옥타데실-3-(4'-하이드록시-3',5'-디. 삼급. 부틸페놀) 프로피오네이트 및 테트라키스[메틸렌-3-(3,5-디-삼급. 부틸-4-하이드록시페닐) 프로피오 네이트] 메탄을 사용할 수 있다. 이들 인화합물 및 방해된 페놀 화합물은 단독으로 사용할 수 있으나, 서로 혼합해서 사용할 때에 보다 좋은 효과가 얻어진다.2,6-di-tert butyl-p-cresol, 2,4,6-tri-tertiary as hindered phenolic compounds. Butylphenol. 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert. Butyl-4-hydroxy benzyl), benzene, n-octadecyl-3- (4'-hydroxy-3 ', 5'-di.tert.butylphenol) propionate and tetrakis [methylene-3- (3,5-di-tert.butyl-4-hydroxyphenyl) propionate] methane can be used. These phosphorus compounds and hindered phenol compounds can be used alone, but better effects are obtained when they are mixed with each other.
충전제의 예로서 석면, 탄소섬유, 폴리아미드섬유, 석고 휘스커 및 티탄산칼륨 휘스커 등의 섬유질 충전제 및 운모, 점토, 활석, 탄산칼슘, 실리카, 장석, 황산칼슘, 이산화티탄, 석묵, 카이본블랙, 글라스비이드, 글라스플레이크, 훼라이트, 아황산칼슘 및 산화마그네슘등의 비섬유질 충전제를 사용할 수 있으며, 이 충전제는 폴리에틸렌테르프탈레이트의 중량에 기초해서 약1∼약80중량%, 적합하기로는 약 5∼약20중량%로 사용한다.Examples of fillers include fibrous fillers such as asbestos, carbon fibers, polyamide fibers, gypsum whiskers and potassium titanate whiskers and mica, clay, talc, calcium carbonate, silica, feldspar, calcium sulfate, titanium dioxide, quartz, carbon black, glass Non-fibrous fillers such as beads, glass flakes, ferrite, calcium sulfite and magnesium oxide may be used, which are about 1 to about 80 weight percent based on the weight of the polyethylene terphthalate, suitably about 5 to about Use at 20% by weight.
대전방지제로서는 스테아르아미도프로필 디메틸-β-하이드록시메틸 암모늄 나이트레이트 등의 양이온계면 활성제, 알킬아릴설페이트 등의 음이온 계면활성제 및 폴리에틸렌옥사이드 등의 비이온 계면활성제를 사용할 수 있으며, 이 대전방지제는 폴리에틸렌 테레프탈레이트의 중량에 기초해서 약 0.01∼약5중량%, 적합하기로는 약 0.05∼약2중량%로 사용한다.As the antistatic agent, cationic surfactants such as stearamidopropyl dimethyl-β-hydroxymethyl ammonium nitrate, anionic surfactants such as alkylaryl sulfate, and nonionic surfactants such as polyethylene oxide can be used. Based on the weight of terephthalate, it is used in an amount of about 0.01 to about 5% by weight, suitably about 0.05 to about 2% by weight.
필요에 따라, 본 발명의 폴리에스테르 조성물은 폴리에틸렌 테레프탈레이트 100중량부에 기초해서 소량의 기타수지, 예를들면 스티렌수지, 아크릴수지, 폴리에틸렌, 폴리프로필렌, 플루오로 카아본수지, 폴리아미드수지, 폴리카아보네이트 수지 및 폴리설폰등의 열가소성수지, 페놀수지, 멜라민수지, 불포화폴리에스테르수지, 실리콘수지 및 에폭시수지 등의 열경화성수지 및 에틸렌/비닐아세테이트공중합체, 폴리에스테르엘라스토머 및 에틸렌/프로필렌/디엔 터폴리머등의 연성열가소성수지를 함유할 수 있다.If desired, the polyester composition of the present invention is based on 100 parts by weight of polyethylene terephthalate in a small amount of other resins such as styrene resin, acrylic resin, polyethylene, polypropylene, fluorocarbon resin, polyamide resin, poly Thermosetting resins such as thermoplastic resins such as carbonate resin and polysulfone, phenol resins, melamine resins, unsaturated polyester resins, silicone resins and epoxy resins, and ethylene / vinylacetate copolymers, polyester elastomers and ethylene / propylene / dieneters. It may contain a flexible thermoplastic resin such as a polymer.
본 발명의 유리섬유 강화 열가소성 폴리에스테르 조성물은 가능하면 폴리에틸렌 테레프탈레이트(A), 몬탄왁스(B)염, 유리섬유(C) 및 에폭시 화합물(D)과 첨가제를 가능한한 균일하게 혼합하여 제조할 수 있다The glass fiber reinforced thermoplastic polyester composition of the present invention may be prepared by mixing the polyethylene terephthalate (A), montan wax (B) salt, glass fiber (C) and epoxy compound (D) with additives as uniformly as possible. have
혼합은 소기의 수단으로 행할 수 있으며, 통상으로 이들 성분들은 가능하면 균일하게 분산시키는 것이 적합하다. 이들 성분들의 전부 또는 일부는 혼합기, 혼련기, 압연기, 압출기 등으로 동시에 또는 분리해서 혼합시켜 균일하게 혼합시키는 것이 적합하다.Mixing can be carried out by any desired means, and it is usually preferable to disperse these components as uniformly as possible. All or part of these components are suitable to be mixed homogeneously by simultaneously or separately mixing with a mixer, kneader, rolling mill, extruder or the like.
