CN1052021C - 稳定、阻燃的聚碳酸酯模塑配合物 - Google Patents
稳定、阻燃的聚碳酸酯模塑配合物 Download PDFInfo
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- CN1052021C CN1052021C CN94115758A CN94115758A CN1052021C CN 1052021 C CN1052021 C CN 1052021C CN 94115758 A CN94115758 A CN 94115758A CN 94115758 A CN94115758 A CN 94115758A CN 1052021 C CN1052021 C CN 1052021C
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- Prior art keywords
- polycarbonate
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- phosphine
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 55
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 55
- 239000000206 moulding compound Substances 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 claims abstract description 9
- -1 triphenyl phosphine Sulfonates Chemical class 0.000 claims description 38
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 16
- 230000004927 fusion Effects 0.000 claims description 11
- 229920001169 thermoplastic Polymers 0.000 claims description 10
- 239000004416 thermosoftening plastic Substances 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 5
- GZQULBBZGMPLRE-UHFFFAOYSA-N C=1C=CC=CC=1P(C=1C=CC=CC=1)(S(=O)(=O)O)C1=CC=CC=C1 Chemical class C=1C=CC=CC=1P(C=1C=CC=CC=1)(S(=O)(=O)O)C1=CC=CC=C1 GZQULBBZGMPLRE-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 24
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- 229960003742 phenol Drugs 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000003063 flame retardant Substances 0.000 description 10
- 150000002989 phenols Chemical class 0.000 description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
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- 238000001816 cooling Methods 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
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- 125000004464 hydroxyphenyl group Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
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- 239000008188 pellet Substances 0.000 description 6
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- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 description 5
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- VXLQXFQDOGUAPA-UHFFFAOYSA-N (4-methoxyphenyl)phosphane Chemical compound COC1=CC=C(P)C=C1 VXLQXFQDOGUAPA-UHFFFAOYSA-N 0.000 description 3
- HUCQPHINKBNKRU-UHFFFAOYSA-N (4-methylphenyl)phosphane Chemical compound CC1=CC=C(P)C=C1 HUCQPHINKBNKRU-UHFFFAOYSA-N 0.000 description 3
- 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 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
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- 150000003818 basic metals Chemical class 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical class CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 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
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
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- ORPNDFMZTDVBGA-UHFFFAOYSA-N (2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P ORPNDFMZTDVBGA-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical class CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- YIYBRXKMQFDHSM-UHFFFAOYSA-N 2,2'-Dihydroxybenzophenone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1O YIYBRXKMQFDHSM-UHFFFAOYSA-N 0.000 description 1
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- HJZJMARGPNJHHG-UHFFFAOYSA-N 2,6-dimethyl-4-propylphenol Chemical compound CCCC1=CC(C)=C(O)C(C)=C1 HJZJMARGPNJHHG-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical class OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical class OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 1
- XSVZEASGNTZBRQ-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfinylphenol Chemical class OC1=CC=CC=C1S(=O)C1=CC=CC=C1O XSVZEASGNTZBRQ-UHFFFAOYSA-N 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical class OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 description 1
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- HXVJDHROZFWXHT-UHFFFAOYSA-N 2-diphenylphosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HXVJDHROZFWXHT-UHFFFAOYSA-N 0.000 description 1
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- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- SUCTVKDVODFXFX-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)sulfonyl-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(S(=O)(=O)C=2C=C(C)C(O)=C(C)C=2)=C1 SUCTVKDVODFXFX-UHFFFAOYSA-N 0.000 description 1
