JPH08199048A - Polyethylene terephthalate resin composition - Google Patents
Polyethylene terephthalate resin compositionInfo
- Publication number
- JPH08199048A JPH08199048A JP808795A JP808795A JPH08199048A JP H08199048 A JPH08199048 A JP H08199048A JP 808795 A JP808795 A JP 808795A JP 808795 A JP808795 A JP 808795A JP H08199048 A JPH08199048 A JP H08199048A
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene terephthalate
- terephthalate resin
- resin composition
- ammonium
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Polyethylene terephthalate Polymers 0.000 title claims abstract description 70
- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract description 45
- 239000005020 polyethylene terephthalate Substances 0.000 title claims abstract description 45
- 239000011342 resin composition Substances 0.000 title claims abstract description 23
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 150000004010 onium ions Chemical class 0.000 claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 claims abstract description 17
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 11
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical group [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 4
- 229910000271 hectorite Inorganic materials 0.000 claims description 4
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 abstract description 7
- 238000007711 solidification Methods 0.000 abstract description 7
- 230000008023 solidification Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- 239000002667 nucleating agent Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003484 crystal nucleating agent Substances 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 229910021647 smectite Inorganic materials 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical class OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 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
- 238000005341 cation exchange Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 125000005496 phosphonium group Chemical group 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- DFPAKSUCGFBDDF-UHFFFAOYSA-N nicotinic acid amide Natural products NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 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
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical class N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- RKMJXTWHATWGNX-UHFFFAOYSA-N decyltrimethylammonium ion Chemical compound CCCCCCCCCC[N+](C)(C)C RKMJXTWHATWGNX-UHFFFAOYSA-N 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- SWSFKKWJEHRFFP-UHFFFAOYSA-N dihexadecyl(dimethyl)azanium Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCC SWSFKKWJEHRFFP-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion 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
- 239000011777 magnesium Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 235000005152 nicotinamide Nutrition 0.000 description 2
- 239000011570 nicotinamide Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- WSNJABVSHLCCOX-UHFFFAOYSA-J trilithium;trimagnesium;trisodium;dioxido(oxo)silane;tetrafluoride Chemical compound [Li+].[Li+].[Li+].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WSNJABVSHLCCOX-UHFFFAOYSA-J 0.000 description 2
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 2
- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 description 2
- UMZDENILBZKMFY-UHFFFAOYSA-N 1,2-dimethylpyridin-1-ium Chemical compound CC1=CC=CC=[N+]1C UMZDENILBZKMFY-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- XAUQWYHSQICPAZ-UHFFFAOYSA-N 10-amino-decanoic acid Chemical compound NCCCCCCCCCC(O)=O XAUQWYHSQICPAZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- RITONZMLZWYPHW-UHFFFAOYSA-N 3-methylhex-1-ene Chemical compound CCCC(C)C=C RITONZMLZWYPHW-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- UQXNEWQGGVUVQA-UHFFFAOYSA-N 8-aminooctanoic acid Chemical compound NCCCCCCCC(O)=O UQXNEWQGGVUVQA-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- ZILXLWDXJIKUHY-UHFFFAOYSA-N C=1C=CC=CC=1C(C=1C=CC=CC=1)(CCCCCCCCCCCCCCCCCP)C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(CCCCCCCCCCCCCCCCCP)C1=CC=CC=C1 ZILXLWDXJIKUHY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JGFDZZLUDWMUQH-UHFFFAOYSA-N Didecyldimethylammonium Chemical compound CCCCCCCCCC[N+](C)(C)CCCCCCCCCC JGFDZZLUDWMUQH-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910015243 LiMg Inorganic materials 0.000 description 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
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- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 125000005131 dialkylammonium group Chemical group 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- 239000002344 surface layer Substances 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
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- 239000010936 titanium Substances 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- SNDRYHUSDCHSDJ-UHFFFAOYSA-N tributyl(dodecyl)phosphanium Chemical compound CCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC SNDRYHUSDCHSDJ-UHFFFAOYSA-N 0.000 description 1
- JWZDVHOYCNIXDA-UHFFFAOYSA-N tributyl(phenyl)phosphanium Chemical compound CCCC[P+](CCCC)(CCCC)C1=CC=CC=C1 JWZDVHOYCNIXDA-UHFFFAOYSA-N 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- SBHRWOBHKASWGU-UHFFFAOYSA-M tridodecyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC SBHRWOBHKASWGU-UHFFFAOYSA-M 0.000 description 1
- ADBMSVFHVFJBFR-UHFFFAOYSA-N triethyl(hexadecyl)azanium Chemical compound CCCCCCCCCCCCCCCC[N+](CC)(CC)CC ADBMSVFHVFJBFR-UHFFFAOYSA-N 0.000 description 1
- JXCCIZBMTUFJKN-UHFFFAOYSA-N triethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](CC)(CC)CC JXCCIZBMTUFJKN-UHFFFAOYSA-N 0.000 description 1
- AUSVCTPDUJVUGB-UHFFFAOYSA-N trimethyl(octadec-1-enyl)azanium Chemical compound CCCCCCCCCCCCCCCCC=C[N+](C)(C)C AUSVCTPDUJVUGB-UHFFFAOYSA-N 0.000 description 1
- ZBMLLSYGUXEKLB-UHFFFAOYSA-N trimethyl(octadeca-1,3-dienyl)azanium Chemical compound CCCCCCCCCCCCCCC=CC=C[N+](C)(C)C ZBMLLSYGUXEKLB-UHFFFAOYSA-N 0.000 description 1
- IKANSXQHJXBNIN-UHFFFAOYSA-N trimethyl(octadecyl)phosphanium Chemical compound CCCCCCCCCCCCCCCCCC[P+](C)(C)C IKANSXQHJXBNIN-UHFFFAOYSA-N 0.000 description 1
- WHAFDJWJDDPMDO-UHFFFAOYSA-N trimethyl(phenyl)phosphanium Chemical compound C[P+](C)(C)C1=CC=CC=C1 WHAFDJWJDDPMDO-UHFFFAOYSA-N 0.000 description 1
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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- 235000019354 vermiculite Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
(57)【要約】
【目的】 射出成形等における固化速度が大きく、滞留
熱安定性にも優れ、幅広い分野の構造材料として有用な
ポリエチレンテレフタレート樹脂組成物を提供する。
【構成】 ポリエチレンテレフタレート樹脂に対し、有
機オニウムイオンを層間に有する層状珪酸塩と、エポキ
シ基を分子内に１以上有する変性ポリオレフィンを添加
して成るポリエチレンテレフタレート樹脂組成物。(57) [Summary] [Object] To provide a polyethylene terephthalate resin composition which has a high solidification rate in injection molding and the like and is excellent in retention heat stability and is useful as a structural material in a wide variety of fields. A polyethylene terephthalate resin composition obtained by adding, to a polyethylene terephthalate resin, a layered silicate having an organic onium ion between layers and a modified polyolefin having one or more epoxy groups in the molecule.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、優れた熱安定性と改善
された結晶性を有するポリエチレンテレフタレート樹脂
組成物に関する。本発明の樹脂組成物は、機械部品、電
気電子部品、自動車部品、耐熱性食品容器等の幅広い分
野における構造材料として有用である。FIELD OF THE INVENTION The present invention relates to a polyethylene terephthalate resin composition having excellent thermal stability and improved crystallinity. The resin composition of the present invention is useful as a structural material in a wide range of fields such as machine parts, electric / electronic parts, automobile parts, and heat-resistant food containers.
【０００２】[0002]
【従来の技術】ポリエチレンテレフタレート樹脂は、結
晶化した場合の優れた耐熱性と剛性を有する材料である
が、溶融状態からの結晶化が遅いという欠点を有する。
従って、ポリエチレンテレフタレート樹脂を溶融成形、
特に射出成形のような早い成形サイクルを要求される方
法に適用しようとする場合には、結晶化速度を上昇させ
ることが必要である。2. Description of the Related Art Polyethylene terephthalate resin is a material having excellent heat resistance and rigidity when crystallized, but has a drawback that crystallization from a molten state is slow.
Therefore, melt molding polyethylene terephthalate resin,
Especially when it is intended to apply a method requiring a fast molding cycle such as injection molding, it is necessary to increase the crystallization rate.
【０００３】ポリエチレンテレフタレート樹脂の結晶化
速度を上昇させる試みとして様々な結晶核剤が検討され
てきた。例えば、無機核剤としてタルク、カオリン、ク
レー等が、有機核剤としてｐ−フェノールスルホン酸や
ｐ−ヒドロキシ安息香酸のナトリウム塩等の芳香族酸誘
導体の塩等が既に知られている。また従来、ポリエチレ
ングリコール等の可塑剤を併用することも知られてい
る。Various crystal nucleating agents have been investigated in an attempt to increase the crystallization rate of polyethylene terephthalate resin. For example, talc, kaolin, clay and the like are known as inorganic nucleating agents, and salts of aromatic acid derivatives such as sodium salts of p-phenolsulfonic acid and p-hydroxybenzoic acid are already known as organic nucleating agents. It is also known that a plasticizer such as polyethylene glycol is used together.