가장 통상의 방법은 가열압출기 중에서 미리 건조 혼합시킨 조성물을 용융 반죽시켜 균일한 조성물을 와이어 형으로 압출시켜 이것을 적합한 길이로 절단해서 조립한다. 생성 용융 조성물은 통상으로 완전히 건조시킨 상태로 유지하며, 성형기의 호퍼에 넣어서 성형시킨다.The most common method is melt kneading a composition which has been previously dry mixed in a heat extruder, extruding a uniform composition into a wire shape, and cutting it into a suitable length to assemble it. The resulting molten composition is usually kept in a completely dried state and put into a hopper of a molding machine to be molded.
다른 방법은 폴리에틸렌 테레프탈레이트(A) 제조시에 증축합 전후 또는 도중에 기타 성분들을 가해서 혼합시키는 것이다.Another method is to add and mix the other components before, during or during the condensation in the production of polyethylene terephthalate (A).
유리섬유는 압출기 중에서 기타 성분들과 용융혼합시키지 않고 건조 혼합시켜 유리섬유의 지나친 분쇄를 방지하고, 조성물의 제조도중 그의 작업성을 개량시킬 수 있다. 예를들면, 조성물의 제조도중 그의 작업성을 개량시킬 수 있다. 예를들면, 입상 폴리에틸렌 테레프탈레이트는 압출기 중에서 제조하며, 이것을 함유하지 않는 유리섬유는 예정량의 분쇄시킨 유리스트랜드 또는 미리 다량의 유리섬유를 함유시켜 제조한 다른 열가소성수지와 함께 성형기의 호퍼에 넣는다. 몬탄왁스 또는 몬탄왁스에스테르의 중성 또는 부분적으로 중화시킨 염을 용융혼합시에 압출기중에 기타 성분들과 함께 넣은 폴리에스테르에 가해서 폴리에스테르 조성물의 입자를 조립하거나 또는 용융혼합시키기 전에 조립시킨 폴리에스테르 조성물을 성형기의 호퍼에 넣어서 상기 효과를 얻는다. 몬탄왁스 또는 그의 에스테르의 염은 조성물의 내면 및(또는) 표면에 넣거나 또는 균일하게 점착시키는 것이 적합하다. 몬탄왁스염의 적합한 양은 폴리에틸렌 테레프탈레이트(A)100중량부당 3중량부 이하이다.The glass fibers may be dry mixed without melt mixing with other components in the extruder to prevent excessive grinding of the glass fibers and to improve their workability during the manufacture of the composition. For example, its workability can be improved during the manufacture of the composition. For example, granular polyethylene terephthalate is produced in an extruder, and glass fibers that do not contain it are placed in a hopper of a molding machine together with a predetermined amount of crushed glass strands or other thermoplastics prepared by containing a large amount of glass fibers in advance. A neutral or partially neutralized salt of montan wax or montan wax ester is added to a polyester which is mixed with other components in an extruder during melt mixing to assemble the particles of the polyester composition, or the granulated polyester composition is assembled prior to melt mixing. It puts in the hopper of a molding machine and the said effect is acquired. Salts of montan wax or esters thereof are suitably placed on the inner and / or surface of the composition or adhered uniformly. A suitable amount of montan wax salt is 3 parts by weight or less per 100 parts by weight of polyethylene terephthalate (A).
본 발명의 적합한 실시예에서, 몬탄왁스염 및 평균입도 5미트론 이하를 갖는 고상 유기핵화제 예정량을 통상으로 분말을 균일하게 혼합시키기 위해 사용하는 혼합장치, 예를들면 V-형 혼합기, 리본 혼합기, 블랜버리형 혼합기 또는 시그마 불레이드형 혼합기등에 넣어 균일하게 혼합시킨다. 이때에 사용하는 고상 유기핵화제의 적당량은 몬탄왁스염에 기초해서 0.25중량%이상이다. 필요에 따라, 기타 성분의 일부 또는 전부를 동시에 또는 분리해서 혼합기에 넣어서 혼합시킨다. 혼합은 균일하게 될때까지 행한다. 생성혼합물을 취술해서 잔여물질과 함께 압출기의 호퍼에 넣고, 이어서 전제 혼합물을 압출시킨다.In a suitable embodiment of the invention, a mixing device, such as a V-type mixer, a ribbon mixer, in which a predetermined amount of a solid organic nucleating agent having a montan wax salt and an average particle size of 5 microns or less is normally used to uniformly mix the powder In a blender or sigma blender, mix them uniformly. The appropriate amount of solid organic nucleating agent used at this time is 0.25 weight% or more based on a montan wax salt. If necessary, some or all of the other ingredients are mixed simultaneously or separately in a mixer. Mixing is performed until uniform. The resulting mixture is blown into the hopper of the extruder with the remainder and the whole mixture is then extruded.
성형 조성물의 펠릿트 표면상에 몬탄왁스(B) 염을 또한 피복시키는 상기 실시예에서 몬탄왁스염 3중량부이하, 적합하기로는 0.05∼3중량부를 펠릿트 표면을 폴리에스테르(A)100중량부당 불활성 유기액체 0.01∼3중량부로 수화시킨 후에 펠릿스 표면을 점착시키는 것이 적합하다. 실온에서 유동성인 불활성 유기액체는 성형도중 분해 또는 증발되지 않으며, 조성물중 기타 물질들을 현저하게 저하시키지 않는다. 적합한 불활성 유기체의 예로서 25℃에서 100포이즈 이하의 점도를 갖는 액체를 사용할 수 있다. 이와같은 액체의 특별한 예로서, 디메틸프탈레이트, 디에틸프탈레이트, 디-n-옥틸프탈레이트 및 디이소데실 프탈레이트 등의 프탈산에스테르, 트리옥틸트리멜리테이트, 이에틸렌글리코올 디벤조에이트 및 옥틸 하이드록시벤조에이트 등의 방향족 카아복실산 에스테르, 디이소데실숙시네이트, 이옥틸아젤레이트 및 디옥틸테트라하이드로프탈레이트 등의 지방족 이염기산 에스테르, 트리아세틴 및 트리부티린등의 지방산유도체, 트리옥틸포스페이트 및 트리크레실 포스페이트 등의 인산에스테르,에폭시화 대두유 및 에폭시화 아마인유등의 에폭시계가소제, 동백유, 참기름, 아마인유, 만하단유, 해리향유 등의 각종유지, 북극산 향유 테래기름등의 액상왁스 스핀들유, 터어빈유, 기계유, 모우터유, 실린더유 및 전기 절연유등의 석유분류물을 정제시켜 제조한 각종 광유, 디알킬디클로로실란을 가수분해시켜 제조한 각종 실리콘유등을 사용할 수 있다. 이들 중에서 파라핀유 및 실리콘유가 특히 적합하다.In the above example, which also coats the Montan wax (B) salt on the pellet surface of the molding composition, the Montan wax salt is 3 parts by weight or less, preferably 0.05 to 3 parts by weight of the pellet surface per 100 parts by weight of polyester (A). It is suitable to stick the pellets surface after hydration with 0.01 to 3 parts by weight of the inert organic liquid. Inert organic liquids that are fluid at room temperature do not degrade or evaporate during molding and do not significantly degrade other materials in the composition. As an example of a suitable inert organism, a liquid having a viscosity of 100 poise or less at 25 ° C. may be used. Specific examples of such liquids include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, di-n-octyl phthalate and diisodecyl phthalate, trioctyl trimellitate, ethylene glycol dibenzoate and octyl hydroxybenzo Aliphatic dibasic acid esters such as aromatic carboxylic acid esters such as ate, diisodecyl succinate, ioctyl azelate and dioctyl tetrahydrophthalate, fatty acid derivatives such as triacetin and tributyrin, trioctyl phosphate and tricresyl Phosphate esters such as phosphate, epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil, various oils and oils such as camellia oil, sesame oil, linseed oil, mandarin oil, and dissociated oil, liquid wax spindle oil such as arctic oil, terra oil, and turbine oil. Refines petroleum products such as machine oil, motor oil, cylinder oil and electric insulating oil Various mineral oils produced by hydrolyzing the various mineral oils produced and dialkyldichlorosilanes can be used. Of these, paraffin oil and silicone oil are particularly suitable.
입상 폴리에스페르 조성물의 표면에 불활성 유기액체를 균일하게 수화시키는 것은 여러가지의 방법으로 행할수 있다. 예를들면, 입상 폴리에스테르를 리본 혼합기에 공급하고, 불활성 유기액체를 위로부터 적가하고 한편으로 이들을 혼합시키는 방법, 입상 폴리에스테르와 불활성 유기액체 모두를 동시에 V형 혼합기에 공급시켜 이들을 서로 혼합시키는 방법, 폴리에스테르입자를 벨트콘베이어에 단층으로 놓고 한편으로 콘베이어를 서서히 이송시키고, 불활성 유기액체를 콘베이어벨트상에 설치한 분무장치의 노즐로부터 입자표면에 분무시킨 다음에 수화시킨 입자를 벨트콘베이어의 단부에 설치한 리시이버 탱크에서 받는 방법등을 사용할 수 있다.The hydration of the inert organic liquid uniformly on the surface of the granular polyester composition can be performed by various methods. For example, a method of supplying particulate polyester to a ribbon mixer, dropping an inert organic liquid from above and mixing them on the other hand, and simultaneously supplying both the particulate polyester and inert organic liquid to a V-type mixer and mixing them together The polyester particles were placed in a single layer on the belt conveyor, and the conveyor was slowly transferred. The inert organic liquid was sprayed onto the particle surface from the nozzle of the spray apparatus installed on the conveyor belt, and then the hydrated particles were placed on the end of the belt conveyor. We can use method to receive in installed receiver tank.
본 발명의 유리섬유 강화-열가소성 폴리에스테르 조성물은 성형펠릿트등의 성형 입자형 또는 적합한 배열을 갖는 성형품으로 성형시킬 수 있다. 이 성형은 예를들면 사출성형 및 압축성형등의 공지방법으로 행할수 있다.The glass fiber reinforced-thermoplastic polyester composition of this invention can be shape | molded into molded particle shape, such as a molding pellet, or the molded article which has a suitable arrangement. This molding can be performed by known methods such as injection molding and compression molding, for example.
성형온도와 성형시간은 조성물의 종류, 성형종류등에 의해 적당하게 선택할 수 있다. 예를들면, 사출성형의 경우에 실린더 온도는 250∼300℃이고, 성형사이클은 15∼120초이며, 사출압력은 600∼1400kg/cm2이다. 성형물은 특별히 가열시킬 필요는 없으나, 성형은 미리 100∼150℃, 적합하기로는 120∼150℃까지 가열시킨 성형기 중에서 행하며, 성형율은 몬탄왁스염을 가해서 촉진시키며, 내외측이 모두 균일한 성형품을 얻을 수 있다.Molding temperature and molding time can be appropriately selected depending on the type of composition, the type of molding and the like. For example, in the case of injection molding, the cylinder temperature is 250 to 300 ° C, the molding cycle is 15 to 120 seconds, and the injection pressure is 600 to 1400 kg / cm 2 . The molded product does not need to be heated in particular, but the molding is carried out in a molding machine heated to 100 to 150 ° C., preferably 120 to 150 ° C. in advance, and the molding rate is accelerated by the addition of a montan wax salt. You can get it.
본 발명을 이하 실시예에 의거 구체적으로 설명하며, 유리섬유의 평균길이와 직경은 다음 방법으로 측정했다.The present invention will be described in detail based on the following examples, and the average length and diameter of the glass fibers were measured by the following method.
[평균길이][Average length]
조성물의 펠릿트 약 0.57∼0.7g을 오르토-클로로페놀 100ml중에 용해시켰다. 용해되지 않은 유리섬유를 여과 분리시켜 길이를 측정하기 위해 사용했다.About 0.57-0.7 g of pellets of the composition were dissolved in 100 ml of ortho-chlorophenol. Undissolved glass fibers were used for filtration to measure length.
원료 유리섬유 또는 펠릿트로부터 분리시킨 유리섬유를 슬라이드글라스위에 올려놓고, 유니버살투광기(프로필 프로젝터 6CT-2, 니혼고가꾸가부시기가이샤제)를 사용하여 50배 크기로 사진을 찍었다. 1000개의 유리섬유 각각의 길이를 측정하고, 측정치에 기준해서 실제길이로서 0.02mm 크기로 섬유길이의 분포를 나타내는 차아트를 만들었다. 이 분포 차아트로부터 의 길이를 갖는 섬유수를 곱한 각 섬유길이의 생성물을 측정하여 모든 섬유길이용 생성물을 요약해서 분모용으로 사용했다. 한편, 이 길이를 갖는 섬유수를 곱한 각 섬유길이를 제곱해서 얻은 생성물을 측정하여 모든 섬유길이용 생성물을 요약해서 분자로서 사용했다. 그리하여 다음 식으로 평균섬유길이를 계산했다.The glass fibers separated from the raw glass fibers or pellets were placed on the slide glass and photographed at 50 times the size using a universal light projector (Profile Projector 6CT-2, manufactured by Nihon Kogaku Co., Ltd.). The length of each of the 1000 glass fibers was measured, and based on the measured values, a car art representing the distribution of the fiber lengths with a size of 0.02 mm as the actual length was made. The product of each fiber length multiplied by the number of fibers having a length from this distribution chart was measured and all products for fiber lengths were summarized and used for denominator. On the other hand, the products obtained by squaring each fiber length multiplied by the number of fibers having this length were measured, and all the products for fiber lengths were summarized and used as molecules. Thus, the average fiber length was calculated by the following equation.
식중, X는 평균 섬유길이,Where X is the average fiber length,
Li는 각 섬유길이Li is each fiber length
ni는 길이 Li를 갖는 섬유수이다.ni is the number of fibers having a length Li.
[섬유직경][Fiber Diameter]
펠릿트중 유리섬유의 직경은 상기한 바와같이 50배 사진으로 측정했다. 이것은 성형에 의해 변하지 않으므로, 이것이 유리섬유원료의 직경과 같게 된다.The diameter of the glass fiber in the pellet was measured by 50 times photograph as described above. Since this does not change by molding, it becomes equal to the diameter of the glass fiber raw material.