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- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- VYFPSYVVFFFYBF-UHFFFAOYSA-N sodium;triphenylphosphane Chemical compound [Na].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VYFPSYVVFFFYBF-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 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
- 238000005809 transesterification reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供了聚碳酸酯类和三苯膦磺酸盐类和任选地使用的氟化聚烯烃类和/或常规的添加剂的共混物,以及制备本发明共混物的方法。
Description
本发明提供了热塑性芳族聚碳酸酯类和下列各组分的共混物:
a)相对于聚碳酸酯重量的0.001%(重量)至1%(重量),优选0.005%(重量)至0.8%(重量)的式(I)的三苯膦磺酸盐类(triphenylphosphane sulphonates):其中R1、R2和R3相同或不同,可以是H、C1-C4烷基、C1-C4烷氧基、F、Cl、羧基或-CN,“X”是氢或-SO3(Y/n),若“Y”是碱金属阳离子,n=1,若“Y”是碱土金属阳离子,n=2,其中磺酸盐基团位于磷的间位或对位,R1、R2和R3在磷的邻、间和对位,和任选地使用的
b)相对于聚碳酸酯重量的0.001%(重量)至2%(重量),优选0.01%(重量)至1%(重量)的氟化聚烯烃类。
本发明的共混物集合了许多优良的性质,它们是阻燃的(根据UL94规定,对不加氟化聚烯烃的3.2mm厚试样和加氟化聚烯烃的1.6mm厚试样的测定均属于V-0级)并且在热环境中具有色稳定性。加入添加剂仅是为了阻燃和稳定作用,所得的模塑配合物是透明的,可以在无卤的情况下具有阻燃性,且尽管磷被电负性取代基取代,仍然具有意想不到的稳定作用。
已知各种碱金属或碱土金属的磺酸盐可使聚碳酸酯具有阻燃性质(例如参见美国专利3,933,734、3,940,366、3,953,399、3,926,908、4,104,246和欧洲专利EP-0 392 252(Le A 26 733))。
据我们所知,这些参考文献既未提及用式(I)的三苯膦磺酸盐类作阻燃剂,也未对其作清楚的说明。
也已知可用膦类化合物来稳定聚碳酸酯(例如参见EP-B1-0 043 998(Le A 20 430)、DE-OS 3 332 065(Le A 22 588)、EP-0 143 906(Le A 22 588-EP)和DE-OS 3 933 545(Le A27 209))。
据我们所知,这些参考文献中既未提及用式(I)的三苯膦磺酸盐类作稳定剂,事实上也未提及用来作阻燃剂。
在最后一篇DE-OS 3 933 545中,仅提到(第8页57行)其中所述的聚碳酸酯类也可含有阻燃剂。
将盐类与氟化聚烯烃类结合起来用于防火聚碳酸酯也是已知的(例如参见DE-OS 2 535 262,DE-OS 2 744 016和已提到的EP-0 392 252)。
据我们所知,这些文献中既没有提及将式(I)的三苯膦磺酸盐类与氟化聚烯烃结合用作阻燃剂,也未对其作清楚的说明。
本发明的热塑性芳族聚磺酸酯类既可是均聚碳酸酯类也可是共聚碳酸酯类;该聚碳酸酯类可以是已知的线形的或支化的。
在本发明适用的聚碳酸酯类中,含量最高达80%(摩尔)(优选20%(摩尔)至50%(摩尔))的碳酸酯基可以用芳族二羧酸酯基代替。这种在其分子链中既有碳酸基又有芳族二羧酸基的聚碳酸酯类正确地应称为芳族聚酯碳酸酯。为简化起见,本申请中将其归于上位概念的热塑性芳族聚碳酸酯类之中。
用本发明方法稳定的聚碳酸酯类可按已知的方法由二元酚类、碳酸衍生物、任选的链终止剂和任选的支化剂来制备,若是制备聚酯碳酸酯类,则其中一些碳酸衍生物可用芳族二羧酸类或其衍生物代替,事实上是根据芳族聚碳酸酯中的碳酸酯结构单元被芳族二羧酸酯结构单元取代的情况。
有关聚碳酸 酯类详细的制备方法是已知的并在过去的近四十年内在几百个专利中公开过。这里仅参考下列一些文献:Schnell,聚碳酸酯类的化学和物理,Polymer Reviews,第9卷,IntersciencePublishers,纽约,伦敦,悉尼1964;D.C.Prevorsek,B.T.Debona和Y.Kesten,联合化学公司,共同研究中心(Morristown,新泽西07960),聚碳酸酯共聚物的合成,Journal of PolymerScience,Polymer Chemistry Edition,第18卷,75-90(1980);D.Freitag,U.Grigo,P.R.Müller,H.Nouvertne’,Bayer公司,聚碳酸酯类,Encyclopedia of Polymer Science andEngineering,第11卷,第2版,1988,648-718页;和Dres.U.Grigo,K.Kircher和P.R.Müller,聚碳酸酯,Becker/Braun,Kunststoff-Handbuch,第3/1卷,聚碳酸酯,聚缩醛,聚酯,纤维素酯,Carl Hanser Verlag Munich,Vienna 1992,117-299页。