【０００４】しかし、最も優れた無機核剤の一つとされ
ているタルクを使用してもその結晶核剤効果は必ずしも
十分ではなく、表層の後結晶化を促進する目的で有機核
剤を併用する必要があるが、有機核剤はポリエチレンテ
レフタレート樹脂を溶融状態で低分子量化させる欠点が
あり、熱安定性に問題を残していた。特開平５−１８６
６７２号公報には、優れた核剤効果が発揮されるチオシ
アン酸金属塩を使用する技術が開示されているものの、
ナトリウムイオン等のアルカリ成分を含むため依然とし
て熱安定性に問題を残していた。However, even if talc, which is considered to be one of the most excellent inorganic nucleating agents, is used, its crystal nucleating agent effect is not always sufficient, and an organic nucleating agent is used in combination for the purpose of promoting post-crystallization of the surface layer. Although necessary, the organic nucleating agent has a drawback of lowering the molecular weight of the polyethylene terephthalate resin in a molten state, and thus has a problem in thermal stability. Japanese Patent Laid-Open No. 5-186
Although Japanese Patent No. 672 discloses a technique of using a metal thiocyanate that exhibits an excellent nucleating agent effect,
Since it contains an alkali component such as sodium ion, there still remains a problem in thermal stability.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、こうしたポ
リエチレンテレフタレート樹脂の結晶核剤に関する技術
の現状に鑑み、射出成形等における固化速度が大きく滞
留熱安定性にも優れ、巾広い分野の構造材料として有用
なポリエチレンテレフタレート樹脂組成物を提供するこ
とを目的とする。DISCLOSURE OF THE INVENTION In view of the current state of the art regarding the crystal nucleating agent for polyethylene terephthalate resin, the present invention has a large solidification rate in injection molding and the like and is excellent in retention heat stability, and is a structural material in a wide range of fields. An object of the present invention is to provide a polyethylene terephthalate resin composition useful as the above.
【０００６】[0006]
【課題を解決するための手段】即ち、本発明は、ポリエ
チレンテレフタレート樹脂に対して、有機オニウムイオ
ンを層間に含有する層状珪酸塩を灰分量として０．０１
〜１０重量％、及びエポキシ基を分子内に１以上有する
変性ポリオレフィンを０．１〜５重量％含有せしめてな
る、結晶化が速く熱安定性に優れたポリエチレンテレフ
タレート樹脂組成物を提供するものである。That is, according to the present invention, a layered silicate containing an organic onium ion between layers is added to a polyethylene terephthalate resin in an ash content of 0.01.
To provide a polyethylene terephthalate resin composition which contains 10 to 10% by weight and 0.1 to 5% by weight of a modified polyolefin having one or more epoxy groups in the molecule, has rapid crystallization and is excellent in thermal stability. is there.
【０００７】以下、本発明を詳細に説明する。ポリエチ
レンテレフタレート樹脂とは、ポリエステルであって、
その繰り返し単位の酸成分としてテレフタル酸を、ジオ
ール成分としてエチレングリコールをそれぞれ必須成分
とする重合体である。本発明に用いられるポリエチレン
テレフタレート樹脂においては、酸成分、ジオール成分
ともに共重合成分を含んでも構わないが、酸成分として
テレフタル酸が、ジオール成分としてエチレングリコー
ルが、各々酸成分及びジオール成分中、５０モル％以
上、好ましくは７０モル％以上、更に好ましくは８０モ
ル％以上、最も好ましくは９０モル％以上であるのが望
ましい。これらの量が５０モル％に満たないと、ポリエ
チレンテレフタレート樹脂の特徴、即ち結晶化した場合
の優れた耐熱性と剛性が失われる場合がある。Hereinafter, the present invention will be described in detail. Polyethylene terephthalate resin is polyester,
It is a polymer containing terephthalic acid as an acid component of its repeating unit and ethylene glycol as an essential component as a diol component. The polyethylene terephthalate resin used in the present invention may contain a copolymerization component in both the acid component and the diol component, but terephthalic acid is used as the acid component, ethylene glycol is used as the diol component, and 50% of the acid component and 50 parts of the diol component are used. It is desirable that the amount is at least mol%, preferably at least 70 mol%, more preferably at least 80 mol%, and most preferably at least 90 mol%. If the amount is less than 50 mol%, the characteristics of the polyethylene terephthalate resin, that is, the excellent heat resistance and rigidity when crystallized, may be lost.
【０００８】ポリエチレンテレフタレート樹脂に用いら
れる共重合成分としては、酸成分として、イソフタル
酸、２，６−ナフタレンジカルボン酸、１，５−ナフタ
レンジカルボン酸、２，７−ナフタレンジカルボン酸等
の芳香族ジカルボン酸；アジピン酸、セバシン酸等の脂
肪族ジカルボン酸等；あるいはこれらのアルキルエステ
ル、酸ハライド等のエステル形成性誘導体等が例示で
き、ジオール成分として、テトラメチレングリコール、
ヘキサメチレングリコール、ジエチレングリコール、シ
クロヘキサンジメタノール、シクロヘキサンジオール、
１，４−ビスオキシエトキシベンゼン、ビスフェノール
Ａ等の低分子ジオール；ポリエチレングリコール、ポリ
テトラメチレングリコール、ポリヘキサメチレングリコ
ール等の高分子ジオール等；あるいはこれらのエステル
形成性誘導体等が例示できる。As the copolymerization component used in the polyethylene terephthalate resin, aromatic dicarboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid are used as acid components. Examples thereof include acids; aliphatic dicarboxylic acids such as adipic acid and sebacic acid; and ester-forming derivatives such as alkyl esters and acid halides thereof. Tetramethylene glycol, tetramethylene glycol, etc.
Hexamethylene glycol, diethylene glycol, cyclohexanedimethanol, cyclohexanediol,
Examples thereof include low-molecular diols such as 1,4-bisoxyethoxybenzene and bisphenol A; polymer diols such as polyethylene glycol, polytetramethylene glycol and polyhexamethylene glycol; and ester-forming derivatives thereof.
【０００９】これらの酸成分及びジオール成分は、それ
ぞれ複数種併用したものであっても構わない。また、異
なる組成のポリエチレンテレフタレート樹脂を複数種組
み合わせて用いても構わない。本発明に用いられる層状
珪酸塩としては、Ａｌ，Ｍｇ，Ｌｉ等を含む八面体シー
ト構造を２枚のシリケート四面体シート構造がはさんだ
形の２：１型が好適であり、その単位構造である１層の
厚みは通常９．５オングストローム程度である。A plurality of these acid components and diol components may be used in combination. Also, a plurality of polyethylene terephthalate resins having different compositions may be used in combination. The layered silicate used in the present invention is preferably a 2: 1 type in which an octahedral sheet structure containing Al, Mg, Li and the like is sandwiched by two silicate tetrahedral sheet structures, and a unit structure thereof is preferable. The thickness of a certain layer is usually about 9.5 Å.
【００１０】具体的にはモンモリロナイト、ヘクトライ
ト、フッ素ヘクトライト、サポナイト、バイデライト、
スチブンサイト等のスメクタイト系粘土鉱物；Ｌｉ型フ
ッ素テニオライト、Ｎａ型フッ素テニオライト、Ｎａ型
四珪素フッ素雲母、Ｌｉ型四珪素フッ素雲母等の膨潤性
合成雲母；バーミキュライト、フッ素バーミキュライ
ト、ハロイサイト等が挙げられ、天然のものでも合成さ
れたものでも良い。Specifically, montmorillonite, hectorite, fluorohectorite, saponite, beidellite,
Smectite-based clay minerals such as stevensite; swelling synthetic mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluoromica, Li-type tetrasilicon fluoromica; vermiculite, fluorovermiculite, halloysite, etc. It may be a synthetic one or a synthetic one.
【００１１】本発明においては、これらの層状珪酸塩の
陽イオン交換容量（ＣＥＣ）は通常３０ミリ当量／１０
０ｇ以上とするが、好適には５０ミリ当量／１００ｇ以
上、さらに好適には７０ミリ当量／１００ｇ以上である
のが望ましい。上限について特に制限はないが、通常経
済的に入手し得る最大のものは１２０ミリ当量／１００
ｇ程度である。陽イオン交換容量は、メチレンブルーの
吸着量測定により求めることで測定される。陽イオン交
換容量が３０ミリ当量／１００ｇ未満では、有機オニウ
ムイオンのインターカレーション量が不十分となる場合
がある。In the present invention, the cation exchange capacity (CEC) of these layered silicates is usually 30 meq / 10.
The amount is 0 g or more, preferably 50 meq / 100 g or more, and more preferably 70 meq / 100 g or more. There is no particular upper limit, but the maximum economically available is usually 120 meq / 100
g. The cation exchange capacity is measured by determining the amount of methylene blue adsorbed. If the cation exchange capacity is less than 30 meq / 100 g, the intercalation amount of the organic onium ion may be insufficient.
【００１２】これらの層状珪酸塩の中でも、陽イオン交
換容量や入手容易性から、モンモリロナイト、ヘクトラ
イト等のスメクタイト系粘土鉱物、Ｌｉ型フッ素テニオ
ライト、Ｎａ型フッ素テニオライト、Ｎａ型四珪素フッ
素雲母等の膨潤性合成雲母が好適に用いられ、特に結晶
核剤効果の点でＬｉ型フッ素テニオライト（下記式
ａ）、Ｎａ型フッ素テニオライト（下記式ｂ）、Ｎａ型
四珪素フッ素雲母（下記式ｃ）等の膨潤性フッ素雲母、
及び合成ヘクトライト（下記式ｄ、但しＸは水酸基また
はフッ素原子を表す）が最適である。なお、式ａ，ｂ，
ｃ，及びｄは理想的な組成を示したものであり、厳密に
一致している必要はない。Among these layered silicates, smectite clay minerals such as montmorillonite and hectorite, Li type fluorine teniolite, Na type fluorine teniolite, Na type tetrasilicon fluorine mica and the like are used because of their cation exchange capacity and availability. A swellable synthetic mica is preferably used, and particularly in view of the effect of a crystal nucleating agent, Li-type fluorine teniolite (the following formula a), Na-type fluorine teniolite (the following formula b), Na-type tetrasilicon fluorine mica (the following formula c), etc. Swelling fluoromica,
And synthetic hectorite (the following formula d, where X represents a hydroxyl group or a fluorine atom) is most suitable. Note that equations a, b,
c and d show an ideal composition and do not need to be in exact agreement.
【００１３】[0013]
【数１】 ＬｉＭｇ2 Ｌｉ（Ｓｉ4 Ｏ10）Ｆ2 （ａ） ＮａＭｇ2 Ｌｉ（Ｓｉ4 Ｏ10）Ｆ2 （ｂ） ＮａＭｇ2.5 （Ｓｉ4 Ｏ10）Ｆ2 （ｃ） Ｎａ0.33Ｍｇ2.67Ｌｉ0.33（Ｓｉ4 Ｏ10）Ｘ2 （ｄ）## EQU1 ## LiMg 2 Li (Si 4 O 10 ) F 2 (a) NaMg 2 Li (Si 4 O 10 ) F 2 (b) NaMg 2.5 (Si 4 O 10 ) F 2 (c) Na 0.33 Mg 2.67 Li 0.33 (Si 4 O 10 ) X 2 (d)
【００１４】ポリエチレンテレフタレート樹脂組成物に
おいては、層状珪酸塩が均一に分散していることが望ま
しく、本発明においては、層状珪酸塩の分散性を高める
目的で層状珪酸塩の層間に有機オニウムイオンを含有せ
しめることが必要であり、その操作は一般に親油化処理
と呼ばれる。ここで言う均一な分散とは、分散粒子の平
均粒径が１０〜５００ｎｍ、好ましくは１０〜３００ｎ
ｍ、最も好ましくは１０〜１００ｎｍである状態を意味
する。該平均粒径は、例えば透過型電子顕微鏡観察によ
る画像により求められる量である。該平均粒径が５００
ｎｍを超えると、成形品の表面平滑性が損なわれる場合
があり、１０ｎｍに満たないと核剤効果が不十分となる
場合がある。本発明において該オニウムイオンの挿入に
より、負に帯電した珪酸塩層の層間に分子間力の小さい
有機構造を導入することができ、これにより剪断劈開性
が向上するものと考えられる。層間への該オニウムイオ
ンの挿入は、該オニウムイオンを負の層格子および交換
可能なカチオンを含有する層状珪酸塩とイオン交換反応
させることにより行われる。該イオン交換反応は、例え
ば特公昭６１−５４９２号公報、特開昭６０−４２４５
１号公報等に記載された公知の方法に準じて行うことが
でき、その好ましい反応条件等は、例えば次の様に行わ
れる。In the polyethylene terephthalate resin composition, it is desirable that the layered silicate be uniformly dispersed. In the present invention, an organic onium ion is provided between the layers of the layered silicate for the purpose of enhancing the dispersibility of the layered silicate. It is necessary to contain it, and the operation is generally called a lipophilic treatment. The term “uniform dispersion” as used herein means that the average particle size of dispersed particles is 10 to 500 nm, preferably 10 to 300 n.
m, most preferably 10 to 100 nm. The average particle size is, for example, an amount obtained from an image observed by a transmission electron microscope. The average particle size is 500
When it exceeds 10 nm, the surface smoothness of the molded product may be impaired, and when it is less than 10 nm, the nucleating agent effect may be insufficient. In the present invention, by inserting the onium ion, an organic structure having a small intermolecular force can be introduced between the layers of the negatively charged silicate layer, which is considered to improve the shear cleavability. The insertion of the onium ion between the layers is performed by subjecting the onium ion to an ion exchange reaction with a layered silicate containing a negative layer lattice and an exchangeable cation. The ion exchange reaction is carried out, for example, in Japanese Examined Patent Publication No. 61-5492 and Japanese Patent Laid-Open No. 60-4245.
It can be carried out according to a known method described in JP-A No. 1, etc., and preferable reaction conditions and the like are as follows, for example.
【００１５】有機オニウムイオンとは、アンモニウムイ
オン、ホスホニウムイオン、スルホニウムイオン、複素
芳香環由来のオニウムイオン等に代表される構造を持つ
ものである。これらのうち入手容易性、安定性の観点か
らは、アンモニウムイオン、ホスホニウムイオン、複素
芳香環由来のオニウムイオンが好適である。アンモニウ
ムイオンとしては、１級アンモニウム類、２級アンモニ
ウム類、３級アンモニウム類、４級アンモニウム類が挙
げられる。The organic onium ion has a structure represented by ammonium ion, phosphonium ion, sulfonium ion, onium ion derived from a heteroaromatic ring and the like. Of these, ammonium ions, phosphonium ions and onium ions derived from a heteroaromatic ring are preferable from the viewpoints of easy availability and stability. Examples of ammonium ions include primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium.
【００１６】具体的には、１級アンモニウム類として、
アルキルアンモニウム（ドデシルアンモニウム、ヘキサ
デシルアンモニウム、オクタデシルアンモニウム等）、
ω−アミノ酸アンモニウム（６−アミノヘキサン酸、８
−アミノオクタン酸、１０−アミノデカン酸、１２−ア
ミノドデカン酸等）が挙げられる。２級アンモニウム類
としては、メチルドデシルアンモニウム、ブチルドデシ
ルアンモニウム、メチルオクタデシルアンモニウム等
が、また３級アンモニウム類としてはジメチルドデシル
アンモニウム、ジメチルヘキサデシルアンモニウム、ジ
メチルオクタデシルアンモニウム、ジフェニルドデシル
アンモニウム、ジフェニルオクタデシルアンモニウム等
が挙げられるSpecifically, as primary ammonium compounds,
Alkyl ammonium (dodecyl ammonium, hexadecyl ammonium, octadecyl ammonium, etc.),
ω-amino acid ammonium (6-aminohexanoic acid, 8
-Aminooctanoic acid, 10-aminodecanoic acid, 12-aminododecanoic acid, etc.). Examples of secondary ammoniums include methyldodecyl ammonium, butyl dodecyl ammonium, and methyl octadecyl ammonium, and examples of tertiary ammoniums include dimethyl dodecyl ammonium, dimethyl hexadecyl ammonium, dimethyl octadecyl ammonium, diphenyl dodecyl ammonium, and diphenyl octadecyl ammonium. Can be mentioned
【００１７】４級アンモニウム類としては、分子中にア
ルキル基のみを有するテトラアルキルアンモニウムと、
アルキル基以外の基を有する４級アンモニウムとが挙げ
られる。テトラアルキルアンモニウムとして、具体的に
は同一アルキル基を４つ有するアンモニウム（テトラエ
チルアンモニウム、テトラブチルアンモニウム、テトラ
オクチルアンモニウム等）；分子中に異種アルキル基を
４つ有するアンモニウム、特に、炭素数１−４の低級ア
ルキル基と炭素数５以上、好ましくは８以上のアルキル
基とを有するアンモニウム、即ち、低級アルキル基を分
子中に３つ有するアンモニウム、例えばトリメチルアン
モニウム（トリメチルオクチルアンモニウム、トリメチ
ルデシルアンモニウム、トリメチルドデシルアンモニウ
ム、トリメチルテトラデシルアンモニウム、トリメチル
ヘキサデシルアンモニウム、トリメチルオクタデシルア
ンモニウム、トリメチルエイコサニルアンモニウム、ト
リメチルオクタデセニルアンモニウム、トリメチルオク
タデカジエニルアンモニウム等）、トリエチルアンモニ
ウム（トリエチルドデシルアンモニウム、トリエチルテ
トラデシルアンモニウム、トリエチルヘキサデシルアン
モニウム、トリエチルオクタデシルアンモニウム等）、
トリブチルアンモニウム（トリブチルドデシルアンモニ
ウム、トリブチルテトラデシルアンモニウム、トリブチ
ルヘキサデシルアンモニウム、トリブチルオクタデシル
アンモニウム等）；低級アルキル基を分子中に２つ有す
るアンモニウム、例えばジメチルジアルキルアンモニウ
ム（ジメチルジオクチルアンモニウム、ジメチルジデシ
ルアンモニウム、ジメチルジテトラデシルアンモニウ
ム、ジメチルジヘキサデシルアンモニウム、ジメチルジ
オクタデシルアンモニウム、ジメチルジオクタデセニル
アンモニウム、ジメチルジオクタデカジエニルアンモニ
ウム等）、ジエチルジアルキルアンモニウム（ジエチル
ジドデシルアンモニウム、ジエチルジテトラデシルアン
モニウム、ジエチルジヘキサデシルアンモニウム、ジエ
チルジオクタデシルアンモニウム等）、ジブチルジアル
キルアンモニウム（ジブチルジドデシルアンモニウム、
ジブチルジテトラデシルアンモニウム、ジブチルジヘキ
サデシルアンモニウム、ジブチルジオクタデシルアンモ
ニウム等）；低級アルキル基を分子中に１つだけ有する
アンモニウム、例えばトリアルキルメチルアンモニウム
（トリオクチルメチルアンモニウム、トリドデシルメチ
ルアンモニウム、トリテトラデシルメチルアンモニウム
等）、トリアルキルエチルアンモニウム（トリオクチル
エチルアンモニウム、トリドデシルエチルアンモニウム
等）、トリアルキルブチルアンモニウム（トリオクチル
ブチルアンモニウム、トリドデシルブチルアンモニウム
等）が挙げられる。The quaternary ammoniums include tetraalkylammonium having only an alkyl group in the molecule,
And quaternary ammonium having a group other than an alkyl group. As the tetraalkylammonium, specifically, an ammonium having four identical alkyl groups (tetraethylammonium, tetrabutylammonium, tetraoctylammonium, etc.); an ammonium having four different alkyl groups in the molecule, particularly, a carbon number of 1-4. Ammonium having a lower alkyl group and an alkyl group having 5 or more, preferably 8 or more carbon atoms, that is, ammonium having 3 lower alkyl groups in the molecule, for example, trimethylammonium (trimethyloctylammonium, trimethyldecylammonium, trimethyldodecyl). Ammonium, trimethyltetradecyl ammonium, trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, trimethyl eicosanyl ammonium, trimethyl octadecenyl ammonium Moniumu, trimethyl octadecadienyl ammonium, etc.), triethylammonium (triethylammonium dodecyl ammonium, triethyl tetradecyl ammonium, triethyl hexadecyl ammonium, triethyl ammonium, etc.),
Tributylammonium (tributyldodecylammonium, tributyltetradecylammonium, tributylhexadecylammonium, tributyloctadecylammonium, etc.); ammonium having two lower alkyl groups in the molecule, such as dimethyldialkylammonium (dimethyldioctylammonium, dimethyldidecylammonium, dimethyl) Ditetradecylammonium, dimethyldihexadecylammonium, dimethyldioctadecylammonium, dimethyldioctadecenylammonium, dimethyldioctadecadienylammonium), diethyldialkylammonium (diethyldidodecylammonium, diethylditetradecylammonium, diethyl) Dihexadecyl ammonium, diethyl dioctadecyl Ammonium etc.), dibutyl dialkyl ammonium (dibutyl dodecyl ammonium,
Dibutylditetradecylammonium, dibutyldihexadecylammonium, dibutyldioctadecylammonium, etc.); ammonium having only one lower alkyl group in the molecule, for example trialkylmethylammonium (trioctylmethylammonium, tridodecylmethylammonium, tritetramethylammonium) Decylmethylammonium etc.), trialkylethylammonium (trioctylethylammonium, tridodecylethylammonium etc.), trialkylbutylammonium (trioctylbutylammonium, tridodecylbutylammonium etc.).
【００１８】また、アルキル基以外の基を有する４級ア
ンモニウムとして、具体的には、芳香環を有する４級ア
ンモニウム（メチルベンジルジヘキサデシルアンモニウ
ム、ジベンジルジヘキサデシルアンモニウム、トリメチ
ルベンジルアンモニウム等）、芳香族アミン由来の４級
アンモニウム（トリメチルフェニルアンモニウム等）が
挙げられる。As the quaternary ammonium having a group other than an alkyl group, specifically, quaternary ammonium having an aromatic ring (methylbenzyldihexadecylammonium, dibenzyldihexadecylammonium, trimethylbenzylammonium, etc.), Examples thereof include quaternary ammonium derived from aromatic amine (trimethylphenylammonium, etc.).
【００１９】更に、ホスホニウムイオンとしては、アル
キル４級ホスホニウム（テトラブチルホスホニウム、テ
トラオクチルホスホニウム、トリメチルデシルホスホニ
ウム、トリメチルドデシルホスホニウム、トリメチルヘ
キサデシルホスホニウム、トリメチルオクタデシルホス
ホニウム、トリブチルドデシルホスホニウム、トリブチ
ルヘキサデシルホスホニウム、トリブチルオクタデシル
ホスホニウム等）や、フェニル基を有する４級ホスホニ
ウム（フェニルトリメチルホスホニウム、フェニルトリ
ブチルホスホニウム、ジフェニルジオクチルホスホニウ
ム、トリフェニルオクタデシルホスホニウム、テトラフ
ェニルホスホニウム等）等の４級ホスホニウム類が挙げ
られ、複素芳香環由来のオニウムイオンとしては、ピリ
ジニウム、メチルピリジニウム、ジメチルピリジニウ
ム、キノリニウム、イソキノリニウム、ニコチン酸やニ
コチンアミド等のオニウムイオンが挙げられる。Further, as the phosphonium ion, alkyl quaternary phosphonium (tetrabutylphosphonium, tetraoctylphosphonium, trimethyldecylphosphonium, trimethyldodecylphosphonium, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, tributyldodecylphosphonium, tributylhexadecylphosphonium, tributyl) is used. Octadecylphosphonium) and quaternary phosphoniums such as quaternary phosphoniums having a phenyl group (phenyltrimethylphosphonium, phenyltributylphosphonium, diphenyldioctylphosphonium, triphenyloctadecylphosphonium, tetraphenylphosphonium, etc.), and derived from heteroaromatic rings. Onium ions include pyridinium and methyl Rijiniumu, dimethyl pyridinium, quinolinium, isoquinolinium, include onium such as nicotinic acid or nicotinamide.
【００２０】これらの有機オニウムイオンのうち珪酸塩
層間の疎水化に寄与する炭化水素構造の有効性の観点か
ら、一分子中にメチル又はエチル基を２つ又は３つ有
し、ドデシル、テトラデシル、ヘキサデシル、オクタデ
シル等の炭素数１２以上のアルキル基を１つ又は２つ有
するアルキル４級アンモニウム、一分子中にメチル、エ
チル又はブチル基を３つと炭素数１２以上のアルキル基
を１つ有する４級ホスホニウム等のイオンが好適に用い
られる。中でも、メチル基３つと炭素数１６以上のアル
キル基を１分子中に１つ有する４級アンモニウム、メチ
ル基２つと炭素数１４以上のアルキル基を１分子中に２
つ有する４級アンモニウム、炭素数１４以上のアルキル
基を有する４級ホスホニウム等のイオンが好適に用いら
れ、最も好適にはトリメチルオクタデシルアンモニウム
イオン、ジメチルジヘキサデシルアンモニウムイオン、
ジメチルジオクタデシルアンモニウムイオン、トリブチ
ルヘキサデシルホスホニウムイオン、トリブチルオクタ
デシルホスホニウムイオンが用いられる。これらの有機
オニウムイオンは、単独でも複数種類の混合物としても
使用できる。Of these organic onium ions, from the viewpoint of the effectiveness of the hydrocarbon structure that contributes to the hydrophobicization between silicate layers, each molecule has two or three methyl or ethyl groups, dodecyl, tetradecyl, Alkyl quaternary ammonium having one or two alkyl groups having 12 or more carbon atoms such as hexadecyl and octadecyl, quaternary ammonium having three methyl, ethyl or butyl groups and one alkyl group having 12 or more carbon atoms in one molecule Ions such as phosphonium are preferably used. Among them, quaternary ammonium having three methyl groups and one alkyl group having 16 or more carbon atoms in one molecule, two methyl groups and two alkyl groups having 14 or more carbon atoms in one molecule
Ions such as quaternary ammonium having four or quaternary phosphonium having an alkyl group having 14 or more carbon atoms are preferably used, most preferably trimethyloctadecyl ammonium ion, dimethyldihexadecyl ammonium ion,
Dimethyldioctadecyl ammonium ion, tributyl hexadecyl phosphonium ion, and tributyl octadecyl phosphonium ion are used. These organic onium ions can be used alone or as a mixture of plural kinds.
【００２１】層状珪酸塩の層間への有機オニウムイオン
の挿入は、極性溶媒、好ましくは水、メタノール、エタ
ノール、プロパノール、ブタノール等のプロトン性溶媒
及びこれら２種以上の混合溶媒中で進行するイオン交換
反応による。本発明に用いられる層間化合物の製造に好
ましい溶媒は、水、メタノール、エタノールであるが有
機オニウム塩の溶解度が極端に低くならない限り水が最
適である。The insertion of the organic onium ion between the layers of the layered silicate is carried out in a polar solvent, preferably a protic solvent such as water, methanol, ethanol, propanol, butanol or a mixed solvent of two or more of these ions. It depends on the reaction. Preferred solvents for producing the intercalation compound used in the present invention are water, methanol and ethanol, but water is most suitable as long as the solubility of the organic onium salt does not become extremely low.
【００２２】生成した層間化合物は、有機オニウムイオ
ンの挿入反応後、層間以外に残存する余分なイオンを除
去するために、溶媒中での撹拌洗浄工程と遠心分離や濾
過等の分離工程を繰り返すバッチ洗浄、あるいは連続的
に溶媒を流して洗浄する連続洗浄等の適切な方法による
精製を行なう。精製度は、例えば４級アンモニウムハラ
イドを原料とした場合、硝酸銀水溶液を洗液に加えて白
色のハロゲン化銀の生成が見られなくなることで確認で
きる。この精製が不十分な場合、有機オニウムイオン由
来の遊離化合物による成形時の熱安定性低下、発煙、金
型汚染、臭気等の原因となる。また層間化合物の精製後
の水分量は、ポリエチレンテレフタレート樹脂との混合
時の加水分解等の望ましくない副反応を低減するため
に、１０ｗｔ％以下、好ましくは５ｗｔ％以下、さらに
好ましくは３ｗｔ％以下に制御する。該水分量が１０ｗ
ｔ％を超えると、ポリエチレンテレフタレート樹脂の加
水分解による分子量低下が顕著となり、ポリエチレンテ
レフタレート樹脂組成物の靱性が大きく低下する。The produced intercalation compound is a batch obtained by repeating the stirring and washing step in a solvent and the separation step such as centrifugation and filtration in order to remove the extra ions remaining other than between the layers after the insertion reaction of the organic onium ion. Purification is carried out by an appropriate method such as washing or continuous washing in which a solvent is continuously flown for washing. The degree of purification can be confirmed, for example, when a quaternary ammonium halide is used as a raw material, an aqueous silver nitrate solution is added to the washing solution, and white silver halide is not produced. If this purification is insufficient, it may cause deterioration of thermal stability at the time of molding due to a free compound derived from an organic onium ion, smoke generation, mold contamination, odor and the like. The water content of the intercalation compound after purification is 10 wt% or less, preferably 5 wt% or less, and more preferably 3 wt% or less in order to reduce undesirable side reactions such as hydrolysis during mixing with the polyethylene terephthalate resin. Control. The water content is 10w
When it exceeds t%, the molecular weight is significantly reduced due to hydrolysis of the polyethylene terephthalate resin, and the toughness of the polyethylene terephthalate resin composition is significantly reduced.
【００２３】層間化合物中の有機オニウムイオンの量
は、原料の層状珪酸塩の陽イオン交換容量に対し０．８
〜２．０当量の範囲であれば特に制限はないが、通常の
反応条件では０．９〜１．３当量程度となる。この量が
０．８当量よりも少ないと分散性が低下し、２．０当量
より多いと該オニウムイオン由来の遊離化合物が顕著と
なり成形時の熱安定性低下、発煙、金型汚染、臭気等の
原因となる場合がある。The amount of the organic onium ion in the intercalation compound is 0.8 with respect to the cation exchange capacity of the starting layered silicate.
There is no particular limitation as long as it is in the range of 2.0 to 2.0 equivalents, but it is about 0.9 to 1.3 equivalents under normal reaction conditions. If this amount is less than 0.8 equivalents, the dispersibility will decrease, and if it is more than 2.0 equivalents, the free compounds derived from the onium ion will be noticeable and the thermal stability will decrease during molding, smoke generation, mold contamination, odor, etc. May cause
【００２４】有機オニウムイオンを層間に含有する層状
珪酸塩の含有量は、ポリエチレンテレフタレート樹脂に
対して、灰分量として０．０１〜１０重量％、好ましく
は０．０５〜７重量％、更に好ましくは０．１〜５重量
％である。この量が０．０１重量％に満たないと核剤効
果が発現せず、１０重量％を越えると靱性が十分でな
く、成形表面性も悪くなるため好ましくない。The content of the layered silicate containing the organic onium ion between the layers is 0.01 to 10% by weight, preferably 0.05 to 7% by weight, more preferably ash content based on the polyethylene terephthalate resin. It is 0.1 to 5% by weight. If this amount is less than 0.01% by weight, the nucleating agent effect will not be exhibited, and if it exceeds 10% by weight, the toughness will be insufficient and the molding surface property will be poor, such being undesirable.
【００２５】また、該層状珪酸塩のポリエチレンテレフ
タレート樹脂組成物における添加量としては、上記灰分
量に相当する範囲で良く、具体的には０．０１〜２０重
量％程度である。灰分量はポリエチレンテレフタレート
樹脂の有機分を６５０℃の電気炉内で完全に燃失せしめ
た残渣の重量分率から求めることができる。本発明のポ
リエチレンテレフタレート樹脂組成物は、エポキシ基を
分子内に少なくとも１つ有する変性ポリオレフィンを含
有する必要がある。該変性ポリオレフィンは、ポリエチ
レンテレフタレート樹脂分子鎖が折りたたみ結晶化する
際の分子鎖可動性を高める可塑剤として機能するものと
推定される。The amount of the layered silicate added to the polyethylene terephthalate resin composition may be in the range corresponding to the above ash content, and is specifically about 0.01 to 20% by weight. The amount of ash can be obtained from the weight fraction of the residue obtained by completely burning off the organic content of the polyethylene terephthalate resin in an electric furnace at 650 ° C. The polyethylene terephthalate resin composition of the present invention needs to contain a modified polyolefin having at least one epoxy group in the molecule. It is presumed that the modified polyolefin functions as a plasticizer that enhances the molecular chain mobility when the polyethylene terephthalate resin molecular chain is folded and crystallized.
【００２６】ポリオレフィンとは、エチレンあるいはα
−オレフィンを共重合せしめた重合体である。α−オレ
フィンの具体例として、プロペン、ブテン、ペンテン、
ヘキセン、ヘプテン、オクテン等の直鎖状オレフィン
類、３−メチルブテン、３−メチルペンテン、３−メチ
ルヘキセン、４−メチルペンテン、４−メチルヘキセン
等の側鎖を持つオレフィン類等が挙げられる。オレフィ
ンの共重合比には特に制限はない。またポリオレフィン
の重合度は、総炭素数にして通常は１０〜５０００、可
塑剤効果から好ましくは２０〜１０００、より好ましく
は２０〜５００、更に好ましくは２０〜２００、最も好
ましくは２０〜１００程度とする。Polyolefin means ethylene or α
A polymer obtained by copolymerizing olefins. Specific examples of the α-olefin include propene, butene, pentene,
Examples include linear olefins such as hexene, heptene, and octene, and olefins having side chains such as 3-methylbutene, 3-methylpentene, 3-methylhexene, 4-methylpentene, and 4-methylhexene. The copolymerization ratio of olefin is not particularly limited. The degree of polymerization of the polyolefin is generally 10 to 5,000 in terms of total carbon number, preferably 20 to 1,000, more preferably 20 to 500, still more preferably 20 to 200, and most preferably 20 to 100 from the plasticizer effect. To do.
【００２７】ポリオレフィンへのエポキシ基の導入方法
及びその結合位置に制限はなく、例えばビニルグリシジ
ルエーテル、アリルグリシジルエーテル、グリシジルア
クリレート、グリシジルメタクリレート、グリシジルク
ロトネート等の共重合性のエポキシ基含有モノマーを共
重合して導入しても良いし、連鎖移動剤、停止剤等にエ
ポキシ基を有する化合物を用いて末端に導入しても良
い。エポキシ基の数は、通常、ポリオレフィンの炭素数
５〜１００に対して１個程度、好ましくは炭素数１０〜
５０に対して１個程度、より好ましくは炭素数１０〜４
０に対して１個程度、最も好ましくは炭素数２０〜４０
に対して１個程度である。There is no limitation on the method of introducing the epoxy group into the polyolefin and the bonding position thereof. For example, a copolymerizable epoxy group-containing monomer such as vinyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, etc. It may be introduced by polymerization, or may be introduced at the terminal by using a compound having an epoxy group as a chain transfer agent, a terminating agent or the like. The number of epoxy groups is usually about 1 to 5 to 100 carbon atoms of polyolefin, preferably 10 to 10 carbon atoms.
About 1 to 50, more preferably 10 to 4 carbon atoms
About 1 to 0, most preferably 20 to 40 carbon atoms
Is about one.
【００２８】エポキシ基を分子内に１以上有する変性ポ
リオレフィンの含有量は、ポリエチレンテレフタレート
樹脂に対して、０．１〜５重量％、好ましくは０．１〜
４重量％、更に好ましくは０．５〜３重量％である。こ
の量が０．１重量％未満であると核剤効果が不十分であ
り、５重量％を越えるとブリードアウトが発現し、耐熱
性が十分に得られない。The content of the modified polyolefin having one or more epoxy groups in the molecule is 0.1 to 5% by weight, preferably 0.1 to 5% by weight based on the polyethylene terephthalate resin.
It is 4% by weight, more preferably 0.5 to 3% by weight. If this amount is less than 0.1% by weight, the nucleating agent effect will be insufficient, and if it exceeds 5% by weight, bleed-out will occur and heat resistance will not be sufficiently obtained.
【００２９】本発明のポリエチレンテレフタレート樹脂
組成物には、必要に応じて結晶核剤、充電材、強化材、
可塑剤等の添加剤を併用できる。例えば結晶核剤、充填
材または強化材としては、タルク、クレー、カリオン、
マイカ、シリカ、窒化ホウ素、窒化珪素等の無機微粒
子、カーボンブラック、グラファイト等の炭素化合物、
アルミナ、チタニア、ジルコニア、二酸化チタン等の金
属酸化物、硫酸カルシウム、硫酸バリウム等の硫酸塩、
リン酸カルシウム、リン酸バリウム等のリン酸塩、炭酸
カルシウム、炭酸バリウム、炭酸マグネシウム等の炭酸
塩が挙げられる。これらの他に、結晶核剤としてｐ−フ
ェノールスルホン酸のナトリウム塩、ｐ−ヒドロキシ安
息香酸のナトリウム塩等の有機酸金属塩が、強化材とし
てガラス繊維、カーボン繊維、ガラスフレーク、ガラス
ビーズ、チタン酸繊維、ほう酸アルミニウム繊維などが
挙げられる。In the polyethylene terephthalate resin composition of the present invention, if necessary, a crystal nucleating agent, a charging material, a reinforcing material,
Additives such as plasticizers can be used in combination. For example, as a crystal nucleating agent, filler or reinforcing material, talc, clay, carion,
Inorganic fine particles such as mica, silica, boron nitride and silicon nitride, carbon compounds such as carbon black and graphite,
Alumina, titania, zirconia, metal oxides such as titanium dioxide, sulfates such as calcium sulfate and barium sulfate,
Examples thereof include phosphates such as calcium phosphate and barium phosphate, and carbonates such as calcium carbonate, barium carbonate and magnesium carbonate. In addition to these, organic acid metal salts such as sodium salt of p-phenolsulfonic acid and sodium salt of p-hydroxybenzoic acid as a crystal nucleating agent, glass fiber, carbon fiber, glass flakes, glass beads, titanium as a reinforcing material. Examples thereof include acid fibers and aluminum borate fibers.
【００３０】これらの充填材や強化材は、エポキシシラ
ンやアミノシランのような官能化シランカップリング剤
で処理して、ポリエチレンテレフタレート樹脂とのなじ
みを改良することもできる。また可塑剤としては、ステ
アリン酸カルシウム、ステアリン酸バリウム等の長鎖脂
肪酸塩、モンタン酸誘導体、金属グリコレート類等が使
用できる。These fillers and reinforcements can also be treated with a functionalized silane coupling agent such as epoxysilane or aminosilane to improve their compatibility with the polyethylene terephthalate resin. As the plasticizer, long-chain fatty acid salts such as calcium stearate and barium stearate, montanic acid derivatives, metal glycolates and the like can be used.
【００３１】本発明のポリエチレンテレフタレート樹脂
組成物には、必要に応じて他の熱可塑性樹脂を配合して
も構わない。かかる熱可塑性樹脂として、ポリブチレン
テレフタレート、ポリブチレンナフタレート、ポリエチ
レンナフタレート、ポリシクロヘキシレンテレフタレー
ト、シクロヘキサンジメタノールとテレフタル酸よりな
るポリエステル等の芳香族ポリエステル樹脂、芳香族ポ
リカーボネート樹脂、ポリアミド樹脂、フェノキシ樹
脂、エポキシ樹脂、ポリフェニレンエーテル樹脂、ポリ
アリーレンスルフィド樹脂、ポリスチレン樹脂、アクリ
ル樹脂、熱可塑性ポリウレタン樹脂、ポリアミドエラス
トマー、ポリエステルエラストマー、ポリエーテルエラ
ストマー、アクリルゴム、コアシェル型アクリルゴム、
スチレン系熱可塑性エラストマー、ポリエチレングリコ
ール、ポリテトラメチレングリコール等が例示できる。The polyethylene terephthalate resin composition of the present invention may be blended with another thermoplastic resin, if necessary. Such thermoplastic resins include polybutylene terephthalate, polybutylene naphthalate, polyethylene naphthalate, polycyclohexylene terephthalate, aromatic polyester resins such as polyesters composed of cyclohexanedimethanol and terephthalic acid, aromatic polycarbonate resins, polyamide resins, phenoxy resins. , Epoxy resin, polyphenylene ether resin, polyarylene sulfide resin, polystyrene resin, acrylic resin, thermoplastic polyurethane resin, polyamide elastomer, polyester elastomer, polyether elastomer, acrylic rubber, core-shell type acrylic rubber,
Examples thereof include styrene-based thermoplastic elastomer, polyethylene glycol, polytetramethylene glycol and the like.
【００３２】本発明の樹脂組成物の製造方法には特に制
限はないが、通常、溶融混合が用いられる。具体的に
は、二軸押出機、単軸押出機、ブラベンダー、ロール、
ヘンシェルミキサー、バンバリーミキサー、ニーダー等
の混練、混合機等が利用される。この時、熱安定剤、紫
外線吸収剤、酸化防止剤、帯電防止剤、難燃剤、顔料、
滑剤等を混合しても良い。The method for producing the resin composition of the present invention is not particularly limited, but usually melt mixing is used. Specifically, twin screw extruder, single screw extruder, Brabender, roll,
A kneading machine such as a Henschel mixer, a Banbury mixer, a kneader, or a mixer is used. At this time, heat stabilizer, ultraviolet absorber, antioxidant, antistatic agent, flame retardant, pigment,
A lubricant or the like may be mixed.
【００３３】[0033]
【実施例】以下、本発明を具体例を挙げて説明するが、
本発明はその主旨を逸脱しない限りにおいてこれら諸例
により何ら制限を受けるものではない。なお、以下の諸
例の評価結果は、表２にまとめた。 ［評価項目］ （１）結晶化度 日本製鋼所（株）製Ｊ２８ＳＡ射出成形機により、２ｍ
ｍ厚の平板（５ｃｍ角）をバレル温度２９０℃、金型温
度８０℃、射出／冷却＝１０／１０秒、射出速度最大の
条件で成形した。次いで、この平板の中央部よりカッタ
ーで小片を切り出し、デュポン（株）製ＤＳＣ２０００
により２５℃から３００℃の間を１６℃／分の速度で昇
降温（３００℃で５分間保持）して、昇温時の平板の後
結晶化温度Ｔｃｃ（℃）及び後結晶化熱△Ｈｃｃ（Ｊ／
ｇ）、試料片の融解熱△Ｈｍ（Ｊ／ｇ）、降温時の結晶
化温度Ｔｃ（℃）及び結晶化熱△Ｈｃ（Ｊ／ｇ）、の各
項目を測定し、下式ｅによりＤｃ（％）を算出して平板
の結晶化度を見積もった。EXAMPLES The present invention will be described below with reference to specific examples.
The present invention is not limited to these examples without departing from the spirit of the invention. The evaluation results of the following examples are summarized in Table 2. [Evaluation Items] (1) Crystallinity 2 m by J28SA injection molding machine manufactured by Japan Steel Works, Ltd.
An m-thick flat plate (5 cm square) was molded under conditions of a barrel temperature of 290 ° C., a mold temperature of 80 ° C., injection / cooling = 10/10 seconds, and a maximum injection speed. Next, a small piece is cut out from the center of this flat plate with a cutter, and manufactured by DuPont DSC2000.