성형성, 표면운탁도, 플래쉬발생 및 강도를 다음과 같이 측정했다ㅣ.Formability, surface turbidity, flash generation and strength were measured as follows.
(i) 성형성(i) formability
이것은 성형물질이 스크류채널에 부드럽게 그리고 균일하게 공급되는지 여부를 나타내는 것이며, 이것은 성형물질의 공급시간과 사출성형에 의해 제조한 성형품의 중량으로 측정할 수 있다.This indicates whether the molding material is supplied smoothly and uniformly to the screw channel, which can be measured by the feeding time of the molding material and the weight of the molded article produced by injection molding.
공급 시간은 성형물은 스크류에 의해 통속적으로 이송시킬때 까지 사출성형기의 호퍼로부터 스크류까지 성형물을 공급시키는데 소요되는 시간을 의미하며, 공급시간이 짧을수록 공급성이 더욱 좋아진다.Feed time means the time taken to feed the molding from the hopper of the injection molding machine to the screw until the molding is transported by the screw in a continuous manner. The shorter the feeding time, the better the supplyability.
성형품의 중량은 실제로 칭량하여 측정한다. 중량이 적을수록 짧은 쇼트도를 크게 해준다.The weight of the molded article is actually measured and measured. The lower the weight, the larger the short shot.
이들 성상을 측정함에 있어서, 시료성형 펠릿트를 150℃에서 4시간 동안 온기중에서 건조시킨 직후에 직경 50mm, 두께 2mm를 갖는 디스크에서 실린더 온도 275℃, 성형온도 140℃ 및 사출압력 800kg/cm2이하에서 5온스 사출성형기를 사용하여 성형했다. 냉각시간은 25초이었고, 전체사이클은 40초이었다.In measuring these properties, the sample forming pellets were dried in warm air at 150 ° C. for 4 hours in a disk having a diameter of 50 mm and a thickness of 2 mm, a cylinder temperature of 275 ° C., a molding temperature of 140 ° C., and an injection pressure of 800 kg / cm 2 or less. Molding was carried out using a 5 oz injection molding machine. The cooling time was 25 seconds and the whole cycle was 40 seconds.
성형품의 공급시간과 중량을 제11번 쇼트 내지 제20번 쇼트사이에서 10회 쇼트시켜 측정하고, 공급시간(초)와 중량(gr)의 평균치를 얻었다.The supply time and the weight of the molded article were measured ten times between the 11th shot and the 20th shot, and the average of the supply time (seconds) and the weight (gr) was obtained.
(ii) 표면 운탁도(ii) surface turbidity
성형성(i) 측정의 경우와 동일한 성형조건하에서 얻은 직경 50mm 및 두께 2mm를 갖는 디스크를 표면광택시험 했다.The surface gloss test was carried out with a disk having a diameter of 50 mm and a thickness of 2 mm obtained under the same molding conditions as in the case of the measurement of moldability (i).
연속사출성형의 경우에, 성형물의 표면을 5쇼오트마다 세정시키고, 성형표면을 닦기 직전에 쇼트시켜 얻은 생성물과 성형표면을 닦은 직후에 얻은 생성물 사이의 광택차이를 ASTM D523-53T에 의해 차색계(닛뽕 덴쇼꾸고오교제, 차색계 101D)를 사용하는 투사각 60도에서 측정했다. 이 조작을 5회 반복하고, 생성치의 평균치를 표면 운탁도로서 정의했다. 표면 운탁도가 작을수록 보다 좋은 결과가 얻어지며, 실제 목적으로 표면 운탁도 20이하가 적합하다.In the case of continuous injection molding, the gloss difference between the product obtained by cleaning the surface of the molding every 5 shots and shot immediately before wiping the molding surface and the product obtained immediately after wiping the molding surface is determined by ASTM D523-53T. It measured at the projection angle of 60 degrees using (Nippon Denshoku Kogyo Co., Ltd., color blocking system 101D). This operation was repeated 5 times, and the average value of the generated value was defined as surface turbidity. The smaller the surface turbidity is, the better the results are obtained, and the surface turbidity of 20 or less is suitable for practical purposes.
(iii) 훌래쉬의 발생(iii) occurrence of flush
성형성 (i)을 측정하기 위해 사용한 것과 동일한 디스크를 사용하며, 이들의 외관을 육안으로 관찰했다 그 결과를 다음과 같이 동급 정했다.The same disks used for measuring moldability (i) were used, and their appearance was visually observed. The results were equally determined as follows.
+ : 전체 주연부에서 훌래쉬가 관찰되었음.+: Flush was observed around the entire periphery.
△ : X보다 적지만 전체 주연부에서 훌래쉬가 관찰되었음.(Triangle | delta): Less than X, but the flush was observed in the whole periphery.
○ : 게이트 근처에서 약간의 훌래쉬가 관찰되었음.○: Some flash was observed near the gate.