包括热塑性芳族聚酯碳酸酯类的热塑性聚碳酸酯类的重均分子量Mw(由在25℃、0.5g/100ml CH2Cl2的浓度下测定其在CH2Cl2中的相对粘度确定)为12,000至120,000,优选18,000至80,000,特别优选22,000至60,000。
适合于制备用本发明方法稳定的聚碳酸酯类的二元酚类为:例如,对苯二酚、间苯二酚、二羟基联 苯类、双(羟苯基)烷烃类、双(羟苯基)环烷烃类、双(羟苯基)硫醚类、双(羟苯基)醚类、双(羟苯基)酮类、双(羟苯基)砜类、双(羟苯基)亚砜类、α,α′-双(羟苯基)二异丙苯类、以及它们的环上烷基取代和环上卤素取代的化合物。
优选的二元酚类是4,4′-二羟基联苯、2,2-双(4-羟基苯基)丙烷、2,4-双(4-羟基苯基)-2-甲基丁烷、1,1-双(4-羟基苯基)-对二异丙苯、2,2-双(3-甲基-4-羟基苯基)丙烷、2,2-双(3-氯-4-羟基苯基)丙烷、双(3,5-二甲基-4-羟基苯基)甲烷、2,2-双(3,5-二甲基-4-羟基苯基)丙烷、双(3,5-二甲基-4-羟基苯基)砜、2,4-双(3,5-二甲基-4-羟基苯基)-2-甲基丁烷、1,1-双(4-羟基苯基)-对二异丙苯、1,1-双(3,5-二甲基-4-羟基苯基)-对二异丙苯、2,2-双(3,5-二氯-4-羟基苯基)丙烷、2,2-双(3,5-二溴-4-羟基苯基)丙烷和1,1-双(4-羟基苯基)-3,3,5-三甲基环己烷。
特别优选的二元酚类是2,2-双(4-羟基苯基)丙烷、2,2-双(3,5-二甲基-4-羟基苯基)丙烷、2,2-双(3,5-二氯-4-羟基苯基)丙烷、2,2-双(3,5-二溴-4-羟基苯基)丙烷、1,1-双(4-羟基苯基)环己烷和1,1-双(4-羟基苯基)-3,3,5-三甲基环己烷。
这些以及其它一些适用的二元酚类可参见例如下列文献:美国专利3,028,635、2,999,835、3,148,172、2,991,273、3,271,367、4,982,014和2,999,846;DE-OS 1 570 703、2 063 050、2 036 052、DE-OS 2 211 956和DE-OS 3 832 396;法国专利1 561 518;H.Schnell的专论:聚碳酸酯类的化学和物理,IntersciencePublishers,纽约,1964和日本公开专利申请62039/1986,62040/1986和105550/1986。
制备均聚碳酸酯类时,仅用一种二元酚,而制备共聚碳酸酯则用两种或更多种二元酚。
一元酚类和一元羧酸类均为适用的链终止剂。适用的一元酚类是苯酚本身,烷基酚类,如甲酚类、对叔丁基苯酚、对正辛基苯酚、对异辛基苯酚、对正壬基苯酚和对异壬基苯酚,卤代酚类,如对氯苯酚、2,4-二氯苯酚、对溴苯酚和2,4,6-三溴苯酚。
适用的一元羧酸类是苯甲酸、烷基苯甲酸类和卤代苯甲酸类。
链终止剂的用量是相对于所用二元酚类的具体摩尔量的0.5%(摩尔)至10%(摩尔)。链终止剂可以在光气化反应之前、期间或之后加入。
适合的支化剂是聚碳酸酯化学中已知的三或多官能化合物,特别是那些带有三个或三个以上酚羟基的化合物。
适用的支化剂为:例如,间苯三酚、4,6-二甲基-2,4,6-三(4-羟基苯基)-2-庚烯、4,6-二甲基-2,4,6-三(4-羟基苯基)庚烷、1,3,5-三(4-羟基苯基)苯、1,1,1-三(4-羟基苯基)乙烷,三(4-羟基苯基)苯甲烷、2,2-双[4,4-双(4-羟基苯基)环己基]丙烷、2,4-双(4-羟基苯基异丙基)苯酚、2,6-双(2-羟基-5′-甲基苄基)-4-甲基苯酚、2-(4-羟基苯基)-2-(2,4-二羟基苯基)丙烷、六[4-(4-羟基苯基异丙基)苯基]原对苯二甲酸酯、四(4-羟基苯基)甲烷、四[4-(4-羟基苯基异丙基)苯氧基]甲烷和1,4-双[(4′,4″-二羟基三苯基)甲基]苯以及2,4-二羟基苯甲酚、1,3,5-苯三酸、氰尿酰氯和3,3-双(3-甲基-4-羟基苯基)-2-氧代-2,3-二氢吲哚。
任选地使用的支化剂的用量是相对于所用二元酚的具体摩尔量的0.05%(摩尔)至2%(摩尔)。
支化剂既可以与二元酚和链终止剂一起加到碱溶液相中,也可以在光气化反应前溶于有机溶剂中加入。
所有这些制备聚碳酸酯类的方法对于本领域内的技术人员都是熟悉的。
适合用于制备聚酯碳酸酯的芳族二羧酸类有:例如,邻苯二甲酸、对苯二甲酸、间苯二甲酸、叔丁基间苯二甲酸、3,3′-联苯二羧酸、4,4′-联苯二羧酸、4,4′-二苯甲酮二羧酸、3,4′-二苯甲酮二羧酸、4,4′-二苯醚二羧酸、4,4′-二苯砜二羧酸、2,2-双(4-羧基苯基)丙烷、三甲基-3-苯基-1,2-二氢化茚-4,5′-二羧酸。
在各种芳族二羧酸中,对苯二甲酸和/或间苯二甲酸是特别优选使用的。
二羧酸衍生物是二酰卤类和二羧酸二芳基酯类,具体地说,是二酰氯类和二羧酸二苯酯类。
芳族二羧酸基取代碳酸酯基的反应基本上是化学计量的,也是定量的,所以反应物的摩尔数也反映在制成的聚酯碳酸酯中。芳族二羧酸酯基可以无规的或嵌段的形式插入。
用本发明方法稳定的聚碳酸酯类(包括聚酯碳酸酯类)的优选的制备方法是已知的界面聚合法和已知的熔融酯交换法。
在第一种方法中,碳酸衍生物优选为光气,在后一种方法中优选碳酸二苯酯。
