EP0118023A1 - Procédé de fabrication de cuirs et peaux imperméables - Google Patents
Procédé de fabrication de cuirs et peaux imperméables Download PDFInfo
- Publication number
- EP0118023A1 EP0118023A1 EP84101000A EP84101000A EP0118023A1 EP 0118023 A1 EP0118023 A1 EP 0118023A1 EP 84101000 A EP84101000 A EP 84101000A EP 84101000 A EP84101000 A EP 84101000A EP 0118023 A1 EP0118023 A1 EP 0118023A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mol
- acid
- weight
- ammonium
- acrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010985 leather Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004078 waterproofing Methods 0.000 title 1
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 238000004043 dyeing Methods 0.000 claims abstract description 6
- 239000001993 wax Substances 0.000 claims abstract description 6
- 150000001408 amides Chemical class 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 5
- 150000002825 nitriles Chemical class 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 150000002148 esters Chemical class 0.000 claims abstract description 3
- 150000003839 salts Chemical group 0.000 claims abstract description 3
- -1 amine salts Chemical class 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000012188 paraffin wax Substances 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 235000011468 Albizia julibrissin Nutrition 0.000 description 2
- 241001070944 Mimosa Species 0.000 description 2
- 235000017343 Quebracho blanco Nutrition 0.000 description 2
- 241000065615 Schinopsis balansae Species 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 240000007857 Castanea sativa Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- AAQCEEMRPKWTMP-UHFFFAOYSA-N [Br].CC1=CC=CC=C1O Chemical compound [Br].CC1=CC=CC=C1O AAQCEEMRPKWTMP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000002316 solid fats Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
Definitions
- the invention in contrast, is a process for the production of waterproof leather and furs by tanning, retanning, dyeing, greasing and fixing, with the aid of copolymers containing carboxyl groups, characterized in that one after the tanning and optionally dyeing in the same bath in succession as a fatliquor (A) oxidized or oxidized and partially sulfated long-chain C18 - C26 hydrocarbons or C32 - C40 waxes, and as impregnating agent (B) copolymers of 60-95 mol% acrylic acid and / or methacrylic acid and 5-40 mol% of the methyl , Ethyl, propyl or butyl ester, amide or nitrile of acrylic acid or methacrylic acid with a molecular weight of 800-10,000, in the form of the alkali, ammonium or amine salts, and then acidified, fixed and finished.
- A oxidized or oxidized and partially sulfated long-chain C18
- the process is carried out using raw hides or skins which are tanned and retanned in the customary manner, inorganic and / or organic, natural or synthetic tanning agents, such as chromium or aluminum salts, or phenol / naphthalene condensation products, or vegetable tanning agents, be used.
- inorganic and / or organic, natural or synthetic tanning agents such as chromium or aluminum salts, or phenol / naphthalene condensation products, or vegetable tanning agents, be used.
- As fatliquoring agents (A) according to the invention oxidized or oxidized and partially sulfonated long-chain C18 - C26 hydrocarbons or C32 - C40 waxes in an amount of 3 - 8% by weight, based on the shaved weight of the leather.
- the products have acid numbers of 5-100 and optionally SO 3 contents of 0.2-2.0% by weight.
- fatliquors examples include sulfoxidized C20-C22 paraffin wax with an SO 3 content of 0.2-0.5% by weight and acid numbers of 5-15, oxidized and sulfated C24-C26 polyethylenes or paraffins with an S03 Content of 0.3-0.8% by weight and acid numbers of 5-20, and oxidized C22-C26 paraffin with acid numbers of 60-70.
- the products are preferably in the form of their alkali metal, ammonium or amine salts applied.
- the fatliquoring agents are preferably used in combination with special W / 0 emulsifiers such as C12 - C18 monoalkyl phosphoric acid esters, C16 - C20 alkenyl succinic acids, fatty acid arcosides, citric acid fatty alcohol monoesters, also fatty acid monoethanolamide ether sulfates or fatty acids, in the form of the alkali metal, ammonium or amine salts .
- W / 0 emulsifiers such as C12 - C18 monoalkyl phosphoric acid esters, C16 - C20 alkenyl succinic acids, fatty acid arcosides, citric acid fatty alcohol monoesters, also fatty acid monoethanolamide ether sulfates or fatty acids, in the form of the alkali metal, ammonium or amine salts .
- copolymers are preferably used as 70-85 mol% of acrylic acid and / or methacrylic acid with 15-30 mol% of the methyl, ethyl, propyl or butyl ester or amide or nitrile of acrylic acid or methacrylic acid in the form of the alkali metal, ammonium or amine salts.
- the molecular weight of the copolymers is 800-10,000. Based on the shaved weight of the leather, 0.5-3% by weight of copolymers are used.
- Suitable copolymers are products based on 75 mol% of acrylic acid and 25 mol% of ethyl acrylate, sodium salt, 85 mol% of acrylic acid and 15 mol% of acrylonitrile, ammonium salt and 70 mol% of acrylic acid and 30 mol% of acrylamide, Na salt.
- limed, decalcified, pickled and pickled pelts are chrome-tanned and folded to approx. 2.8 mm. After washing with 200% water at 25 ° C, neutralized against bromine - cresol green.
- the coloring and greasing is done according to the following procedure
- soft leather After completion, soft leather is obtained which also has a much better behavior towards water in case A than in case B.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Fittings On The Vehicle Exterior For Carrying Loads, And Devices For Holding Or Mounting Articles (AREA)
- Supports For Pipes And Cables (AREA)
- Soil Working Implements (AREA)
- Escalators And Moving Walkways (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
- Ultra Sonic Daignosis Equipment (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT84101000T ATE23366T1 (de) | 1983-02-08 | 1984-02-01 | Verfahren zur herstellung wasserdichter leder und pelze. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19833304120 DE3304120A1 (de) | 1983-02-08 | 1983-02-08 | Verfahren zur herstellung wasserdichter leder und pelze |
DE3304120 | 1983-02-08 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0118023A1 true EP0118023A1 (fr) | 1984-09-12 |
EP0118023B1 EP0118023B1 (fr) | 1986-11-05 |
Family
ID=6190223
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84101000A Expired EP0118023B1 (fr) | 1983-02-08 | 1984-02-01 | Procédé de fabrication de cuirs et peaux imperméables |
Country Status (8)
Country | Link |
---|---|
US (1) | US4527992A (fr) |
EP (1) | EP0118023B1 (fr) |
AT (1) | ATE23366T1 (fr) |
BR (1) | BR8400513A (fr) |
CA (1) | CA1207954A (fr) |
DE (2) | DE3304120A1 (fr) |
ES (1) | ES529550A0 (fr) |
FI (1) | FI840131A (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0278267A1 (fr) * | 1987-01-26 | 1988-08-17 | Chemische Fabrik Stockhausen GmbH | Procédé de retannage |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TNSN89128A1 (fr) * | 1988-12-02 | 1991-02-04 | Rohn And Haas Company Independance Mall West | Traitement du cuir avec des copolymeres amphiphites choisis |
US5330537A (en) * | 1990-06-07 | 1994-07-19 | Rohm And Haas Company | Leather treatment selected amphiphilic copolymer |
DE4139090A1 (de) * | 1991-11-28 | 1993-06-03 | Stockhausen Chem Fab Gmbh | Verwendung von copolymerisaten mit polysiloxan-einheiten zur behandlung von leder und pelzen |
DE4227974C2 (de) * | 1992-08-26 | 1996-04-18 | Stockhausen Chem Fab Gmbh | Alkoxygruppenhaltige Copolymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung zum Nachgerben von Leder |
US5417723A (en) * | 1993-03-25 | 1995-05-23 | Bayer Aktiengesellschaft | Use of ester urethanes for retanning |
DE4334796A1 (de) * | 1993-10-13 | 1995-04-20 | Bayer Ag | Weichmachende und hydrophobierende Nachgerbstoffe |
DE4402029A1 (de) * | 1994-01-25 | 1995-07-27 | Basf Ag | Wäßrige Lösungen oder Dispersionen von Copolymerisaten |
DE4439990A1 (de) * | 1994-11-09 | 1996-05-15 | Bayer Ag | Ledergerbstoffe und Stellmittel für Farstoffe |
DE19516961A1 (de) * | 1995-05-12 | 1996-11-28 | Stockhausen Chem Fab Gmbh | Verfahren zur Hydrophobierung von Leder bei niedrigen pH-Werten und damit hergestellte Leder |
US6211283B1 (en) * | 1996-02-21 | 2001-04-03 | Henkel Corporation | Electrically insulated metallic surfaces with interior corners and methods and compositions therefor |
US6479612B1 (en) | 1999-08-10 | 2002-11-12 | E. I. Du Pont De Nemours And Company | Fluorochemical water and oil repellents |
US20060188729A1 (en) * | 2005-02-22 | 2006-08-24 | Kai-Volker Schubert | Washable leather with repellency |
US7160480B2 (en) * | 2005-02-22 | 2007-01-09 | E. I. Du Pont De Nemours And Company | Leather treated with fluorochemicals |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE896697C (de) * | 1941-10-11 | 1953-11-16 | Basf Ag | Lederfettungsmittel |
DE971898C (de) * | 1943-02-02 | 1959-04-09 | Roehm & Haas G M B H | Emulgiermittel fuer Emulsionen mineralischer, pflanzlicher und tierischer Fettstoffefuer die Lederzurichtung |
DE1800244B1 (de) * | 1968-10-01 | 1970-04-02 | Roehm & Haas Gmbh Chem Fab | Verfahren zum gleichzeitigen Fetten und Impraegnieren von Leder |
DE2538280A1 (de) * | 1975-08-28 | 1977-03-03 | Zschimmer & Schwarz Chemische | Verfahren zur herstellung von weichmachern fuer materialien faseriger struktur aus abfallstoffen der polyalkylenproduktion und deren verwendung |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2061618A (en) * | 1936-11-24 | Sulphonated hydrocarbon | ||
DE30028C (de) * | J. LESSING in Lippstadt | Kober zum Verpacken und Aufbewahren von Eiern, Obst und dergl. • | ||
US2115509A (en) * | 1936-08-08 | 1938-04-26 | American Cyanamid & Chem Corp | Lubricating of leather |
US2630408A (en) * | 1948-01-30 | 1953-03-03 | Nopco Chem Co | Fat composition |
US3765833A (en) * | 1970-10-07 | 1973-10-16 | Henkel & Cie Gmbh | Fat-liquoring compositions |
DE2930342A1 (de) * | 1979-07-26 | 1981-02-19 | Roehm Gmbh | Verbessertes verfahren zur herstellung von leder |
DE3013912A1 (de) * | 1980-04-11 | 1981-10-29 | Röhm GmbH, 6100 Darmstadt | Polymerprodukte zur behandlung von bloessen und leder |
-
1983
- 1983-02-08 DE DE19833304120 patent/DE3304120A1/de not_active Withdrawn
- 1983-09-08 US US06/530,244 patent/US4527992A/en not_active Expired - Fee Related
-
1984
- 1984-01-05 CA CA000444712A patent/CA1207954A/fr not_active Expired
- 1984-01-13 FI FI840131A patent/FI840131A/fi not_active Application Discontinuation
- 1984-02-01 EP EP84101000A patent/EP0118023B1/fr not_active Expired
- 1984-02-01 AT AT84101000T patent/ATE23366T1/de not_active IP Right Cessation
- 1984-02-01 DE DE8484101000T patent/DE3461200D1/de not_active Expired
- 1984-02-07 BR BR8400513A patent/BR8400513A/pt unknown
- 1984-02-08 ES ES529550A patent/ES529550A0/es active Granted
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE896697C (de) * | 1941-10-11 | 1953-11-16 | Basf Ag | Lederfettungsmittel |
DE971898C (de) * | 1943-02-02 | 1959-04-09 | Roehm & Haas G M B H | Emulgiermittel fuer Emulsionen mineralischer, pflanzlicher und tierischer Fettstoffefuer die Lederzurichtung |
DE1800244B1 (de) * | 1968-10-01 | 1970-04-02 | Roehm & Haas Gmbh Chem Fab | Verfahren zum gleichzeitigen Fetten und Impraegnieren von Leder |
DE2538280A1 (de) * | 1975-08-28 | 1977-03-03 | Zschimmer & Schwarz Chemische | Verfahren zur herstellung von weichmachern fuer materialien faseriger struktur aus abfallstoffen der polyalkylenproduktion und deren verwendung |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0278267A1 (fr) * | 1987-01-26 | 1988-08-17 | Chemische Fabrik Stockhausen GmbH | Procédé de retannage |
Also Published As
Publication number | Publication date |
---|---|
US4527992A (en) | 1985-07-09 |
FI840131A0 (fi) | 1984-01-13 |
EP0118023B1 (fr) | 1986-11-05 |
DE3461200D1 (en) | 1986-12-11 |
ES8501446A1 (es) | 1984-11-16 |
ATE23366T1 (de) | 1986-11-15 |
ES529550A0 (es) | 1984-11-16 |
DE3304120A1 (de) | 1984-08-09 |
FI840131A (fi) | 1984-08-09 |
BR8400513A (pt) | 1984-09-11 |
CA1207954A (fr) | 1986-07-22 |
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