◎ : 훌래쉬가 관찰되지 않았음.◎: No flush was observed.
(iv ) 성형품의 강도(iv) strength of molded parts
시료성형 펠릿트를 150℃ 온기에서 4시간 동안 건조시킨 직후에 실린더온도 270℃와 사출압력 1000kg.m2하의 성형온도 140℃에서 5온스 사출 성형기를 성형시켰다. 냉각시간은 25초이고, 전체 사이클은 40초이었다. 그리하여, ASTM시험편을 제조했다. 이들 시험편을 사용하여, ASTM D-790에 의해 굴곡강도를 측정했고, ASTM D-638에 의해 항장력을 측정했다.Immediately after drying the sample-forming pellets at 150 ° C. for 4 hours, a 5 oz injection molding machine was molded at a cylinder temperature of 270 ° C. and a molding temperature of 140 ° C. under an injection pressure of 1000 kg.m 2 . The cooling time was 25 seconds and the whole cycle was 40 seconds. Thus, an ASTM test piece was produced. Using these test pieces, flexural strength was measured by ASTM D-790, and tensile strength was measured by ASTM D-638.
[실시예 1∼3 및 비교예 1∼7][Examples 1-3 and Comparative Examples 1-7]
각 실시예에서, 120℃에서 5시간 동안 건조시킨 폴리에틸렌 테레프탈레이트를 표1에 나타낸 비율로 표1에 나타낸 기타물질과 V형 혼합기를 사용해서 혼합시켰다.In each example, polyethylene terephthalate dried at 120 ° C. for 5 hours was mixed with the other materials shown in Table 1 using a Type V mixer in the proportions shown in Table 1.
이 혼합물을 융용상태로 실린더온도 280℃에서 65mm 압출기 중에서 혼합시키고, 다이로부터 압출시킨 스레트를 냉각시켜 절단해서 성형펠릿트를 제조했다.The mixture was melted in a 65 mm extruder at a cylinder temperature of 280 ° C., and the pellets extruded from the die were cooled and cut to prepare molding pellets.
성형 펠릿트를 성형시키고, 이들의 성형성 및 성형품의 외관(표면운탁 및 훌래쉬)와 강도를 측정하여 그 결과를 표1에 나타냈다.Molded pellets were molded, and their moldability and appearance (surface haze and flush) and strength of the molded articles were measured, and the results are shown in Table 1.
표1에 나타낸 결과로부터 알수있는 바와 같이, 비교예 1및 2에서와 같이 높은 고유점도를 갖는 폴리에틸렌테레프탈레이트를 함유하는 조성물의 성형성은 양호하며, 성형품의 외관은 몬탄산나트륨의 존재 또는 부재 여하에 따라 명백히 달라진다. 그러나, 이들 성형품은 충분한 강도를 나타내지 않는다.As can be seen from the results shown in Table 1, the moldability of the composition containing polyethylene terephthalate having a high intrinsic viscosity as in Comparative Examples 1 and 2 is good, and the appearance of the molded article depends on the presence or absence of sodium moncarbonate. Obviously different. However, these molded articles do not exhibit sufficient strength.
사용하는 조성물을 비교예 1및 2의 조성물에 유리섬유를 혼합시켜 얻은 비교예 3및 4에서 펠릿트용 물질들의 균일한 혼합은 어려우며, 수지로 포화시키지 않은 유리섬유가 펠릿트 표면상에 침술되었다. 이들 펠릿트를 사출 성형기에 공급시킬때에 스크류의 회전력은 범상적으로 높게 되었다. 그리하여 성형이 멈추게 되었다In Comparative Examples 3 and 4 obtained by mixing the glass fibers in the compositions of Comparative Examples 1 and 2, uniform mixing of materials for pellets was difficult, and glass fibers not saturated with resin were acupunctured on the surface of the pellets. When these pellets were fed to the injection molding machine, the rotational force of the screw became unusually high. Thus the molding stopped
저고유점도를 갖는 폴리에틸렌테레이트를 사용하고 유리섬유를 또한 혼합시키는 비교예 5에서 펠릿트의 표면상에서 유리섬유는 충분한 양의 수지로 포화되며, 균일하게 반죽된 상태를 나타냈다. 그러나, 생성조성물은 성형성이 약했다. 경우에 따라서 미터링이 단축되어 짧은 쇼트를 갖는 생성물이 얻어졌다.In Comparative Example 5 in which polyethylene terate having a low intrinsic viscosity was used and glass fibers were also mixed, the glass fibers on the surface of the pellets were saturated with a sufficient amount of resin, and showed a uniformly kneaded state. However, the resulting composition was poor in formability. In some cases the metering was shortened to give a product with a short shot.
성형을 계속할때에, 성형품 표면의 광택은 나빠지게되며, 성형물의 표면은 혼탁하게 되었다. 이것을 방지하기 위해 성형물 표면을 3회 쇼트마다 1회씩 헝겊으로 닦아줄 필요가 있다.As the molding continued, the gloss of the surface of the molded part became worse, and the surface of the molded part became cloudy. To prevent this, the surface of the moldings needs to be wiped with a cloth once every three shots.
실시예 1에서, 비교예 5와 비교하여 명백한 바와 같이 조성물의 성형성과 성형품의 표면운탁도는 개량되었다.In Example 1, the moldability of the composition and the surface turbidity of the molded article were improved as is apparent in comparison with Comparative Example 5.
실시예 2및 3에서 폴리에틸렌테레프탈레이트의 고유점도 및 유리섬유의 양은 본 발명에서 지정한 범위내에서 변화시킨다. 조성물의 성형성과 성형물의 표면운탁도는 몬탄산나트륨과 혼합시킴으로써 개량되었다.In Examples 2 and 3, the intrinsic viscosity of polyethylene terephthalate and the amount of glass fibers are varied within the range specified in the present invention. The moldability of the composition and the surface turbidity of the moldings were improved by mixing with sodium montanate.
비교예 6에서 몬탄산나트륨의 사용량은 본 발명에서 정한 한계치보다 적다. 조성물의 성형성은 좋지못하며, 운탁물질이 성형품의 표면에 점착되었다.In Comparative Example 6, the amount of sodium montanate used is less than the limit defined in the present invention. The moldability of the composition was poor, and the haze material adhered to the surface of the molded article.
비교예 7에서, 몬탄산나트륨의 사용량은 본 발명에서 정한 한계치보다 크다. 성형물에 점착물질의 점착은 관찰되지 않으나, 조성물의 성형성은 극히 나빴다.In Comparative Example 7, the amount of sodium montanate used is greater than the limit defined in the present invention. Adhesion of the adhesive substance to the molding was not observed, but the moldability of the composition was extremely bad.
[표 1]TABLE 1
(
(
[표 1(계속)]Table 1 (continued)
[실시예 4∼7]EXAMPLES 4-7
각 실시예에서, 표2에 나타낸 각 농도에서 커플링제로서 비스페놀 A형 에폭시 화합물(EDIKOTE 828, 쉘화학회사의 상품명)의 유화액을 사용하여 제조한 유리섬유의 분쇄스트랜드(섬유직경 13미크론 및 섬유길이 3mm) 40중량부와 융점 176℃의 몬탄산나트륨 0.3중량부를 120℃에서 5시간 건조시킨후 고유점도 0.62를 갖는 폴리에틸렌 테레프탈레이트 100중량부에 가해서 회전통에서 3분동안 혼합시켰다. 생성 혼합물을 용융상태로 반죽시키고, 실린더온도 280℃에서 65mm압출기를 사용하여 압출시켰다.In each example, the crushed strands (fiber diameter 13 micron and fiber length) of glass fibers prepared using an emulsion of a bisphenol A type epoxy compound (EDIKOTE 828, trade name of Shell Chemical Company) as a coupling agent at each concentration shown in Table 2. 3 mm) 40 parts by weight and 0.3 parts by weight of sodium montanate at a melting point of 176 ° C. were dried at 120 ° C. for 5 hours, and then added to 100 parts by weight of polyethylene terephthalate having an intrinsic viscosity of 0.62 and mixed in a rotating tube for 3 minutes. The resulting mixture was kneaded in a molten state and extruded using a 65 mm extruder at a cylinder temperature of 280 ° C.
다이로부터 압출시킨 스레드를 냉각시키고, 절단해서 성형 펠릿트를 제제했다. 성형 펠릿트의 성형성과 성형품의 외관및 강도를 측정하여 그 결과를 표2에 나타냈다.The thread extruded from the die was cooled, cut and a molding pellet was prepared. The moldability of the molded pellet and the appearance and strength of the molded article were measured, and the results are shown in Table 2.
표 2에서 성형품의 강도는 유리섬유에 점착하는 에폭시 화합물의 양이 증가함에 따라 증가함을 알수있다It can be seen from Table 2 that the strength of the molded article increases as the amount of epoxy compound adhering to the glass fiber increases.
조성물의 성형성 및 외관과 이들 실시예의 생성물은 많이 동일했다.The formability and appearance of the composition and the products of these examples were much the same.
[표 2]TABLE 2
[실시에 8∼11][Examples 8-11]
각 실시예에서, 유리섬유의 분쇄스트랜드(직경 13미크론 및 길이 3mm) 40중량부, 융점 170℃를 갖는 몬탄산나트륨 0.3중량부 및 에폭시 화합물(EPIKOBE 815, 쉘화학회사의 상품명) 0.05, 0.5, 1.0 또는 3.0중량부를 120℃에서 5시간동안 건조시킨 고유점도 0.600을 갖는 폴리에틸렌테레프탈레이트 100중량부에 가했다. 이들을 통속에서 혼합시킨 뒤 용융상태로 반죽시키고, 실린더온도 260℃에서 그안에 진공상태를 유지하면서 65mm 압출기로 압출시켰다.In each example, 40 parts by weight of crushed strands of glass fibers (13 microns in diameter and 3 mm in length), 0.3 parts by weight of sodium montanate having a melting point of 170 ° C. and an epoxy compound (EPIKOBE 815, trade name of Shell Chemical Co., Ltd.) 0.05, 0.5, 1.0 Or 100 parts by weight of polyethylene terephthalate having an intrinsic viscosity of 0.600 dried at 120 ° C. for 5 hours. These were mixed in a cylinder and kneaded in a molten state and extruded with a 65 mm extruder while maintaining a vacuum therein at a cylinder temperature of 260 ° C.
