EP0118023A1 - Process for water-proofing leather and furs - Google Patents
Process for water-proofing leather and furs 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
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- EP
- European Patent Office
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- acid
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- ammonium
- acrylic acid
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- 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)
- Supports For Pipes And Cables (AREA)
- Soil Working Implements (AREA)
- Fittings On The Vehicle Exterior For Carrying Loads, And Devices For Holding Or Mounting Articles (AREA)
- Ultra Sonic Daignosis Equipment (AREA)
- Escalators And Moving Walkways (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
Abstract
Das Verfahren zur Herstellung wasserdichter Leder und Pelze durch Gerbung, Nachgerbung, Färbung, