SE430168B - SUBSTANCE PACKAGING PLASTIC COMPOSITION CONTAINING REINFORCEMENT OR FILLER AND USE OF IT - Google Patents
SUBSTANCE PACKAGING PLASTIC COMPOSITION CONTAINING REINFORCEMENT OR FILLER AND USE OF ITInfo
- Publication number
- SE430168B SE430168B SE7900801A SE7900801A SE430168B SE 430168 B SE430168 B SE 430168B SE 7900801 A SE7900801 A SE 7900801A SE 7900801 A SE7900801 A SE 7900801A SE 430168 B SE430168 B SE 430168B
- Authority
- SE
- Sweden
- Prior art keywords
- carbon atoms
- formula
- organic
- component
- composition according
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 46
- 229920003023 plastic Polymers 0.000 title claims description 21
- 239000004033 plastic Substances 0.000 title claims description 21
- 230000002787 reinforcement Effects 0.000 title claims description 7
- 238000004806 packaging method and process Methods 0.000 title 1
- 239000000126 substance Substances 0.000 title 1
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- -1 polyethylene terephthalate Polymers 0.000 claims description 24
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 13
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 10
- 150000002895 organic esters Chemical class 0.000 claims description 9
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 150000002430 hydrocarbons Chemical group 0.000 claims description 7
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- 229920000620 organic polymer Polymers 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 150000003457 sulfones Chemical class 0.000 claims description 5
- 150000003462 sulfoxides Chemical class 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000012744 reinforcing agent Substances 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 150000003857 carboxamides Chemical class 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- 239000012763 reinforcing filler Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 235000014347 soups Nutrition 0.000 claims 1
- 239000000654 additive Substances 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011152 fibreglass Substances 0.000 description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 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 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- ZHYZQXUYZJNEHD-CLFYSBASSA-N (2z)-3,7-dimethylocta-2,6-dienoic acid Chemical compound CC(C)=CCC\C(C)=C/C(O)=O ZHYZQXUYZJNEHD-CLFYSBASSA-N 0.000 description 1
- OGTSHGYHILFRHD-UHFFFAOYSA-N (4-fluorophenyl)-phenylmethanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC=C1 OGTSHGYHILFRHD-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- 229910000759 E-Material Inorganic materials 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 101000579226 Homo sapiens Renin receptor Proteins 0.000 description 1
- 241000556720 Manga Species 0.000 description 1
- 102100028254 Renin receptor Human genes 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 1
- PJLLCGNQPWXWGL-UHFFFAOYSA-N [3-benzoyloxy-2-(benzoyloxymethyl)-2-methylpropyl] benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(COC(=O)C=1C=CC=CC=1)(C)COC(=O)C1=CC=CC=C1 PJLLCGNQPWXWGL-UHFFFAOYSA-N 0.000 description 1
- NZSIEUJMXKIAOM-UHFFFAOYSA-N [CH2]C[K] Chemical group [CH2]C[K] NZSIEUJMXKIAOM-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- KFEVDPWXEVUUMW-UHFFFAOYSA-N docosanoic acid Natural products CCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 KFEVDPWXEVUUMW-UHFFFAOYSA-N 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
79008 01- 7 2 Det är önskvärt att få fram en armerings- eller fyllme- delshaltig etentereftalatplast, som kan formas vid formtemperatu- rer under ca 110°C under bildning av ett format alster med en jämn och glatt yta. De armerings- eller fyllmedelshaltiga etenterefta-1 latplasterna enligt uppfinningen uppnår de ovan angivna målen ge- nom att man försätter dem med (1) ett natrium- eller kaliumsalt av en utvald karboxylsyra av ett kolväte eller ett natrium- eller kaliumsalt av en utvald organisk polymer, innehållande förgrenin- gar av karboxylgrupper, och (2) en utvald, lâgmolekylär, organisk ester, keton, sulfon, sulfoxid, nitril eller amid. _ Närmare bestämt avser uppfinningen en plastkomposition, (vilken är kännetecknad av att den väsentligen består av: A) polyetentereftalat med en inre viskositet av minst ca 0,4, t B) mellan ca 10 och ca 60 viktprocent armerings- eller fyllmedel, 1 C) 0,5 - 12 viktprocent, räknat på vikten polyetenteref- talat, av ett material som samtidigt föreligger i en tillräckligt stor manga för att ge ett AnH/Anc-förhåiiende under 0,25 åt en blandning av komponenterna A, B och C, vilket material inkluderar material som erhållits av ' (i) kolvätekarboxylsyror med mellan 7 och 25 kolatomer eller organiska polymerer som innehåller karboxyl- gruppsförgreningar och _ (ii) natriumf och/eller kaliumjonkällor med förmåga att reagera med karboxylgrupperna i (i), 7 D) 1 - 12 viktprocent, räknat på vikten polyetenteref- talat, av minst en förening, som samtidigt föreligger i tillräck- ligt stor mängd för att ge en Tpk, som är minst 4°C lägre än Tpk för en blandning av komponenter A, B och C vilken förening är vald bland I i a) organiska estrar, bestående av produkten av en aroma- tisk karboxylsyra med 7 - 11 kolatomer, som innehåller minst 1 karboxylgrupp per aromatisk kärna, och en alkohol, som ntgöres av en alkohol med formeln (HOCH2+xR', där x är 1, 2 eller 3 och R' är en kolväteradikal med 2 - 15 kolatomer,(företrädesvis 2 - 10 kolatomerL eller en alkohol med formeln HO+R“O%yR"', där_y är ett helt tal mellan 1 och 15, R" är en kolväteradikal med 2 - 15 kolatomer och R"' är -H eller en kolväteradikal med 2 -"2O kol- atomer (företrädesvis 2 - 12 kolatomer) eller 75900801-7 0 b) organiska ketoner med formeln RER, c) organiska sulfoner med formeln RSOOR, d) organiska sulfoxider med formeln RZSO, e) organiska nitriler med formeln RCN eller f) organiska amider med formeln 0 0 RENR' R eller RåONR' R, varvid var och en av de med R betecknade grupperna i formlerna b) t.o.m. f) kan vara identisk med eller olik någon annan R-grupp och utgöres av en kolvätegrupp med 1 - 25 kolatomer, medan R' i de i f) angivna formlerna betecknar väte eller en kolvätegrupp med 1 - 25 kolatomer. ' Vidare avser föreliggande uppfinning användning av en plastkomposition enligt ovan för tillverkning av ett format als- ter, varvid kompositionen formas i en form med en yttemperatur av 1100C eller lägre. 79008 01- 7 2 It is desirable to obtain a reinforcement or filler partially containing ethylene terephthalate plastic, which can be formed at mold temperature. below about 110 ° C to form a molded article with a smooth and smooth surface. The reinforcing or filler-containing ethylene terephtha-1 the lathe plastics according to the invention achieve the above stated goals by adding them with (1) a sodium or potassium salt of a selected carboxylic acid of a hydrocarbon or a sodium or potassium salt of a selected organic polymer, containing branched of carboxyl groups, and (2) a selected, low molecular weight, organic ester, ketone, sulfone, sulfoxide, nitrile or amide. More particularly, the invention relates to a plastic composition, (which is characterized in that it essentially consists of: A) polyethylene terephthalate with an intrinsic viscosity of at least approx 0.4, t B) between about 10 and about 60% by weight of reinforcement or fillers, 1 C) 0,5 to 12% by weight, based on the weight of polyethylene spoken, of a material which at the same time is present in a sufficient large manga to give an AnH / Anc ratio below 0.25 to one mixture of components A, B and C, which material includes materials obtained by ' (i) hydrocarbon carboxylic acids having between 7 and 25 carbon atoms or organic polymers containing carboxylic group branches and _ (ii) sodium and / or potassium ion sources capable of: react with the carboxyl groups in (i), 7 D) 1 to 12% by weight, based on the weight of polyethylene by at least one association, which at the same time exists in sufficient large amount to give a Tpk which is at least 4 ° C lower than Tpk for a mixture of components A, B and C which compound is selected among I i (a) organic esters, consisting of the product of an aromatic carboxylic acid having 7 to 11 carbon atoms, containing at least 1 carboxyl group per aromatic nucleus, and an alcohol which is made of an alcohol of the formula (HOCH2 + xR ', where x is 1, 2 or 3 and R 'is a hydrocarbon radical having 2 to 15 carbon atoms, (preferably 2 - 10 carbon atoms or an alcohol of the formula HO + R "O% yR" ', where_y is an integer between 1 and 15, R "is a hydrocarbon radical with 2 - 15 carbon atoms and R "'is -H or a hydrocarbon radical having 2 -" 20 carbon atoms (preferably 2 to 12 carbon atoms) or 75900801-7 0 b) organic ketones of the formula RER, c) organic sulfones of the formula RSOOR, d) organic sulfoxides of the formula RZSO, (e) organic nitriles of the formula RCN or f) organic amides of the formula 0 0 RENR 'R or RåONR' R, wherein each of the groups denoted by R in the formulas b) t.o.m. f) may be identical to or different from any other R group and consists of a hydrocarbon group having 1 to 25 carbon atoms, while R the formulas given in (f) represent hydrogen or a hydrocarbon group with 1 - 25 carbon atoms. ' Furthermore, the present invention relates to the use of a plastic composition as above for the manufacture of a molded wherein the composition is formed into a mold having a surface temperature of 1100C or lower.
Den i samband med uppfinningen utnyttjade etentereftalat- plasten är en plast, som har en inre viskositet av minst 0,4. Före- trädesvis har polyetentereftalatet en övre gräns vad gäller inre viskositet av ca 1,2. Inre viskositet mätes i en blandning av mety- lenklorid och trifluorättiksyra i ett volymsförhållande av 3 : 1 och vid en temperatur av 30OC, varvid 0,5 g polyetentereftalat användes per 100 cm3 lösningsmedelsblandning (ASTM D-2857). Poly- etentereftalatet kan innehålla mindre mängder av andra sammonome- rer, som t.ex. dietylenglykol eller glutarsyra.The ethylene terephthalate used in connection with the invention the plastic is a plastic, which has an internal viscosity of at least 0.4. Before- thirdly, the polyethylene terephthalate has an upper limit in terms of internal viscosity of about 1.2. Internal viscosity is measured in a mixture of methyl len chloride and trifluoroacetic acid in a volume ratio of 3: 1 and at a temperature of 30 ° C, 0.5 g of polyethylene terephthalate was used per 100 cm 3 of solvent mixture (ASTM D-2857). Poly- The ethylene terephthalate may contain minor amounts of other commonomers. such as diethylene glycol or glutaric acid.
Det i samband med uppfinningen utnyttjade armerings- eller fyllmedlet innefattar glasfibrer, glaspärlor, aluminiumsilikat, asbest, glimmer och liknande material eller kombinationer därav, t.ex. en blandning av glimmer och glasfibrer.The reinforcement or the filler includes glass fibers, glass beads, aluminum silicate, asbestos, mica and similar materials or combinations thereof, for example a mixture of mica and fiberglass.
Bland material, som föreligger i en tillräckligt stor mängd för att göra så att kompositionerna enligt uppfinningen har ett AHH/AHC-förhållande under 0,25 (ovan definierade komponent C) in- går natrium- eller kaliumsalterna av kolvätekarboxylsyror med mellan 7 och 25 kolatomer, företrädesvis mer än 12 kolatomer.Among materials, which are present in a sufficiently large amount to cause the compositions of the invention to have one AHH / AHC ratio below 0.25 (component C defined above) the sodium or potassium salts of hydrocarbon carboxylic acids between 7 and 25 carbon atoms, preferably more than 12 carbon atoms.
Som exempel pâ dessa syror (vilka är fettsyror) kan nämnas stea- rinsyra, pelargonsyra och dokosansyra. Dessa material omfattar även natrium- eller kaliumsalterna av karboxylgruppsinnehâllande, organiska polymerer, som t.ex. sampolymerer av olefiner och akryl- syra eller metakrylsyra eller sampolymerer av aromatiska olefiner och maleinsyraanhydrid. Lämpligen innefattar dessa material natri- i79io:n;:aeso1- 7 um- eller kaliumsaltet av stearinsyra, natrium- eller kaliumsal- tet av eten/metakrylsyra-sampolymerer (däribland såväl helt som partiellt neutraliserade salter, t.ex. neutraliserade till minst ca 30%), natriumsaltet av styren/maleinsyraanhydrid-sampolymerer (däribland både helt eller delvis neutraliserade salter, tlex. neutraliserade till minst ca 30%), och natriumversatet. I de ovan uppräknade sampolymererna utgör vanligen olefindelen el- 'ler den aromatiska olefindelen 50 - 98 viktprocent av sampoly- meren och företrädesvis 80 - 98%. Ett särskilt föredraget mate- rial är natriumsaltet av eten/-metakrylsyra-sampolymerer. Sam- polymererna kan framställas medelst konventionell högtryckspo- _lymerisationsteknik.Examples of these acids (which are fatty acids) are stea- tartaric acid, geranium acid and docosanoic acid. These materials include also the sodium or potassium salts of carboxyl group-containing, organic polymers, such as copolymers of olefins and acrylic acid or methacrylic acid or copolymers of aromatic olefins and maleic anhydride. Suitably these materials comprise sodium i79io: n;: aeso1- 7 um or the potassium salt of stearic acid, sodium or potassium salt ethylene / methacrylic acid copolymers (including both whole and partially neutralized salts, e.g. neutralized to at least about 30%), the sodium salt of styrene / maleic anhydride copolymers (including both fully or partially neutralized salts, tlex. neutralized to at least about 30%), and the sodium versate. I de the copolymers listed above usually form the olefin moiety or The aromatic olefin moiety contains 50 to 98% by weight of the copolymer. and preferably 80-98%. A particularly preferred material rial is the sodium salt of ethylene / methacrylic acid copolymers. Sam- the polymers can be prepared by conventional high pressure _lymerization technique.
Föredragna organiska estrar som den ovan angivna kompo- W nenten D är de, vari de aromatiska karboxylsyrorna är syror av 7 kolväten med 1 - 3 karboxylgrupper och vari alkoholerna är alifatiska. Med andra ord är R-grupperna i àlkoholerna alkyl- eller alkylengrupper beroende på den i det speciella fallet utnyttjade R-gruppen. När karboxylsyrorna innehåller två eller flera karboxylgrupper, har dessutom lämpligen samtliga karb- oxylgrupper reagerat under bildning av ester (C00)-bindningar, dvs det förekommer inte några fria karboxylgrupper i estern.Preferred organic esters such as the above composition The values D are those in which the aromatic carboxylic acids are acids of 7 hydrocarbons having 1 to 3 carboxyl groups and wherein the alcohols are aliphatic. In other words, the R groups in the alcohols are alkyl- or alkylene groups depending on the particular case exploited the R group. When the carboxylic acids contain two or several carboxyl groups, in addition, suitably all oxyl groups reacted to form ester (C00) bonds, that is, there are no free carboxyl groups in the ester.
Lämpligen omsätts också alla hydroxylgrupperna i alkoholerna 'under bildning av ester (C00)-bindningar, dvs det förekommer inte några fria hydroxylgrupper i estern.g( , En föredragen klass av estrar är de, vari syran utgö- res av bensoesyra och alkoholen är (H0CH2)2-R*, vari R' är en alkylengrupp med 4 - 6 kolatomer (företrädesvis neopentyl- glykol) eller HO(R"O%yH, där R" är eten eller propen och y är 2 eller 3. , Föredragna ketoner, sulfoner, sulfoxider, nitriler och amider är de, vari R-grupperna i de.för dessa organiska för- eningar ovan angivna formlerna utgöres av arylgrupper med 6 - 10 kolatomer eller alkylgrupper med 1 - 10 kolatomer.Suitably all the hydroxyl groups in the alcohols are also reacted 'during the formation of ester (C00) bonds, ie it occurs no free hydroxyl groups in the ester.g (, A preferred class of esters are those in which the acid benzoic acid and the alcohol is (HOCH 2) 2 -R *, wherein R 'is one alkylene group having 4 to 6 carbon atoms (preferably neopentyl glycol) or HO (R "0% yH, where R" is ethylene or propylene and y is 2 or 3., Preferred ketones, sulfones, sulfoxides, nitriles and amides are those in which the R groups in the The above formulas are aryl groups having 6 - 10 carbon atoms or alkyl groups having 1 to 10 carbon atoms.
Specifika exempel inom dessa definitioner anges i föl- jande uppräkning (talet inom parentes efter varje förening an- ger det antal grader Celcius som 1 viktprocent av föreningen (räknat på polyetentereftalatet) sänker Tpk i den armerings- eller fyllmedelshaltiga etentereftalatplasten): 7 7900801-7 Dibensoat av neopentylglykol (2,0), dibensoat av tri- etylenglykol (3,0), dibensoat av dietylenglykol (3,2), diben- soat av dipropylenglykol (3,0), tris-2-etylhexyltrimellitat (2,5), fenylbensoat (3,0), trimetyloletantribensoat (1,53), di- oktylftalat (1,3), diisodekylftalat (0,8), bensofenon (2,5), 4-fluorbensofenon (1,9), difenylsulfon (2,8), N-etyl-o,p-tolu- ensulfonamid (2,3), tolylsulfoxid (2,6), laurylnitril (2,9) och erukylnitril (2,3).Specific examples within these definitions are given in the following enumeration (the number in parentheses after each association gives the number of degrees Celsius as 1% by weight of the compound (calculated on the polyethylene terephthalate) lowers Tpk in the reinforcement or filler-containing ethylene terephthalate plastic): 7 7900801-7 Dibenzoate of neopentyl glycol (2.0), dibenzoate of tri- ethylene glycol (3.0), dibenzoate of diethylene glycol (3.2), dibenzoate dipropylene glycol (3.0) soot, tris-2-ethylhexyl trimellitate (2.5), phenyl benzoate (3.0), trimethylolethane tribenzoate (1.53), di- octyl phthalate (1.3), diisodecyl phthalate (0.8), benzophenone (2.5), 4-fluorobenzophenone (1,9), diphenylsulfone (2,8), N-ethyl-o, p-toluene ensulfonamide (2,3), tolylsulfoxide (2,6), laurylnitrile (2,9) and erucylnitrile (2,3).
Komponenterna (C) och (D) i kompositionerna enligt upp- finningen bidrar till att man erhåller formade alster med hög ytglans vid formningstemperaturer under 110°C genom att öka kristallisationshastigheten hos polyetentereftalatet.Components (C) and (D) of the compositions according to the finning contributes to obtaining shaped articles high surface gloss at molding temperatures below 110 ° C by increase the crystallization rate of the polyethylene terephthalate.
Komponent (C) antas i första hand hjälpa till att öka kristal- liseringshastigheten, medan komponent (D) antages i första hand förbättra pylyetentereftalatets rörlighet i underkylt tillstånd genom att reducera viskositeten i detta tillstånd.Component (C) is primarily believed to help increase the crystal the lysis rate, while component (D) is assumed in the first improve the mobility of pylyene terephthalate in the subcooled condition by reducing the viscosity of this condition.
Båda komponenterna är nödvändiga för att erhålla den höga glans, som man funnit hos alster, vilka formats av kompositio- nen.Both components are necessary to obtain the high gloss, which has been found in articles which are formed by nen.
Den mängd av komponent (C) som ingâr i kompositioner- na enligt uppfinningen, är en mängd vilken resulterar i ett AHH/AI%;fiïhållande hos kompositionen under 0,25. För att få fram AHH/AQ;förhâllandet formas polyetentereftalatet vid 70°C till 1,6 mm tjocka stänger. Stängerna uppvärmes och vid mel- lan 95°C och 120°C upptages en exoterm (betecknad AHH) med en differentialavsökningskalorimeter (DSC)-cell, som är kopplad till en differentialtermisk analysapparatur av typen "Du Pont 900 Differential Thermal Analysis" (DTA).The amount of component (C) contained in the composition according to the invention, is an amount which results in a AHH / Al%; fi content of the composition below 0.25. To get AHH / AQ, the polyethylene terephthalate is formed at 70 ° C to 1.6 mm thick rods. The rods are heated and at intermediate at 95 ° C and 120 ° C, an exotherm (designated AHH) is taken up with a differential scanning calorimeter (DSC) cell, which is connected to a differential thermal analysis apparatus of the type "Du Pont 900 Differential Thermal Analysis "(DTA).
Stången uppvärmes till 290°C (som ligger över dess smältpunkt) och det smälta provet kyles med 10°C/min. En annan exoterm vid mellan ca 200 och 220°C (betecknad AHC) är den exoterm, som upptas vid nedfrysning av provet. Det har visat sig, att AHH/AHC-förhållandet är en lämplig metod för mätning av kristallisationsgraden. ~ Den uppfinningsenliga kompositionens Tpk är den tem- peratur, vid vilken värme utvecklas snabbast under det i före- gående stycke angivna uppvärmningsförloppet. Såsom angivits tidigare är den mängd av komponent (D), som ingår i kompositio- nen enligt uppfinningen, en mängd som sänker Tpk för komposi- 79oosofi-7 tionen med minst 4°C utöver Tpk för en identisk komp0sition,' som inte innehåller någon komponent (D). I Ä De övre gränserna för mängderna av komponenterna C och D ärli och för sig inte kritiska. De fysikaliska egenskaper- na kan emellertid bli påverkade på ogynnsamt sätt allteftersom mängderna ökar. Den övre gränsen för den utnyttjade mängden av endera av de båda komponenterna har därför satts vid 12 viktprocent, räknat på vikten polyetentereftalat, medan den undre gränsen ligger vid 0,5 resp. 1 viktprocent. För de före- dragna komponent (C)-salterna av eten/metakrylsyra-sampolymer ligger den övre gränsen för ingående mängd vid ca 12 viktpro- cent, räknat på vikten polyetentereftalat, medan den undre grän- sen ligger omkring 0,5%, men företrädesvis användes en mängd -inom området 1 - 5%.The rod is heated to 290 ° C (which is above it melting point) and the molten sample is cooled at 10 ° C / min. Another exotherm at between about 200 and 220 ° C (designated AHC) is it exotherm, which is taken up when the sample is frozen. It has shown that the AHH / AHC ratio is a suitable method of measurement of the degree of crystallization. ~ The Tpk of the composition according to the invention is the temperature, at which heat develops most rapidly during the going paragraph specified heating process. As indicated previously, the amount of component (D) contained in the composition according to the invention, an amount which lowers the Tpk of the composition. 79ooso fi-7 at least 4 ° C in addition to Tpk for an identical composition, ' which does not contain any component (D). IN Ä The upper limits for the quantities of components C and D ärli and in itself not critical. The physical properties- however, they can be adversely affected as time goes on the quantities increase. The upper limit of the amount used of either of the two components has therefore been set at 12 weight percent, by weight of polyethylene terephthalate, while the lower limit is 0.5 resp. 1% by weight. For those drawn component (C) salts of ethylene / methacrylic acid copolymer the upper limit for the amount contained is about 12% by weight by weight of polyethylene terephthalate, while the lower limit then is about 0.5%, but preferably an amount is used -in the range 1 - 5%.
.Förutom de ovan diskuterade komponenterna kan kompo- sitionerna enligt uppfinningen innehålla tillsatsmedel, vil- ka vanligen utnyttjas tillsammans med polyesterplatser, som t.ex. färgämnen, formsläppmedel, antioxidanter, stabilisato- rer mot inverkan av ultraviolett ljus, flamskyddsmedel och ~ liknande ämnen. Tillsatsmedel, som förbättrar fysikaliska egen- skaper, som t.ex. draghållfasthet och töjning, kan dessutom användas och bland sådana tillsatsmedel kan nämnas epoxiför- eningar (t.ex. en epoxiförening som bildas av bisfenol A och epikiørhyarin), 'vilka ingår i mängder av 0,1 - 1,5 vikt- procent, räknat på kompositionens vikt. i Kompositionerna-enligt uppfinningen beredes genom att man blandar samman komponenterna med hjälp av någon lämp- lig metod. Varken temperatur- eller tryckförhâllandena är kri- tiska. Polyetentereftalatet kan t.ex. blandas torrt i någon lämplig blandare eller trumma tillsammans med komponenterna B, C och D, varefter blandningen strängpressas i smält till- stånd. Det ur sprutmaskinen utgående materialet kan sedan hac- kas och blandas med armeringsmedel, varefter denna blandning strängpressas i smält tillstånd. _ En lämpligare metod är emellertid att blanda samman alla komponenterna i torrt tillstånd i någon lämplig blandare eller trumma, varefter blandningen strängpressas i smält till- stånd. I _ Följande exempel belyser den bästa utföringsformen 790-0807-7 '7 ,- . . vid tillämpning av uppfinningen. AHH/AHc-förhållandet och EPpk-värdet bestämdes såsom beskrivits ovan, medan glansen hos det formade provet mättes med en glansmätningsapparatzlr av typen "Gardner Multi Angle Gloss (Model GG-9095)" vid en ut- vald' vinkel, såsom angives i respektive exempel..In addition to the components discussed above, components the compositions of the invention contain additives, which can usually be used with polyester sites, such as for example dyes, mold release agents, antioxidants, stabilizers against the effects of ultraviolet light, flame retardants and ~ similar topics. Additives that improve physical properties creates, such as tensile strength and elongation, can in addition be used and among such additives may be mentioned epoxy compounds (eg an epoxy compound formed by bisphenol A. and epicurean hyarin), which are present in amounts of 0.1 to 1.5% by weight. percent, based on the weight of the composition. in The compositions of the invention are prepared by mixing the components using any suitable equal method. Neither the temperature nor the pressure conditions are critical. tiska. The polyethylene terephthalate can e.g. mix dry in someone suitable mixer or drum together with the components B, C and D, after which the mixture is extruded in molten stand. The material leaving the spraying machine can then be and mixed with reinforcing agents, after which this mixture extruded in the molten state. _ A more suitable method, however, is to mix all components in the dry state in a suitable mixer or drum, after which the mixture is extruded in molten stand. I _ The following example illustrates the best embodiment 790-0807-7 '7 , -. . in the practice of the invention. The AHH / AHc ratio and The EPpk value was determined as described above, while the gloss of the shaped sample was measured with a gloss measuring apparatus type "Gardner Multi Angle Gloss (Model GG-9095)" at a selected angle, as indicated in the respective examples.
Exempel 'I En torr blandning av 92,57 viktproc/ent torrt poly- etentereftalat med en inre viskositet av ca 0,5 till 0,6, 1 viktprocent natriumstearat, 5 viktprocent bensofenon och 1 A5 viktprocent N-stearylenzkamid (en släppmedelstillsats) sträng- sprutades genom en 28 mm dubbelskruvsprutmaskin vid en tempe- ratur av ungefär 26490 i smältan. De hackade strängar-na av den strängsprutade smältan torkades vid ca 110°O i 16 timmar _ i en vakuumugn. De torkade, hackade strängarna torr-blandades; med tillräckligt mycket "OCF 419.49." glasfiber (skuren till 0,48 om) för att erhålla 30 viktprocent glasfiber och sträng- sprutades genom en Z-stegs strängsprutmaskin med en enda ma- tarskruv vid en temperatur av ca 264°C i ,.sm'a'ltan.' ÅHH/Å H c- -förhållandet uppgick till 0,06 och Tpk var 12° lägre än för samma komposition utan något bensofenon. De strängpressade strängarna kyldes och skars, varefter de torkades vid. ca 110°C i '16 timmar i en vakuumugn. De torkade, skurna strängarna for- mades i en 170 g formsprutmaskin vid ungefär 290°G med en snabb- gående sprutkolv, 20 sekunders injektionstid och 20 sekunders formslutningstid samt en formrumstemperatïzr av 95°C. Den for- made produktens glans var mçycket god. Mätt med en glansmätare av typen "Gardner Multi Angle Gloss Meter (Model GG-9095)", som var inställd vid en vinkel av 20°, fastställdes glansen till 25. vid en fomumseemperam av 7o°c uppgick den på sam- ma sätt mätta glansen till 5.Example 'I A dry mixture of 92.57% by weight / dry polymer ethylene terephthalate with an intrinsic viscosity of about 0.5 to 0.6, 1 % by weight sodium stearate, 5% by weight benzophenone and 1 A5 % by weight of N-stearylenzkamide (a release agent additive) was sprayed through a 28 mm twin-screw sprayer at a temperature of about 26,490 in the melt. They chopped the strings off the extruded melt was dried at about 110 ° 0 for 16 hours in a vacuum oven. The dried, chopped strands were dry-mixed; with sufficient "OCF 419.49." fiberglass (cut to 0.48 om) to obtain 30% by weight of glass fiber and was sprayed through a single-stage Z-stage extruder tar screw at a temperature of about 264 ° C in ".sm'a'ltan." ÅHH / Å H c- the ratio was 0.06 and Tpk was 12 ° lower than before the same composition without any benzophenone. They extruded the strands were cooled and cut, after which they were dried. about 110 ° C for '16 hours in a vacuum oven. The dried, cut strands were in a 170 g injection molding machine at approximately 290 ° G with a walking syringe, 20 seconds injection time and 20 seconds mold closing time and a mold cavity temperature of 95 ° C. The pre- made the gloss of the product was very good. Measured with a gloss meter of the type "Gardner Multi Angle Gloss Meter (Model GG-9095)", which was set at an angle of 20 °, the gloss was determined to 25. at a forum temperature of 7 ° C, it amounted to ma way saturate the gloss to 5.
Exempel 2 - '15 och .jämförelseexempel A - F I följande exempel och jämförelseexempel tillämpades allmänt följande förfarande för att bereda kompositionerna en- ligt uppfinningen: Torrt polyetentereftalat med en inre viskositet av ca 0,5 - 0,65 blandades manuellt med glasfiber, såsom närmare anges i tabellerna nedan, och med eten/metakrylsyra-sampoly- mer (viktförhållande 85/15), som hade neutraliserats till 60 36 fvanosoí-7 8 F . med natrium (som utgör komponent C häri) i en mängd, som spe- cificeras i tabellerna nedan och med komponenten D, som när- mare 'anges i tabellerna; andra tillsatser kan inga för att förbättra hållfastheten hos formade alster eller för att för- bättra släppegenskaperna. Dessa eventuellt ingående tillsat- ser finnes närmare angivna i tabellerna. ' 7 p Den erhållna blandningen strängsprutadefs sedan ge- nom en tvâstegs 5 cm enskruvssprutmaskin vid en smälttempera- tur av 285°C och med ett vakuum av 71 om. De strängsprutade strängarna skar-s i bitar, och de erhållna plastgrynen torka- des vid 110°C i en vakuumugn under ca 16 timmar. Pla-stgrynen formades sedan till fomstycken, som hade formen av ett dricksglas utan fot och var 9,2 cm höga, hade en diameter av 7,5 cm längst upp och 5,5 cm vid botten samt en väggtjocklek av 0,49 cm. Smältans temperatur i sprutmaskinen uppgick till 295005 medan yttemperaturen i formen var 85°C. Arbetsför- loppstíder och släpptryck återfinnas i tabellerna.Examples 2 - '15 and .Comparative Examples A - F In the following examples and comparative examples were applied generally the following procedure for preparing the compositions according to the invention: Dry polyethylene terephthalate with an intrinsic viscosity of about 0.5 - 0.65 was manually mixed with fiberglass, as specified listed in the tables below, and with ethylene / methacrylic acid copolymers more (weight ratio 85/15), which had been neutralized to 60 36 fvanosoí-7 8 F. with sodium (which constitutes component C herein) in an amount specified in the tables below and with component D, which mare 'are given in the tables; other additives can no to improve the strength of shaped articles or to improve the release properties. These optional ingredients are specified in the tables. 7 p The resulting mixture was then extruded. by a two-stage 5 cm single-screw sprayer at a melting temperature 285 ° C and with a vacuum of 71 om. They extruded the strands are cut into pieces, and the resulting plastic groats are dried. at 110 ° C in a vacuum oven for about 16 hours. Pl-stgrynen was then formed into mouthpieces, which had the shape of a drinking glass without foot and was 9.2 cm high, had a diameter of 7.5 cm at the top and 5.5 cm at the bottom and a wall thickness of 0.49 cm. The temperature of the melt in the sprayer was 295005 while the surface temperature of the mold was 85 ° C. Employment race times and release pressures are found in the tables.
Glansen mättes vid en vinkel av 60° med hjälp av ovan- nämnda glansmätare av typen "Gardner Multi Angle Gloss Meter (Model GG-9095)“ flera gånger för varje prov. Glansen mättes runt det glasformade formstyckets periferi vid en tredjedel av den totala höjden uppifrån räknat. han mätte även det tryck, som erfordrades för att få det glasformade forms-trycket att släppa genom att registrera det lufttryck, som är nödvän- digt för att röra utlösaren. Tabellerna visar .ade-högsta och I lägsta glansvärdena, som erhölls vid samtliga glansmätningar som utfördes på provet. I tabellerna anges även ytans visuel- la utseende hos formstyckena.The gloss was measured at an angle of 60 ° using the above the said Gardner Multi Angle Gloss Meter (Model GG-9095) “several times for each sample. The gloss was measured around the periphery of the glass-shaped molding by one third of the total height from the top. he also measured it pressure required to obtain the glass-shaped mold pressure to release by registering the air pressure required to touch the shutter-release button. The tables show .ade-highest and I the lowest gloss values, which were obtained in all gloss measurements performed on the test. The tables also indicate the visual added appearance to the moldings.
I tabellerna är mángderna i procent: av kompo- nenterna C och D räknade på den utnyttjade vzlktsmängden poly- etentereftalat. De procentuella mängderna av fyllmedel eller armeringsmedel och andra tillsatsmedel är baserade på vikten av den blandning, som skall strängsprutas. p i I tabellerna har den som komponent D utnyttjade före- ningen betecknats med en enda bokstav. Bokstäver-na betecknar den i det enskilda fallet utnyttjade komponenten D på föl- jande sätt: 7900801-7 - dibensoat av neopentylglykol - laurylnitril - dibensoat av dipropylenglykol - erukylnivril bensofenon trioktyltrimellitat difenylsulfon N-etyl-o gp-toluensulfonamid dibensoat av dietylenglykol.In the tables, the quantities are in percent: of compos- components C and D calculated on the amount of polymer used. ethylene terephthalate. The percentage of fillers or reinforcement and other additives are based on weight of the mixture to be extruded. p i In the tables, the company used as component D has denoted by a single letter. The letters denote the component D used in the individual case way: 7900801-7 - dibenzoate of neopentyl glycol - laurylnitrile - dibenzoate of dipropylene glycol - erucylnivril benzophenone trioctyl trimellitate diphenyl sulfone N-ethyl-o gp-toluenesulfonamide dibenzoate of diethylene glycol.
Det utnyttjade armeringsmedlet eller fyllmedlet identi- fieras i tabellerna med hjälp av två. bokstäver. Bokstäverna be- tecknar följande specifika material: AA - glasfiber "OCF 2773" BB - glimmar "(Suzorite A60)" i form av små tunna plattor CC - glasfiber "OCF 419AA" De andra tillsatserna kan identifieras med hjälp av Hmfiïfilí-'ZIÜOIJ-'JP Il I följande bokstäver: X - epoxiförening, bildad av bisfenol A och epiklor- hydrin Y - tetrakis [metylen (5,B-di-tertwbutyl-Ll-hydroxi- hydrocinnamafljmetan.The reinforcing agent or filler used is identified in the tables using two. letters. The letters draws the following specific materials: AA - fiberglass "OCF 2773" BB - glimmers "(Suzorite A60)" in the form of small barrels plates CC - fiberglass "OCF 419AA" The other additives can be identified using Hm fi ï fi lí-'ZIÜOIJ-'JP Il I the following letters: X - epoxy compound, formed by bisphenol A and epichloro- hydrin Y - tetrakis [methylene (5, B-di-tert-butyl-L1-hydroxy- hydrocinnama fl jmetan.
T a b e 1 l 'l Ex Mängd Komponent Fyllmedel Andra ingående kompo- D och och mängd tillsatser nent C mängd dër- därav (0/2) (%) av (96) (95) 2 5,8 n (5,7) n. (25) X (0,6) Y (0,5) 5 5,5 A (5,4) ÅA (55) X (0,55) Y 03,25) 4 5,9 Å (5,4) AA (55) X (0,5) Y (ons) 5 5,7 A (5,5) BB (50) insen 6 5,8 A (5,6) G0 (25) insen 7 6,1 A (me) 00 (25) ingen 8 5,6 B (2,8) CC (25) ingen 9 5,5 0 (5,7) ÅA (25) X (0,6) Y (0,5) 6 7500601-7 10 [_ Tabell 1 forts.T a b e 1 l 'l Ex Quantity Component Filler Second included compo- D and and amount of additives amount C thereof (0/2) (%) of (96) (95) 2 5.8 n (5.7) n. (25) X (0.6) Y (0.5) 5.5 A (5.4) ÅA (55) X (0.55) Y 03.25) 4 5.9 Å (5.4) AA (55) X (0.5) Y (us) 5.7 A (5.5) BB (50) 6 5.8 A (5.6) G0 (25) insen 7 6.1 A (me) 00 (25) none 8 5.6 B (2.8) CC (25) none 9 5.5 0 (5.7) ÅA (25) X (0.6) Y (0.5) 6 7500601-7 10 [_ Table 1 cont.
Ex I mängd Komponent Fyllmedel ' Andra ingående kompo- 1D och och mängd 5 tillsatser nent G m" d där- _ därav %) (°//) av %) (%) 10 5,6 1) (4,5) 00; (25) samma 11 . 2,91 5 E (5,1) 00 (25) ingen '12 5,7 F (3,7) 0G (25) 6 insen 15 5,8 6G (5,5) cc (25) ingen 14 o 5,3' H (5,5) CC (25) j iflâen 15 ' 5,7 I (5,7) - 00 (25) men 5 mabell 52 ÅH-(H/ Arbets- Tryck Glans i Yüans utseen- o s förlopp vid format de pà form- Ex Ånc Am; vid släpp- skick: (lägsta stycket: ning värde/högsta _ j (%) värde) 5 2 0,16 -11 10/15 6,54 61/67 5 mycket jämn _ 5 0,16 -10 10/10 6,48 52/60 mycket jämn 4 0,16 -10 10/15 0,48 24/42 mycket jämn 5 A 0,16 . -10 10/50 2, 56 27/52 mycket jämn , 6 0,16 -11 10/15 7,52 62/69 mycket jämn ' 7 0 ,,1.6 ' -24 ' 10/15 7,45 56/62 p jämn över ' * hela ytan 8 0,16 -8,1 10/15 4,96 65/67 jämn över 5 _ hela ytan 9 0,16 -17 10/10 6,68 55/65 I mycket jämn 10 0,16 -10 10/15 5,04 51/54 mycket jämn 11' 0,16 -15 10/15 11,9 7 56/65 7 mycket jämn 12 0,16 -9,5 10/15 7,95 14/40 jämn 15 0,16 -15 10/20 8,48 24/58 mycket jämn 14 0,16 -12 10/25 8,90 20/40 jämn 1 5 0,16 -12 10/1 5 9 ,85 64/70 mycket ~ . over he a s ytan I följande jämförelseexempel användes samma tillväga- gångssätt som det som användes i föjregående exempel, och föl- jande tabeller innehåller samma kolumnhuvud som föregående tabeller. Komponent C varierades i jämförelseexemplen och upp- ges .íörvart och ett av dessas exempel. 79100801- 7 inget formnings- förlopp etable- rades 11 T a 'b e l 1 å Jämförelse- Komponent Komponent Fyll- Andra till- exempel (%) D (%) medel (%) satser (96) A ingen A (5,4) AA (25) X (G6) Y (0,5) talk (097) B material, som ingen GC (25) N-stearyl- användes i ezmzkamid ' exem len 2-15 som släpp- (5,5 medel (0,9) C ingen E (10) GG (25) ingen D natriumstea- ingen GC (25) metylstea- rß-'G (0,5) rat (Oöš) E- material, som A(1,4)ä CC (25) ingen användes i exem len 2-15 (515 F material, som E (5,0) CC (25) ingen användes i e exemplen 2-15 (0155) 35 *f Mängden är för liten.Ex In quantity Component Filler 'Second included compo- 1D and and amount of 5 additives nent G m "d there- _ hence%) (° //) of%) (%) 5.6 1) (4.5) 00; (25) same 11. 2.91 5 E (5.1) 00 (25) none '12 5.7 F (3.7) 0G (25) 6 insen 5.8 6G (5.5) cc (25) none 14 o 5.3 'H (5.5) CC (25) j i fl âen 15 '5.7 I (5.7) - 00 (25) men 5 mabell 52 ÅH- (H / Work- Press Gloss in Yüan Appearance- o s course of formatting de on form- Ex Ånc Am; in case of release condition: (lowest paragraph: value / maximum _ j (%) value) 5 2 0.16 -11 10/15 6.54 61/67 5 very even _ 5 0.16 -10 10/10 6.48 52/60 very even 4 0.16 -10 10/15 0.48 24/42 very even 5 A 0.16. -10 10/50 2, 56 27/52 very even, 6 0.16 -11 10/15 7.52 62/69 very even '7 0 ,, 1.6' -24 '10/15 7.45 56/62 p even over '* the whole surface 8 0.16 -8.1 10/15 4.96 65/67 even over 5 _ the whole surface 9 0.16 -17 10/10 6.68 55/65 In very even 10 0.16 -10 10/15 5.04 51/54 very even 11 '0.16 -15 10/15 11.9 7 56/65 7 very even 12 0.16 -9.5 10/15 7.95 14/40 even 15 0.16 -15 10/20 8.48 24/58 very even 14 0.16 -12 10/25 8.90 20/40 even 1 5 0.16 -12 10/1 5 9, 85 64/70 much ~. over he a s surface In the following comparative examples, the same procedures such as those used in the previous example, and tables contain the same column header as the previous one tables. Component C was varied in the comparative examples and given .íörvart and one of their examples. 79100801- 7 no forming course established rades 11 T a 'b e l 1 å Comparison- Component Component Fill- Other additives example (%) D (%) means (%) rates (96) A none A (5.4) AA (25) X (G6) Y (0.5) talk (097) B material, as no GC (25) N-stearyl used in ezmzkamid ' Examples 2-15 as release (5.5 means (0.9) C none E (10) GG (25) none D sodium steanings GC (25) methyl stea- rß-'G (0.5) rat (Oöš) E-material, such as A (1,4) ä CC (25) none was used in exem len 2-15 (515 F materials such as E (5.0) CC (25) none was used in e examples 2-15 (0155) 35 * f The quantity is too small.
Tabell fortsätt' _ Arbete- Tryck Glans Ytans ut- AHH/Afic Aïpk förlopp vid lägsta/ seende på. tid släpp- högsta formstycket ning (MPa) A ca 0,14- ej mätt 10/45 14,8 29/58 :mycket ojämn B ej mätt 0 10/50 9,9 15/25 måjguigm ojamn yta ' 0 en 0,5 e; mätt 10/50 formen 56/47 eäämn yta måste sprutas D ej mätt e; mätt 10/25 10,7 16/25 åket ojämn E 0,16 -5 10/50 12,5 9/18 jämn 0111 mattligt ogamn F ca 0,45 ej mätt vidhäftning/sprut- 5/8 mycket ojämn ning ' 79íIO-8-f01- 7, ¶ 12 Fastän glansvärdena för vissa ¶av försöken i tabell 5 ligger i samma storleksorclning som de glansvärden, som er- hölls för några av exemplen i tabell 2,¶ är ytans ojämnhet icke godtagbar i jämförelseförsöken.Table continue '_ Work- Print Gloss Surface- AHH / A fi c Aïpk course at lowest / sight on. time drop- highest molding ning (MPa) A approx. 0.14- not measured 10/45 14.8 29/58: very uneven B not measured 0 10/50 9.9 15/25 måjguigm ojamn yta '0 and 0.5 e; measured 10/50 form 56/47 eäämn surface must sprayed D not measured e; measured 10/25 10.7 16/25 ride uneven E 0.16 -5 10/50 12.5 9/18 even 0111 mattligt ogamn F approx. 0.45 not measured adhesion / spray- 5/8 very uneven ning ' 79íIO-8-f01- 7, ¶ 12 Although the gloss values for some of the experiments in Table 5 is in the same order of magnitude as the gloss values held for some of the examples in Table 2, ¶ is the surface roughness not acceptable in comparative trials.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US88221978A | 1978-02-28 | 1978-02-28 | |
| US06/000,631 US4352904A (en) | 1978-02-28 | 1979-01-05 | Molding resins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| SE7900801L SE7900801L (en) | 1979-08-29 |
| SE430168B true SE430168B (en) | 1983-10-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE7900801A SE430168B (en) | 1978-02-28 | 1979-01-30 | SUBSTANCE PACKAGING PLASTIC COMPOSITION CONTAINING REINFORCEMENT OR FILLER AND USE OF IT |
Country Status (15)
| Country | Link |
|---|---|
| AU (1) | AU521662B2 (en) |
| BE (1) | BE874468A (en) |
| BR (1) | BR7901204A (en) |
| CA (1) | CA1133643A (en) |
| CH (1) | CH644618A5 (en) |
| DD (1) | DD142199A5 (en) |
| DE (1) | DE2907729C2 (en) |
| ES (1) | ES478146A1 (en) |
| FR (1) | FR2418254A1 (en) |
| GB (1) | GB2015014B (en) |
| IT (1) | IT1207176B (en) |
| LU (1) | LU80979A1 (en) |
| NL (1) | NL173537C (en) |
| RO (1) | RO78442A (en) |
| SE (1) | SE430168B (en) |
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| CA1166781A (en) * | 1979-11-19 | 1984-05-01 | Peter Bier | Process for injection molding a rapidly crystallizing polyethylene terephthalate composition at reduced mold temperatures |
| EP0031201A3 (en) * | 1979-12-12 | 1981-07-15 | Imperial Chemical Industries Plc | Fast crystallising polyester compositions |
| AU535008B2 (en) | 1980-04-28 | 1984-02-23 | Teijin Limited | Polyester composition |
| US4338243A (en) * | 1980-05-07 | 1982-07-06 | E. I. Du Pont De Nemours And Company | Polyethylene terephthalate blends |
| EP0041315A1 (en) * | 1980-05-29 | 1981-12-09 | E.I. Du Pont De Nemours And Company | Polyethylene terephthalate molding blends and molded articles thereof |
| US4483955A (en) * | 1980-08-06 | 1984-11-20 | Celanese Corporation | High gloss polyethylene terephthalate reinforced resin compositions |
| US4351758A (en) | 1980-08-06 | 1982-09-28 | Celanese Corporation | Polyester blends |
| US4444931A (en) * | 1980-08-06 | 1984-04-24 | Celanese Corporation | Polyester blends |
| US4425457A (en) | 1980-08-06 | 1984-01-10 | Celanese Corporation | High gloss polyethylene terephthalate reinforced resin compositions |
| US4316866A (en) | 1980-09-26 | 1982-02-23 | R. Martin & Associates | Process and apparatus involving a cutting wire spooling system for cutting brick and tile |
| US4351757A (en) * | 1980-10-24 | 1982-09-28 | E. I. Du Pont De Nemours And Company | Molding material of polyethylene terephthalate and alkai metal salt of C30 -C54 substantially aliphatic carboxylic acid |
| US4357268A (en) | 1980-12-29 | 1982-11-02 | Allied Corporation | Nucleation agents for crystalline polymers |
| DE3276178D1 (en) * | 1981-01-30 | 1987-06-04 | Teijin Ltd | Polyester resin composition |
| DE3110906A1 (en) * | 1981-03-20 | 1982-10-14 | Akzo Gmbh, 5600 Wuppertal | HYDROPHILE POLYESTER MATERIAL |
| US4349503A (en) | 1981-05-15 | 1982-09-14 | Allied Corporation | Polyester compositions containing sodium nitrite |
| US4486561A (en) * | 1981-08-21 | 1984-12-04 | Ethyl Corporation | Injection-moldable thermoplastic polyester composition |
| US4539352A (en) * | 1981-08-21 | 1985-09-03 | Ethyl Corporation | Injection-moldable thermoplastic polyester composition |
| US4368285A (en) * | 1981-12-07 | 1983-01-11 | Dart Industries Inc. | Fast crystallizing polyethylene terephthalate containing neopentyl dibenzoate |
| JPS58117246A (en) * | 1981-12-28 | 1983-07-12 | Daicel Chem Ind Ltd | Polyester composition |