다이로부터 추출되는 스레드를 냉각시키고 절단해서 용융펠릿트를 형성했다.The threads extracted from the die were cooled and cut to form molten pellets.
이들 펠릿트를 사용하여 펠릿트의 성형성, 성형품의 외관및 강도를 측정했다. 이 결과를 표3에 요약했다These pellets were used to measure the formability of the pellets, the appearance and strength of the molded article. The results are summarized in Table 3.
표3의 결과에서 몬탄산나트륨을 에폭시화합물과 혼합해서 사용할 경우에 성형품의 외관은 개량되었고, 훌래쉬형성은 현저하게 감소되었다.In the results of Table 3, when the sodium montanate was mixed with the epoxy compound, the appearance of the molded article was improved, and the flush formation was significantly reduced.
[표 3]TABLE 3
[실시예 12∼21]Examples 12 to 21
각 실시예에서, 섬유길이 6mm 및 직경 13미크론을 갖는 유리섬유 30중량부 및 표4에 나타낸 아민산화합물 또는 방해 페놀화합물 각각의 표시량을 고유점도 0.85이고 120℃에서 5시간 동안 건조시킨 폴리에틸렌테레프탈레이트 100중량부를 가했다. 이들을 270℃에서 65mm압출기에서 용융상태로 반죽시키고, 압출시켜 펠릿트를 만들었다.In each example, polyethylene terephthalate having 30 parts by weight of glass fiber having a fiber length of 6 mm and a diameter of 13 microns and the indicated amount of each of the amine or hindered phenol compounds shown in Table 4 and having an intrinsic viscosity of 0.85 and dried at 120 ° C. for 5 hours. 100 parts by weight was added. They were kneaded at 270 ° C. in a 65 mm extruder and extruded to form pellets.
펠릿트 100중량부에 몬탄산나트륨(수산화나트륨 0.75당량으로 부분 중화시켜 얻은 몬타네이트) 0.3부 또는 몬탄산칼슘(몬탄산을 1.3-부탄디올 9.75당량으로 에스테르화시킨 다음에 이 에스테르를 산화칼슘으로 중화시켜 얻은 몬탄산염) 0.3부를 가했다.To 100 parts by weight of pellets, 0.3 parts of sodium montanate (montanate obtained by partial neutralization of 0.75 equivalents of sodium hydroxide) or calcium montanate (monsteric acid to 9.75 equivalents of 1.3-butanediol) was then neutralized with calcium oxide. 0.3 parts of obtained montanates) were added.
이 혼합물을 사출성형시키고, 조성물의 성형형 및 성형품의 조성 및 외관을 측정했다.The mixture was injection molded, and the composition and appearance of the molding of the composition and the molded article were measured.
성형성을 측정하기 위해 사용한 성형품과 동일한 디스크를 훈터색도계를 사용하여 색도를 시험하여 L,a 및 b치를 얻었다. 그 결과를 표4에 나타냈다.The same disks as the molded articles used for measuring the formability were tested for chromaticity using a Hunter colorimeter to obtain L, a and b values. The results are shown in Table 4.
표4에 나타낸 결과로부터 알수있는 바와같이 아인산화합물 또는 방해 페놀화합물을 함유하는 조성물은 치가 작고, 우수한 색상을 나타냈다. 조성물의 성형성 및 성형물의 외관은 아인산 화합물 또는 방해페놀화합물을 부가했을 경우 저하되지 않았다.As can be seen from the results shown in Table 4, the composition containing the phosphorous acid compound or the hindered phenolic compound had a small value and exhibited excellent color. The moldability of the composition and the appearance of the molded product did not decrease when a phosphorous acid compound or a hindered phenol compound was added.
[표 5]TABLE 5
[표 4(계속)]Table 4 (continued)
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019790003750A KR830000856B1 (en) | 1979-10-27 | 1979-10-27 | Glass Fiber Reinforced Thermoplastic Polyester Composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019790003750A KR830000856B1 (en) | 1979-10-27 | 1979-10-27 | Glass Fiber Reinforced Thermoplastic Polyester Composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR830000856B1 true KR830000856B1 (en) | 1983-04-21 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019790003750A KR830000856B1 (en) | 1979-10-27 | 1979-10-27 | Glass Fiber Reinforced Thermoplastic Polyester Composition |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR830000856B1 (en) |
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1979
- 1979-10-27 KR KR1019790003750A patent/KR830000856B1/en active
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