The temperature of the flat plate is raised and lowered between 25 ° C. and 300 ° C. at a rate of 16 ° C./min (holding at 300 ° C. for 5 minutes), and the post-crystallization temperature Tcc (° C.) and the post-crystallization heat ΔHcc of the flat plate during the temperature increase (J /
g), the heat of fusion of the sample piece ΔHm (J / g), the crystallization temperature Tc (° C.) during cooling, and the heat of crystallization ΔHc (J / g) are measured, and Dc is calculated by the following equation e. (%) Was calculated to estimate the crystallinity of the flat plate.
【００３４】[0034]
【数２】 Ｄｃ＝（△Ｈｍ−△Ｈｃｃ）／△Ｈｃ （ｅ）## EQU00002 ## Dc = (. DELTA.Hm-.DELTA.Hcc) /. DELTA.Hc (e)
【００３５】ｅ式は、金型中での実冷却速度が上記ＤＳ
Ｃ測定の冷却速度１６℃／分よりもはるかに大きいこと
から、該ＤＳＣ測定での降温結晶化により、実質的に結
晶化可能な部分の到達結晶化度は１００％となるものと
して定義した。実成形での結晶化度は△Ｈｃｃが小さい
程、Ｄｃが大きい程大きく、試料の結晶化能力はＴｃｃ
が低い程、Ｔｃが高い程、△Ｈｃが大きい程高いと評価
できる。In the equation e, the actual cooling rate in the mold is the above DS.
Since the cooling rate for C measurement was much higher than 16 ° C./min, the ultimate crystallinity of the substantially crystallizable portion was defined as 100% by the temperature-down crystallization in the DSC measurement. The crystallinity in actual molding is larger as ΔHcc is smaller and Dc is larger, and the crystallization ability of the sample is Tcc.
It can be evaluated that the lower is, the higher is Tc, and the higher is ΔHc.
【００３６】（２）分子量 試料をフェノール／ｓｙｍ−テトラクロロエタン（５０
／５０重量％）混合溶液に１ｇ／ｄｌ濃度で溶解し、溶
液粘度測定を３０℃で行い、極限粘度［η］（ｄｌ／
ｇ）で評価した。 （３）熱安定性 島津製作所（株）製フローテスタＣＦＴ５００Ｃにて、
２８０℃のシリンダ内に上記平板試料を詰め７分間滞留
した場合の極限粘度［η］（ｄｌ／ｇ）の変化を測定し
た。 （４）使用した層状珪酸塩 表１に使用した層状珪酸塩の名称、鉱物名、種類、メチ
レンブルー吸着法により測定した陽イオン交換容量、メ
ーカーを記載した。(2) Molecular weight A sample was prepared from phenol / sym-tetrachloroethane (50
/ 50% by weight) in a mixed solution at a concentration of 1 g / dl, and the solution viscosity is measured at 30 ° C. to obtain an intrinsic viscosity [η] (dl /
It was evaluated in g). (3) Thermal stability With a flow tester CFT500C manufactured by Shimadzu Corporation,
The change in the intrinsic viscosity [η] (dl / g) when the flat plate sample was packed in a cylinder at 280 ° C. and retained for 7 minutes was measured. (4) Layered silicate used Table 1 shows the name, mineral name, type, cation exchange capacity measured by the methylene blue adsorption method, and manufacturer of the layered silicate used.
【００３７】[0037]
【表１】 [Table 1]
【００３８】（５）層状珪酸塩の親油化処理（実施例２
および３） 層状珪酸塩約１００ｇを精秤しこれを室温の水１０リッ
トルに撹拌分散し、ここにイオン交換容量の１．２倍当
量のアンモニウムイオンの塩酸塩を添加して６時間撹拌
した。精製した沈降性の個体を濾別し、次いで３０リッ
トルの脱塩水中で撹拌洗浄後再び濾別した。この洗浄と
濾別の操作を少なくとも３回行い、洗液の硝酸銀試験で
塩化物イオンが検出されなくなるのを確認した。得られ
た個体は３〜７日の風乾後乳鉢で粉砕し、更に５０℃の
温風乾燥を３〜１０時間行い再度乳鉢で粉砕した。乾燥
条件はゲストのアンモニウムイオンの種類により変動す
るが、最大粒径が１００ミクロン程度となる粉砕性の確
保と、窒素気流下１２０℃で１時間保持した場合の熱重
量減少で評価した残留水分量が２〜３ｗｔ％となること
を指標とした。(5) Lipophilic treatment of layered silicate (Example 2)
And 3) About 100 g of layered silicate was precisely weighed and dispersed in 10 liters of water at room temperature with stirring, and 1.2 times equivalent of ion exchange capacity of ammonium ion hydrochloride was added thereto and stirred for 6 hours. The purified precipitated solid was filtered off, washed with stirring in 30 liters of demineralized water, and then filtered off again. This washing and filtering operation was performed at least three times, and it was confirmed by the silver nitrate test of the washing liquid that chloride ions could not be detected. The obtained solid was air-dried for 3 to 7 days, then pulverized in a mortar, and then dried in warm air at 50 ° C. for 3 to 10 hours, and pulverized again in the mortar. Drying conditions vary depending on the type of guest's ammonium ion, but the residual water content evaluated by securing pulverizability with a maximum particle size of about 100 microns and thermogravimetric reduction when kept at 120 ° C for 1 hour under nitrogen flow Was used as an index.
【００３９】［実施例１］三酸化アンチモンを重合触媒
として製造したポリエチレンテレフタレート（［η］＝
０．６４（ｄｌ／ｇ））９７重量部、親油化合成スメク
タイト（合成ヘクトライト層間にジメチルジステアリル
アンモニウムを１．１当量挿入したもの） ［コープケミカル（株）製ＳＡＮ］１．３重量部、及び
片末端にエポキシ基を有するα−オレフィン重合体（炭
素数約３０）［アデカ・アーガス（株）製ＡＯＥ−Ｚ］
２重量部をドレイブレンドし、東芝機械（株）製ＴＥＭ
３５Ｂ二軸押出機により溶融混練した。混練条件は、バ
レル温度設定は２８０℃、スクリュはニーディングディ
スクを一カ所有する構成とし１５０ｒｐｍの回転速度と
した。得られる溶融ストランドを水冷しペレット化し
た。この組成物ペレットを真空乾燥後、上記評価に使用
した。[Example 1] Polyethylene terephthalate prepared by using antimony trioxide as a polymerization catalyst ([η] =
0.64 (dl / g)) 97 parts by weight, lipophilic synthetic smectite (inserted 1.1 equivalents of dimethyl distearyl ammonium between synthetic hectorite layers) [Cop Chemical Co., Ltd. SAN] 1.3 parts by weight Part and an α-olefin polymer having an epoxy group at one end (having about 30 carbon atoms) [AOE-Z manufactured by Adeka Argus Co., Ltd.]
2 parts by weight of Dray blend, TEM manufactured by Toshiba Machine Co., Ltd.
It was melt-kneaded by a 35B twin-screw extruder. The kneading conditions were such that the barrel temperature was set to 280 ° C., the kneading disk was used as a single screw, and the rotation speed was 150 rpm. The resulting melt strand was water cooled and pelletized. The composition pellet was vacuum dried and then used for the above evaluation.
【００４０】［実施例２］実施例１に於いて、親油化合
成スメクタイトのかわりに、膨潤性合成雲母（フッ素テ
ニオライト構造）［コープケミカル（株）製ＭＥ−１０
０］に同様の親油化処理、即ちジメチルジステアリルア
ンモニウムを１．０５当量挿入したものを使用して同様
の実験を行った。 ［実施例３］実施例１に於いて、親油化合成スメクタイ
トＳＡＮのかわりに、未処理合成スメクタイト（ヘクト
ライト構造）［コープケミカル（株）製ＳＷＮ］にトリ
メチルデシルアンモニウムを１．０５当量挿入したもの
を使用して同様の実験を行った。Example 2 In Example 1, instead of the lipophilic synthetic smectite, a swelling synthetic mica (fluorine teniolite structure) [ME-10 manufactured by Corp Chemical Co., Ltd.]
0] was subjected to the same lipophilic treatment, that is, the same experiment was carried out using 1.05 equivalents of dimethyl distearyl ammonium. [Example 3] In Example 1, in place of the lipophilic synthetic smectite SAN, 1.05 equivalent of trimethyldecyl ammonium was inserted into untreated synthetic smectite (hectorite structure) [SWN manufactured by Corp Chemical Co., Ltd.]. The same experiment was performed using the prepared one.