| US4378444A (en) * | 1982-05-12 | 1983-03-29 | E. I. Du Pont De Nemours And Company | Molding material |
| WO1983004038A1 (en) * | 1982-05-13 | 1983-11-24 | Ethyl Corporation | Polyester composition |
| US4533679A (en) * | 1982-06-28 | 1985-08-06 | Mobay Chemical Corporation | Reinforced polyester composition having an improved strength |
| GB2124637A (en) * | 1982-08-03 | 1984-02-22 | Bip Chemicals Ltd | Polyethylene terephthalate moulding compositions |
| US4425470A (en) | 1982-08-06 | 1984-01-10 | E. I. Du Pont De Nemours And Company | Alkali metal salts of low molecular weight polyethylene terephthalate as nucleating agents for polyethylene terephthalates |
| US4429067A (en) | 1982-10-27 | 1984-01-31 | E. I. Du Pont De Nemours And Company | Polyethylene terephthalate molding compositions |
| DE3370489D1 (en) * | 1982-11-11 | 1987-04-30 | Akzo Nv | Thermoplastic block copolyester resin composition containing a nucleating agent and an accelerator |
| US4548996A (en) * | 1984-01-09 | 1985-10-22 | Monsanto Company | Hot melt adhesive compositions |
| US4581410A (en) * | 1984-01-09 | 1986-04-08 | Monsanto Company | Hot melt adhesive compositions |
| EP0174343B1 (en) * | 1984-02-24 | 1992-04-29 | E.I. Du Pont De Nemours And Company | Toughened thermoplastic polyester compositions |
| DE3532033A1 (en) * | 1985-09-09 | 1987-03-19 | Hoechst Ag | QUICK CRYSTALIZING POLYESTER MATERIALS AND METHOD FOR THE PRODUCTION THEREOF |
| IT1197798B (en) * | 1986-08-01 | 1988-12-06 | Montefibre Spa | QUICK CRYSTALLIZATION POLYESTER COMPOSITIONS |
| EP0288398A3 (en) * | 1987-04-23 | 1989-08-09 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Fiber-reinforced polyester of improved strength |
| US4908428A (en) * | 1987-07-27 | 1990-03-13 | Montefibre S.P.A. | Quick-crystallizing polyester composition |
| US5554120A (en) * | 1994-07-25 | 1996-09-10 | Advanced Cardiovascular Systems, Inc. | Polymer blends for use in making medical devices including catheters and balloons for dilatation catheters |
| US5849846A (en) * | 1994-07-25 | 1998-12-15 | Advanced Cardiovascular Systems, Inc. | Balloons for medical catheters |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6608999A (en) * | 1965-11-20 | 1967-02-27 | ||
| US3639527A (en) * | 1967-09-05 | 1972-02-01 | Hoechst Ag | Polyester-ionic copolymer thermoplastic moulding compositions |
| US3533994A (en) * | 1968-02-20 | 1970-10-13 | Fmc Corp | Stabilized polyesters |
| US3516957A (en) * | 1968-04-29 | 1970-06-23 | Eastman Kodak Co | Thermoplastic polyester composition containing organic ester mold release agent |
| DE2014770B2 (en) * | 1969-04-01 | 1978-07-20 | Mitsubishi Rayon Co. Ltd., Tokio | Polyethylene terephthalate molding compound and nucleating agent |
| BE757093A (en) * | 1969-10-06 | 1971-04-06 | Hoechst Ag | THERMOPLASTIC MOLDING MATERIALS BASED ON POLYESTERS |
| JPS4914564A (en) * | 1972-05-22 | 1974-02-08 | ||
| JPS4928640A (en) * | 1972-07-13 | 1974-03-14 | ||
| GB1485841A (en) * | 1974-02-22 | 1977-09-14 | Ici Ltd | Polyester composition |
| AU500523B2 (en) * | 1975-12-08 | 1979-05-24 | General Electric Company | Thermoplastic molding composition |
-
1979
- 1979-01-30 SE SE7900801A patent/SE430168B/en unknown
- 1979-02-23 BR BR7901204A patent/BR7901204A/en unknown
- 1979-02-26 FR FR7904843A patent/FR2418254A1/en active Granted
- 1979-02-26 AU AU44592/79A patent/AU521662B2/en not_active Ceased
- 1979-02-27 CH CH192879A patent/CH644618A5/en not_active IP Right Cessation
- 1979-02-27 CA CA322,518A patent/CA1133643A/en not_active Expired
- 1979-02-27 BE BE0/193708A patent/BE874468A/en not_active IP Right Cessation
- 1979-02-27 ES ES478146A patent/ES478146A1/en not_active Expired
- 1979-02-27 IT IT7920606A patent/IT1207176B/en active
- 1979-02-27 DD DD79211257A patent/DD142199A5/en unknown
- 1979-02-28 NL NLAANVRAGE7901605,A patent/NL173537C/en not_active IP Right Cessation
- 1979-02-28 RO RO7996741A patent/RO78442A/en unknown
- 1979-02-28 GB GB7907034A patent/GB2015014B/en not_active Expired
- 1979-02-28 LU LU80979A patent/LU80979A1/en unknown
- 1979-02-28 DE DE2907729A patent/DE2907729C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2418254A1 (en) | 1979-09-21 |
| GB2015014B (en) | 1982-09-08 |
| NL7901605A (en) | 1979-08-30 |
| AU4459279A (en) | 1980-01-03 |
| FR2418254B1 (en) | 1981-01-30 |
| BR7901204A (en) | 1979-10-02 |
| BE874468A (en) | 1979-08-27 |
| LU80979A1 (en) | 1979-09-07 |
| CH644618A5 (en) | 1984-08-15 |
| IT7920606A0 (en) | 1979-02-27 |
| AU521662B2 (en) | 1982-04-22 |
| CA1133643A (en) | 1982-10-12 |
| IT1207176B (en) | 1989-05-17 |
| NL173537B (en) | 1983-09-01 |
| DE2907729A1 (en) | 1980-01-10 |
| ES478146A1 (en) | 1980-01-16 |
| SE7900801L (en) | 1979-08-29 |
| RO78442A (en) | 1982-03-24 |
| DD142199A5 (en) | 1980-06-11 |
| GB2015014A (en) | 1979-09-05 |
| NL173537C (en) | 1988-08-16 |
| DE2907729C2 (en) | 1982-08-26 |
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