在这二种方法中的催化剂、溶剂、处理、反应条件等已有充分的报道并且广为所知。
在式(I)的三苯膦磺酸盐类中,R1至R3优选为H、CH3或CH3-O-,特别优选为H;优选至少一个X是H,特别优选两个X均为H;Y优选为Li、Na、K、Mg或Ca,特别优选为Na、K、Mg或Ca;磺酸盐基优选在磷的间位,R1至R3基优选在磷的邻位或对位,极其优选在对位。
本发明所用的磺酸盐类(I)可以从文献中了解(例如参见EP-0 287 066、0 355 837、0 041 134,DE-OS 4 006 112、2 627 354、3 235 030、3 431 643、2 700 904、2 733 516和2 627 354以及Monatshefte 96,2051-2057页(1965)或J.Chem.Soc.1958 276-288页),或可用文献中的方法得到。
适合的式(I)的三苯膦磺酸盐类有:例如,下列化合物的碱金属或碱土金属盐类:(对磺苯基)二苯膦、(间磺苯基)二苯膦、(对磺基邻甲基苯基)二(邻甲基苯基)膦、(间磺基对甲基苯基)二(对甲基苯基)膦、(对磺基邻甲氧基苯基)二(邻甲氧基苯基)膦、(间磺基对甲氧基苯基)二(对甲氧基苯基)膦、(间磺苯基)(对羧基苯基)苯基膦、(间磺基对甲基苯基)二苯膦、(对磺苯基)二(对甲氧基苯基)膦、(对磺苯基)二(对甲基苯基)膦、(间磺基对乙基苯基)二(对乙基苯基)膦和(间磺基对氯苯基)二(对氯苯基)膦;
下列化合物的碱金属和碱土金属盐类:二(间磺苯基)联苯基膦(di-(m-sulphophenyl)-diphenyl phosphane)、二(间磺基邻甲基苯基)(邻甲基苯基)膦、二(对磺苯基)苯基膦、二(间磺基对甲基苯基)(对甲苯基)膦、二(间磺基对甲氧基苯基)(对甲氧基苯基)膦、二(间磺基对氯苯基)(对氯苯基)膦和(对磺苯基)(间磺苯基)苯基膦;
下列化合物的碱金属盐类:三(对磺苯基)膦、三(间磺苯基)膦、三(间磺基对甲苯基)膦、三(间磺基对氯苯基)膦、三(间磺基对甲氧基苯基)膦、三(间磺基对乙苯基)膦和三(对磺基邻甲苯基)膦。
盐类特别优选的用量为0.01至0.6%(重量),极其优选的用量为0.02至0.5%(重量)(相对于聚碳酸酯的重量)。
适用的本发明的组分b)-氟化聚烯烃为氟含量为65至76%(重量)、优选70至76%(重量)的聚合物。实例有聚四氟乙烯、四氟乙烯/六氟丙烯共聚物或四氟乙烯与少量不含氟的可共聚的烯不饱和单体的共聚物。这些聚合物都是已知的,它们可用已知方法制备,例如,四氟乙烯在水性介质中用自由基引发剂(如过硫酸钠、钾、铵)在7至71kg/cm2压力、0至200℃温度(优选20至100℃)下进行的聚合(更详细的描述可参见例如美国专利2,393,967)。氟化聚烯烃的平均颗粒大小优选为0.05μm至20μm。
本发明共混物可按已知的方法制备,即在组分a)和任选的组分b)在25℃(室温)或更高温度下顺次或同时与聚碳酸酯类混合后,再在260℃至360℃、优选260℃至300℃下进行熔融配合或熔融挤出。
本发明也提供了一种由热塑性芳族聚碳酸酯类和组分a)及任选的b)制备本发明共混物的方法,该方法的特征在于组分a)和任选的组分b)在25℃或更高的温度下混入聚碳酸酯中,然后在260℃至360℃、优选260℃至300℃温度下,在常规的设备中进行熔融配合或熔融挤出。
组分a)和任选的组分b)也可用所谓母炼胶的方法以浓缩物的形式加到适当的热塑性芳族聚碳酸酯中,在聚碳酸酯中,此类浓缩物含有5至20%(重量)的组分a)和任选的组分b)。
热塑性聚碳酸酯中常见的适用的添加剂或添加物料(如玻璃纤维、填料、颜料、UV稳定剂和脱模剂)也可用聚碳酸酯类常用的方法加入。
所以本发明也提供了一种由热塑性芳族聚碳酸酯类、组分a)和任选的组分b)制成的本发明的共混物,这种共混物的特征在于它们还含有聚碳酸酯类中常用量的玻璃纤维、填料、颜料、UV稳定剂和/或脱模剂。
本发明还提供了一种制备最后所述的这些共混物的方法,其特征在于热塑性芳族聚碳酸酯类与组分a)和任选的组分b)以及任选的玻璃纤维、填料、颜料、UV稳定剂和/或脱模剂在25℃或更高温度下进行混合,然后在260℃至360℃、优选260℃至300℃温度下,在常规的设备中进行熔融配合或熔融挤出。
这里也可用母炼胶的方法,各添加剂可以浓缩物的形式加到聚碳酸酯中。
本发明的共混物可用已知的方法在已知的设备上加工成任何所需的模制物,例如片材、管材、瓶子和薄膜。
这些产品和制备这些产品的本发明共混物的特征是具有良好的阻燃性和热稳定性,并且如果不添加离散性的添加剂(如颜料、玻璃纤维、填料等),还具有良好的透明性。
这些产品具有很多工业应用,例如在电子工程、电气工程和建筑上的应用。
适用的模制品有:例如,片材、开关箱外壳和电子扇形扫描中的视窗。
将用本发明共混物制成的模制品在高温下进行处理,例如在130℃的热空气中老化1,000小时。按ASTM 1003规定测透光率,按ASTMD1925规定测泛黄指数。
三苯膦磺酸盐类的合成实施例I.将26g三苯膦在室温、搅拌和氮气氛下于15至30分钟内加到260g20%的发烟硫酸中,继续在25℃下反应18小时。将反应混合物倒入2kg冰中,用浓氢氧化钠溶液调节pH值至6.5,在静置过夜后,沉淀的晶体用抽滤法分离并干燥,得28g产物。
将这些晶体用甲醇煎煮三次,合并透明的滤液并蒸发,将残余物在真空下干燥,得到20.7g无色晶体,
元素分析 P% S%
