EP0193832B1 - Verfahren zur Herstellung wasserdichter Leder oder Pelze - Google Patents
Verfahren zur Herstellung wasserdichter Leder oder Pelze Download PDFInfo
- Publication number
- EP0193832B1 EP0193832B1 EP86102381A EP86102381A EP0193832B1 EP 0193832 B1 EP0193832 B1 EP 0193832B1 EP 86102381 A EP86102381 A EP 86102381A EP 86102381 A EP86102381 A EP 86102381A EP 0193832 B1 EP0193832 B1 EP 0193832B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fat
- leather
- liquoring
- impregnating
- agents
- 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.)
- Expired
Links
- 239000010985 leather Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 230000020477 pH reduction Effects 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000003925 fat Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 235000019197 fats Nutrition 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 235000015278 beef Nutrition 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 241001494479 Pecora Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- -1 metal complex salts Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 206010000496 acne Diseases 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000037308 hair color Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000002316 solid fats Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000004078 waterproofing 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
-
- 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
- C14C9/04—Fixing tanning agents in the leather
Definitions
- Stabilizing the licker liquor with anionic and nonionic emulsifiers such as alkyl sulfates, alkylarylsulfonates or fatty alcohol ethoxylates, is out of the question because of the increase in water absorbency.
- DE-OS-1 669 347 discloses the use of water-emulsifiable sulfosuccinic acid esters for greasing leather, but no waterproofing effects are achieved.
- EP-A-0 165 481 describes a process for the production of leather and furs, a combination of sulfosuccinic acid esters with certain anionic or nonionic emulsifiers during chrome or aluminum tanning or retanning being used as the fatliquor in the tanning liquor. A waterproof effect is not achieved with this method either.
- the invention thus relates to a process for the production of waterproof leather or furs using sulfosuccinic acid monoesters in combination with impregnating and / or hydrophobizing greasing agents, characterized in that the leather or furs are subsequently impregnated in an aqueous liquor with impregnating and / or hydrophobizing agents Fatting agents that contain sulfosuccinic acid monoester salts with C 12 -C 24 fat residues, treated and fixed after acidification by adding a chromium and / or aluminum salt.
- the sulfosuccinic acid monoester salts are preferably used in combination with impregnating fatliquoring agents. These include, in particular, oxidized or oxidized and partly sulfonated C 18 -C 26 hydrocarbons or C 32 -C 4 O waxes, Phosphorklamon O C 12 -C 24 -alkyl esters, partial esters of polycarboxylic acids such as Citronenhoffreniono-C 6 -C 24 -alkyl Partial esters of polyalcohols, such as sorbitan, glycerol or pentaerythritol C 16 -C 24 fatty acid esters.
- the proportion of sulfosuccinic acid monoester salts in the fatliquor combination is 10 to 60, preferably 20 to 40 percent by weight.
- greasing agents are used in licker lubrication, depending on the type of leather, in an amount of 5 to 20 percent by weight, based on the shaved weight of the leather.
- the leather When the sulfosuccinic acid monoesters are used in combinations with neutral oils, such as long-chain hydrocarbons, chlorinated paraffin, animal and vegetable oils and fats or their methyl esters and chlorinated fatty acid methyl esters, the leather also has a reduced water absorbency if acidified after greasing and then with chromium and / or aluminum salts is fixed.
- neutral oils such as long-chain hydrocarbons, chlorinated paraffin, animal and vegetable oils and fats or their methyl esters and chlorinated fatty acid methyl esters
- fatty agents containing sulfosuccinic acid monoester salts can also be used in part in normal leaching with sulfated, sulfited and / or synthetic fatliquors based on chloroparaffin sulfonates, depending on the proportion of impregnating and / or hydrophobizing fatliquoring, a more or less pronounced water resistance is achieved.
- the sulfosuccinic acid monoester salts are prepared in a known manner by esterification of maleic anhydride with approximately one equivalent of the desired esterification component and subsequent reaction with an amount of a sulfite or bisulfite approximately equivalent to the maleic anhydride, e.g. B. according to DE-OS-1 669 347.
- esterification component fat residues with 12 to 24 carbon atoms and compounds containing hydroxyl groups are suitable.
- the fat residues can be saturated or unsaturated. They can be derived from fatty alcohols or fatty acid mono- or diglycerides, e.g. B.
- the sulfosuccinic acid monoester salts are preferably prepared as sodium or ammonium salts, but other alkalis or organic amines can also be used as cations.
- Water-soluble chromium and / or aluminum salts are used to fix the sulfosuccinic acid monoester salts.
- the application amount is 1 to 10 percent by weight in the liquor.
- the claimed process is carried out in such a way that the sulfosuccinic acid monoester salts and, if appropriate, further fatliquoring agents are used as a licker after the retanning and, if appropriate, dyeing and subsequent washing out of excess tanning agent. High temperatures above 50'C can be avoided.
- the aftertreatment is initially carried out in a customary manner by acidification, preferably with formic acid, it being possible, if appropriate, to precede a brief treatment with a polyacrylate tanning agent. Then fix with the chrome and / or aluminum salts at about pH 3.5.
- the claimed fatliquors are well absorbed by the leather and are distributed very evenly over the entire leather cross section. They have a remarkable resistance to water and give the leather excellent waterproofness, especially under dynamic loads. The result is soft, firm-grain leather with a pleasantly slim handle, which are particularly suitable for the production of upper leather, clothing velor and fur velor.
- the leathers showed good softness, coloring and sanding with a pronounced beading effect.
- the sheepskins are worked up to the hair color as usual via switches, laundry, pimples / tanning, retanning and greasing.
- the velor color is impregnated according to the following procedure.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Insulated Conductors (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Gloves (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86102381T ATE36349T1 (de) | 1985-03-01 | 1986-02-24 | Verfahren zur herstellung wasserdichter leder oder pelze. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853507241 DE3507241A1 (de) | 1985-03-01 | 1985-03-01 | Verfahren zur herstellung wasserdichter leder oder pelze |
DE3507241 | 1985-03-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0193832A1 EP0193832A1 (de) | 1986-09-10 |
EP0193832B1 true EP0193832B1 (de) | 1988-08-10 |
Family
ID=6263905
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86102381A Expired EP0193832B1 (de) | 1985-03-01 | 1986-02-24 | Verfahren zur Herstellung wasserdichter Leder oder Pelze |
Country Status (11)
Country | Link |
---|---|
US (1) | US4755187A (es) |
EP (1) | EP0193832B1 (es) |
JP (1) | JPS61211399A (es) |
AT (1) | ATE36349T1 (es) |
BR (1) | BR8600857A (es) |
CA (1) | CA1256655A (es) |
DE (2) | DE3507241A1 (es) |
ES (1) | ES8706211A1 (es) |
IN (1) | IN166295B (es) |
MX (1) | MX164625B (es) |
TR (1) | TR22674A (es) |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3620780A1 (de) * | 1986-06-20 | 1987-12-23 | Henkel Kgaa | Fettungsmittel auf basis von sulfobernsteinsaeuremonoamiden |
GB8800299D0 (en) * | 1988-01-07 | 1988-02-10 | Manzo G | Process for production of improved lubricated leather |
EP0362134B1 (de) * | 1988-09-28 | 1994-11-30 | Ciba-Geigy Ag | Lederbehandlungsmittel |
DE3909614A1 (de) * | 1989-03-23 | 1990-09-27 | Zschimmer & Schwarz Gmbh & Co | Verfahren zum fetten und hydrophobieren von leder und pelzfellen |
US5069935A (en) * | 1990-11-07 | 1991-12-03 | Wilson Sporting Goods Co. | Method of making water-repellent leather game ball |
DE4129244A1 (de) * | 1991-09-03 | 1993-03-04 | Henkel Kgaa | Waessrige dispersionen von neuen amphiphilen co-oligomeren fuer die wasch- und reinigungsbestaendige fettende ausruestung von leder und pelzfellen sowie ihre verwendung |
DE4214150A1 (de) * | 1992-04-29 | 1993-11-11 | Stockhausen Chem Fab Gmbh | Verfahren zur Hydrophobierung von Materialien faseriger Struktur und Mittel zur Durchführung des Verfahrens |
DE4223111A1 (de) * | 1992-07-14 | 1994-01-20 | Henkel Kgaa | Neue Lederfettungsmittel und ihre Verwendung |
DE4223110A1 (de) * | 1992-07-14 | 1994-01-20 | Henkel Kgaa | Neue Lederfettungsmittel und ihre Verwendung (II) |
DE4240159A1 (de) * | 1992-11-30 | 1994-06-01 | Henkel Kgaa | Sulfitierte Fettstoffe mit vermindertem Gehalt an freiem Hydrogensulfit |
DE4400508A1 (de) * | 1994-01-12 | 1995-07-13 | Henkel Kgaa | Verwendung von Aminopropionsäurederivaten zur fettenden Ausrüstung von Leder |
DE4400507A1 (de) * | 1994-01-12 | 1995-07-13 | Henkel Kgaa | Mittel zur fettenden Ausrüstung von Leder |
DE4405205A1 (de) * | 1994-02-18 | 1995-08-24 | Henkel Kgaa | Neue Lederfettungsmittel und ihre Verwendung |
DE19524268A1 (de) * | 1995-07-04 | 1997-01-09 | Henkel Kgaa | Sulfosuccinate |
US5972037A (en) * | 1995-07-26 | 1999-10-26 | Scheen Industries, Inc | Leather tanning processes and the products thereof |
US7066852B1 (en) | 1998-11-02 | 2006-06-27 | Callaway Golf Company | Game ball with improved moisture resistance |
US6123632A (en) * | 1998-11-02 | 2000-09-26 | Spalding Sports Worldwide, Inc. | Game ball with improved moisture resistance |
US6726582B1 (en) * | 2000-01-11 | 2004-04-27 | Classic Sport Companies, Inc. | Sport ball having improved surface and method for manufacture thereof |
DE10012722A1 (de) * | 2000-03-16 | 2001-09-20 | Basf Ag | Mischungen von Halbestern mehrbasiger organischer Säuren und langkettiger Alkanole, ihre Herstellung und Verwendung |
DE10111196A1 (de) * | 2001-03-08 | 2002-09-19 | Basf Ag | Mischungen von Sulfogruppen enthaltenden Estern mehrbasiger organischer Säuren mit langkettigen Alkanolen |
KR100469808B1 (ko) * | 2002-07-27 | 2005-02-02 | 김홍립 | 단면염색 가죽지의 제조방법 |
KR100617978B1 (ko) * | 2006-03-08 | 2006-08-28 | 한국신발피혁연구소 | 숫소 원피를 이용한 암소 유사 육면가죽의 제조방법 |
CN103060483B (zh) * | 2013-01-08 | 2015-01-28 | 四川大学 | 一种双防水型无铬鞣绵羊毛皮及其制备方法 |
DE102016000243A1 (de) | 2016-01-12 | 2017-07-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Lederhydrophobierungsverfahren und damit hergestelltes Leder |
CN114622043B (zh) * | 2022-04-13 | 2023-12-01 | 瑞泰(漳浦)皮业有限公司 | 头层防水革的制作方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2693996A (en) * | 1949-11-28 | 1954-11-09 | Fuchs George Hugo Von | Water resistant leather and process of making the same |
US3291557A (en) * | 1963-01-07 | 1966-12-13 | Battelle Development Corp | Alkyl dicarboxylic acid treatment of leather |
DE1669347A1 (de) * | 1967-03-25 | 1971-05-06 | Henkel & Cie Gmbh | Verfahren zum Fetten von Leder |
US3668124A (en) * | 1970-05-13 | 1972-06-06 | Pennwalt Corp | Composition and method for treating dry-cleanable soil-resistant leathers |
US4386491A (en) * | 1980-11-17 | 1983-06-07 | Sunkist Growers, Inc. | Apparatus for selectively packing layers of objects in boxes of different depths |
DE3419405A1 (de) * | 1984-05-24 | 1985-11-28 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur herstellung von leder und pelzen |
-
1985
- 1985-03-01 DE DE19853507241 patent/DE3507241A1/de not_active Withdrawn
- 1985-10-31 IN IN872/MAS/85A patent/IN166295B/en unknown
-
1986
- 1986-02-24 DE DE8686102381T patent/DE3660494D1/de not_active Expired
- 1986-02-24 EP EP86102381A patent/EP0193832B1/de not_active Expired
- 1986-02-24 AT AT86102381T patent/ATE36349T1/de not_active IP Right Cessation
- 1986-02-28 BR BR8600857A patent/BR8600857A/pt not_active IP Right Cessation
- 1986-02-28 TR TR10291/86A patent/TR22674A/xx unknown
- 1986-02-28 CA CA000502991A patent/CA1256655A/en not_active Expired
- 1986-02-28 ES ES552548A patent/ES8706211A1/es not_active Expired
- 1986-02-28 MX MX1714A patent/MX164625B/es unknown
- 1986-03-01 JP JP61045137A patent/JPS61211399A/ja active Granted
- 1986-03-03 US US06/835,499 patent/US4755187A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
IN166295B (es) | 1990-04-07 |
TR22674A (tr) | 1988-02-26 |
EP0193832A1 (de) | 1986-09-10 |
ES552548A0 (es) | 1987-05-16 |
BR8600857A (pt) | 1986-11-11 |
US4755187A (en) | 1988-07-05 |
DE3660494D1 (en) | 1988-09-15 |
ATE36349T1 (de) | 1988-08-15 |
ES8706211A1 (es) | 1987-05-16 |
MX164625B (es) | 1992-09-10 |
CA1256655A (en) | 1989-07-04 |
JPS61211399A (ja) | 1986-09-19 |
JPH0574640B2 (es) | 1993-10-18 |
DE3507241A1 (de) | 1986-09-04 |
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