【００４１】［比較例１］実施例１のポリエチレンテレ
フタレートのみを用いて、実施例１同様の溶融混練操作
と評価を行ったところ、平板の成形時金型内での固化が
遅く結晶化速度が低かった。 ［比較例２］実施例１にて、親油化合成スメクタイトＳ
ＡＮを添加せずに同様の実験を行ったところ、平板の成
形時金型内での固化が遅く結晶化速度が低かった。[Comparative Example 1] When only the polyethylene terephthalate of Example 1 was used and the same melt-kneading operation and evaluation were carried out as in Example 1, the solidification in the mold during the molding of the flat plate was slow and the crystallization rate was low. It was low. [Comparative Example 2] In Example 1, the lipophilic synthetic smectite S was used.
When the same experiment was conducted without adding AN, solidification was slow in the mold during flat plate formation, and the crystallization rate was low.
【００４２】［比較例３］実施例２にて、膨潤性合成雲
母ＭＥ−１００の親油化処理を行わずに、ＭＥ−１００
を１重量部使用し同様の実験を行った。 ［比較例４］実施例１にて、変性α−オレフィン重合体
ＡＯＥ−Ｚのかわりに、フェニル基で末端封鎖したポリ
エチレングリコール（数平均分子量６０００）を使用し
て同様の実験を行ったところ、平板の成形時、金型内で
の固化が明らかに遅く結晶化速度が低かったので評価は
行わなかった。COMPARATIVE EXAMPLE 3 In Example 2, the swelling synthetic mica ME-100 was not subjected to the lipophilic treatment, but the ME-100 was used.
The same experiment was conducted using 1 part by weight of. [Comparative Example 4] In the same manner as in Example 1, except that the modified α-olefin polymer AOE-Z was replaced with polyethylene glycol (number average molecular weight 6000) end-capped with a phenyl group, At the time of molding the flat plate, solidification in the mold was apparently slow and the crystallization rate was low, so evaluation was not performed.
【００４３】［比較例５］実施例１にて、変性α−オレ
フィン重合体ＡＯＥ−Ｚを添加せずに同様の実験を行っ
たところ、平板の成形時金型内での固化が明らかに遅く
結晶化速度が低かったので評価は行わなかった。 ［比較例６］実施例１にて、ポリエチレンテレフタレー
トを９０重量部、変性α−オレフィン重合体ＡＯＥ−Ｚ
の添加量を１０重量部にし、実施例１と同様の実験を行
ったところ、平板の表面にブリードアウトが認められた
ので評価は行わなかった。[Comparative Example 5] The same experiment as in Example 1 was carried out without adding the modified α-olefin polymer AOE-Z. As a result, the solidification of the flat plate in the mold was obviously slow. The crystallization rate was low, so no evaluation was performed. [Comparative Example 6] In Example 1, 90 parts by weight of polyethylene terephthalate and modified α-olefin polymer AOE-Z were used.
The same amount of 10 parts by weight was added and the same experiment as in Example 1 was carried out. Bleedout was observed on the surface of the flat plate. Therefore, evaluation was not carried out.
【００４４】［比較例７］（一般的な射出成形用グレー
ドのポリエチレンテレフタレート樹脂組成物との比較） 実施例１のポリエチレンテレフタレート９７重量％、タ
ルク０．７重量％、ｐ−ヒドロキシ安息香酸・２Ｎａを
０．３重量％、及び比較例４のフェニル基で末端封鎖し
たポリエチレングリコール２重量％をドライブレンド
し、実施例１同様の溶融混練と評価を行った。表２に示
した様に、本発明のポリエチレンテレフタレート樹脂組
成物は、一般的な射出成形用グレードの組成物と比べ、
熱安定性に特にすぐれている。Comparative Example 7 (Comparison with general injection molding grade polyethylene terephthalate resin composition) 97% by weight of polyethylene terephthalate of Example 1, 0.7% by weight of talc, p-hydroxybenzoic acid / 2Na Was dry-blended with 0.3% by weight of polyethylene glycol and 2% by weight of polyethylene glycol end-capped with phenyl groups in Comparative Example 4, and the same melt-kneading as in Example 1 was performed. As shown in Table 2, the polyethylene terephthalate resin composition of the present invention is superior to general injection molding grade compositions.
It has excellent thermal stability.
【００４５】[0045]
【表２】 [Table 2]
【００４６】[0046]
【発明の効果】本発明のポリエチレンテレフタレート樹
脂組成物は優れた結晶性と熱安定性を有するため、射出
成形等における固化速度が大きく滞留熱安定性にも優
れ、幅広い分野の構造材料として有用である。Since the polyethylene terephthalate resin composition of the present invention has excellent crystallinity and thermal stability, it has a high solidification rate in injection molding and the like and has excellent retention thermal stability, and is useful as a structural material in a wide variety of fields. is there.
Claims (6)
て、有機オニウムイオンを層間に含有する層状珪酸塩を
灰分量として０．０１〜１０重量％、及びエポキシ基を
分子内に１以上有する変性ポリオレフィンを０．１〜５
重量％含有せしめてなるポリエチレンテレフタレート樹
脂組成物。1. A polyethylene terephthalate resin containing 0.01 to 10% by weight of a layered silicate containing an organic onium ion between layers as an ash content, and a modified polyolefin having one or more epoxy groups in its molecule in an amount of 0. 1-5
A polyethylene terephthalate resin composition which is contained by weight percent.
１に記載のポリエチレンテレフタレート樹脂組成物。2. The polyethylene terephthalate resin composition according to claim 1, wherein the layered silicate is hectorite.
求項１に記載のポリエチレンテレフタレート樹脂組成
物。3. The polyethylene terephthalate resin composition according to claim 1, wherein the layered silicate is swellable fluoromica.
アルキル基を有する４級アンモニウムイオンである請求
項１ないし３に記載のポリエチレンテレフタレート樹脂
組成物。4. The polyethylene terephthalate resin composition according to claim 1, wherein the organic onium ion is a quaternary ammonium ion having an alkyl group having 12 or more carbon atoms.
アルキル基と炭素数１２以上のアルキル基とを有するテ
トラアルキルアンモニウムである請求項４記載のポリエ
チレンテレフタレート樹脂組成物。5. The polyethylene terephthalate resin composition according to claim 4, wherein the quaternary ammonium ion is tetraalkylammonium having a lower alkyl group and an alkyl group having 12 or more carbon atoms in the molecule.
炭素数５〜１００個に対してエポキシ基を１個有するα
−オレフィン重合体である請求項１ないし５記載のポリ
エチレンテレフタレート樹脂組成物。6. A modified polyolefin having one epoxy group per 5 to 100 carbon atoms of the polyolefin.
-The polyethylene terephthalate resin composition according to any one of claims 1 to 5, which is an olefin polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00808795A JP3336787B2 (en) | 1995-01-23 | 1995-01-23 | Polyethylene terephthalate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00808795A JP3336787B2 (en) | 1995-01-23 | 1995-01-23 | Polyethylene terephthalate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08199048A true JPH08199048A (en) | 1996-08-06 |
| JP3336787B2 JP3336787B2 (en) | 2002-10-21 |
Family
ID=11683548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00808795A Expired - Fee Related JP3336787B2 (en) | 1995-01-23 | 1995-01-23 | Polyethylene terephthalate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3336787B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000212408A (en) * | 1998-11-17 | 2000-08-02 | Toray Ind Inc | Polyester resin composition |
| JP2000212294A (en) * | 1998-11-17 | 2000-08-02 | Toray Ind Inc | Automotive part |
| CN1058034C (en) * | 1997-12-22 | 2000-11-01 | 中国纺织科学研究院 | PET composite material and preparing method thereof |
| JP2005298751A (en) * | 2004-04-15 | 2005-10-27 | Teijin Ltd | Polyester resin composition and polyester film |
| JPWO2005085349A1 (en) * | 2004-03-05 | 2008-01-24 | 帝人株式会社 | Polyester resin composition |
| CN109293896A (en) * | 2018-09-29 | 2019-02-01 | 王庭辉 | A kind of aromatic heterocyclic polymer resin of UV resistant and preparation method thereof and application in fiber or film |
-
1995
- 1995-01-23 JP JP00808795A patent/JP3336787B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058034C (en) * | 1997-12-22 | 2000-11-01 | 中国纺织科学研究院 | PET composite material and preparing method thereof |
| JP2000212408A (en) * | 1998-11-17 | 2000-08-02 | Toray Ind Inc | Polyester resin composition |
| JP2000212294A (en) * | 1998-11-17 | 2000-08-02 | Toray Ind Inc | Automotive part |
| JPWO2005085349A1 (en) * | 2004-03-05 | 2008-01-24 | 帝人株式会社 | Polyester resin composition |
| JP2005298751A (en) * | 2004-04-15 | 2005-10-27 | Teijin Ltd | Polyester resin composition and polyester film |
| CN109293896A (en) * | 2018-09-29 | 2019-02-01 | 王庭辉 | A kind of aromatic heterocyclic polymer resin of UV resistant and preparation method thereof and application in fiber or film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3336787B2 (en) | 2002-10-21 |
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