实 际 值 6.5 13.2
计 算 值 6.6 13.7
计算值是按三苯膦二磺酸二钠盐计算的。II.将26g三苯膦在室温、搅拌、冷却和氮气氛下于约30分钟内分批加到108g 20%发烟硫酸中,将该透明混合物加热至82℃,保持40分钟。在加热以后,反应混合物的试样可在水中形成透明溶液。混合物冷却后,将其倒入60g冰中,用浓氢氧化钠溶液调节pH值至7。将从冷溶液中析出的晶体抽滤,干燥并用甲醇煎煮二至三次,合并的透明滤液蒸发后将残余物在真空下干燥,得到25g无色晶体,
元素分析 P% S%
实 际 值 7.9 8.9
计 算 值 8.5 8.8
计算值是按三苯膦磺酸钠盐计算的。实施例1
将99.9%(重量)的由2,2-双(4-羟基苯基)丙烷用苯酚作链终止剂制备的芳族聚碳酸酯(熔融指数为8,按DIN 53 735测定)在280℃的双螺杆挤出机中熔融。然后将0.1%(重量)的三苯膦磺酸钠(合成实施例II)直接加到聚碳酸酯熔体中。将聚合物条冷却、造粒,将粒料在80℃的真空干燥箱中干燥,然后在280℃下注塑成尺寸为127×12×3.2mm的试样。
然后将样条进行UL 94(Underwriters′实验室的固体塑料试样的可燃性测试)的可燃性试验,并且归于可燃性V0类。实施例2
将99.9%(重量)的由2,2-双(4-羟基苯基)丙烷用苯酚作链终止剂制备的芳族聚碳酸酯(熔融指数为8,按DIN 53 735测定)在280℃的双螺杆挤出机中熔融。然后将0.1%(重量)的三苯膦二磺酸二钠(合成实施例I)直接加到聚碳酸酯熔体中。将聚合物条冷却、造粒,将粒料在80℃的真空干燥箱中干燥,然后在280℃下注塑成尺寸为127×12×3.2mm的试样。
然后将样条进行UL94(Underwriters′实验室的固体塑料试样的可燃性测试)的可燃性试验,并且归于可燃性V0类。实施例3
将99.7%(重量)的由2,2-双(4-羟基苯基)丙烷用苯酚作链终止剂制备的芳族聚碳酸酯(熔融指数为11,按DIN 53 735测定)在280℃的双螺杆挤出机中熔融。然后将0.2%(重量)的三苯膦磺酸钠和0.1%(重量)的氟化聚烯烃的混合物直接加到聚碳酸酯熔体中。将聚合物条冷却、造粒,将粒料在80℃的真空干燥箱中干燥,然后在280℃下注塑成尺寸为127×12×1.6mm的试样。
然后将样条进行UL 94(Underwriters′实验室的固体塑料试样的可燃性测试)的可燃性试验,并且归于可燃性V0类。实施例4
将99.7%(重量)的由2,2-双(4-羟基苯基)丙烷用苯酚作链终止剂制备的芳族聚碳酸酯(熔融指数为11,按DIN 53 735测定)在280℃的双螺杆挤出机中熔融。然后将0.2%(重量)的三苯膦二磺酸二钠和0.1%(重量)的氟化聚烯烃的混合物直接加到聚碳酸酯熔体中。将聚合物条冷却、造粒,将粒料在80℃的真空干燥箱中干燥,然后在280℃下注塑成尺寸为127×12×1.6mm的试样。
然后将样条进行UL 94(Underwriters′实验室的固体塑料试样的可燃性测试)的可燃性试验,并且归于可燃性V0类。比较例1
将100%(重量)的由2,2-双(4-羟基苯基)丙烷用苯酚作链终止剂制备的芳族聚碳酸酯(熔融指数为8,按DIN 53 735测定)在280℃的双螺杆挤出机中熔融。将聚合物条冷却并造粒。
将粒料在80℃的真空干燥箱中干燥,然后在280℃下注塑成尺寸为127×12×3.2mm和127×12×1.6mm的试样。
然后将样条进行UL 94(Underwriters′实验室的固体塑料试样的可燃性测试)的可燃性试验,两种厚度的试样均归于可燃性V2类。比较例2
将99.9%(重量)的由2,2-双(4-羟基苯基)丙烷用苯酚作链终止剂制备的芳族聚碳酸酯(熔融指数为8,按DIN 53 735测定)在280℃的双螺杆挤出机中熔融。然后将0.1%(重量)的全氟丁烷磺酸钾直接加到聚碳酸酯熔体中。将聚合物条冷却并造粒。
将粒料在80℃的真空干燥箱中干燥,然后在280℃下注塑成尺寸为127×12×3.2mm和127×12×1.6mm的试样。
然后将样条进行UL 94(Underwriters′实验室的固体塑料试样的可燃性测试)的可燃性试验,两种厚度的试样均归于可燃性V2类。
将实施例1、2和比较例1的模塑化合物在300℃和360℃的熔融温度下注塑成尺寸为60×40×4mm的着色小样片,在各种不同的曝光周期后立即测定其泛黄指数(NY)和透光率TY(参见下表)。
泛黄指数按DIN 6164 ASTM D 1925用无反光的Hunterlab光源C(℃/d)测定 | |||
试样 | 曝光(小时) | 标准明度TY | 泛黄指数 |
比较例1 | 0500 | 89.3689.65 | 5.06.1 |
实施例2 | 0500 | 88.7788.67 | 5.35.8 |
实施例1 | 0500 | 88.2988.57 | 5.76.2 |
比较例1 | 0500 | 89.7689.47 | 5.26.7 |
实施例2 | 0500 | 88.9688.91 | 5.26.1 |
实施例1 | 0500 | 88.3383.50 | 5.46.8 |
Claims (4)
1.热塑性芳族聚碳酸酯类和下列组分的共混物:
a)相对于聚碳酸酯重量的0.001%(重量)至1%(重量)的式(I)的三苯膦磺酸盐类:其中R1、R2和R3相同或不同,可以是H1、C1-C4烷基、C1-C4烷氧基、F、Cl、羧基或-CN,“X”是氢或-SO3(Y/n),若“Y”是碱金属阳离子,n=1,若“Y”是碱土金属阳离子,n=2,其中磺酸盐基团位于磷的间位或对位,R1、R2和R3在磷的邻、间和对位,和任选地使用的
b)相对于聚碳酸酯重量的0.001%(重量)至1%(重量)的氟化聚烯烃类。
2.根据权利要求1的共混物,其特征在于它们还含有聚碳酸酯类中常用量的玻璃纤维、填料、颜料、UV稳定剂和/或脱模剂。
3.制备权利要求1的共混物的方法,其特征在于将组分a)和任选的组分b)在25℃或更高温度下与聚碳酸酯混合,然后在260℃至360℃温度下,在常规设备中进行熔融配合或熔融挤出。
4.根据权利要求3的方法,其特征在于将热塑性芳族聚碳酸酯类与组分a)和任选的组分b),以及玻璃纤维、填料、颜料、UV稳定剂和/或脱模剂一起在25℃或更高温度下混合,然后在260℃至360℃温度下,在常规的设备中进行熔融配合或熔融挤出。
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DEP4328384.5 | 1993-08-24 | ||
DE4328384A DE4328384A1 (de) | 1993-08-24 | 1993-08-24 | Stabilisierte, flammwidrige Polycarbonatformmassen |
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CN1052021C true CN1052021C (zh) | 2000-05-03 |
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US (1) | US5399600A (zh) |
EP (1) | EP0643096B1 (zh) |
JP (1) | JP3252882B2 (zh) |
CN (1) | CN1052021C (zh) |
DE (2) | DE4328384A1 (zh) |
ES (1) | ES2122110T3 (zh) |
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DE29514672U1 (de) * | 1995-09-13 | 1995-12-07 | LTS Licht & Leuchten GmbH, 88069 Tettnang | Stromleitersystem |
JP5237511B2 (ja) * | 1999-10-19 | 2013-07-17 | 出光興産株式会社 | ポリカーボネート樹脂組成物 |
FR2806088B1 (fr) * | 2000-03-07 | 2003-07-18 | Atofina | Composition thermoplastique transparente contenant des particules de polytetrafluoroethylene et articles faconnes obtenus a partir de cette composition |
US6730720B2 (en) * | 2000-12-27 | 2004-05-04 | General Electric Company | Method for reducing haze in a fire resistant polycarbonate composition |
ES2746204T3 (es) * | 2010-10-11 | 2020-03-05 | Novomer Inc | Mezclas de polímeros |
CN103073586A (zh) * | 2013-01-11 | 2013-05-01 | 天津师范大学 | 双(3-磺酸-4-卤苯基)-3’-磺酸苯基氧膦及其盐的制备方法 |
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EP0143906A1 (de) * | 1983-09-06 | 1985-06-12 | Bayer Ag | Verfahren zur Herstellung stabilisierter Polycarbonat-Formkörper nach dem Entgasungsspritzguss--oder dem Entgasungsextrusionsverfahren |
EP0175919A1 (de) * | 1984-08-29 | 1986-04-02 | Ruhrchemie Aktiengesellschaft | Verfahren zur Abtrennung und Reindarstellung von Salzen der Diphenylphosphinphenyl-m-sulfonsäure, Phenylphosphin-di-(m-phenylsulfonsäure) und/oder Triphenylphosphin-tri(m-sulfonsäure) |
EP0422438A2 (de) * | 1989-10-07 | 1991-04-17 | Bayer Ag | Polycarbonate aus Dihydroxydiphenylcycloalkanen mit Additiven |
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DE2238221A1 (de) * | 1972-08-03 | 1974-02-14 | Hoechst Ag | Dialkyl-phosphinyl-alkansulfonate und verfahren zu ihrer herstellung |
US3978024A (en) * | 1973-12-28 | 1976-08-31 | General Electric Company | Flame retardant polycarbonate composition |
NL8220052A (nl) * | 1981-02-20 | 1983-01-03 | Gen Electric | Vlamvertragende, polyestercarbonaat bevattende samenstellingen. |
FR2550202B1 (fr) * | 1983-08-03 | 1986-03-21 | Rhone Poulenc Rech | Procede de preparation de tri(m-sulfophenyl) phosphine |
US4826900A (en) * | 1988-03-31 | 1989-05-02 | The Dow Chemical Company | Ignition resistant modified carbonate polymer composition |
-
1993
- 1993-08-24 DE DE4328384A patent/DE4328384A1/de not_active Withdrawn
-
1994
- 1994-08-11 DE DE59407219T patent/DE59407219D1/de not_active Expired - Fee Related
- 1994-08-11 EP EP94112546A patent/EP0643096B1/de not_active Expired - Lifetime
- 1994-08-11 ES ES94112546T patent/ES2122110T3/es not_active Expired - Lifetime
- 1994-08-12 US US08/289,777 patent/US5399600A/en not_active Expired - Lifetime
- 1994-08-18 JP JP21522294A patent/JP3252882B2/ja not_active Expired - Fee Related
- 1994-08-24 CN CN94115758A patent/CN1052021C/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0143906A1 (de) * | 1983-09-06 | 1985-06-12 | Bayer Ag | Verfahren zur Herstellung stabilisierter Polycarbonat-Formkörper nach dem Entgasungsspritzguss--oder dem Entgasungsextrusionsverfahren |
EP0175919A1 (de) * | 1984-08-29 | 1986-04-02 | Ruhrchemie Aktiengesellschaft | Verfahren zur Abtrennung und Reindarstellung von Salzen der Diphenylphosphinphenyl-m-sulfonsäure, Phenylphosphin-di-(m-phenylsulfonsäure) und/oder Triphenylphosphin-tri(m-sulfonsäure) |
EP0422438A2 (de) * | 1989-10-07 | 1991-04-17 | Bayer Ag | Polycarbonate aus Dihydroxydiphenylcycloalkanen mit Additiven |
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ES2122110T3 (es) | 1998-12-16 |
DE59407219D1 (de) | 1998-12-10 |
EP0643096B1 (de) | 1998-11-04 |
JPH0797509A (ja) | 1995-04-11 |
DE4328384A1 (de) | 1995-03-02 |
EP0643096A1 (de) | 1995-03-15 |
JP3252882B2 (ja) | 2002-02-04 |
CN1101360A (zh) | 1995-04-12 |
US5399600A (en) | 1995-03-21 |
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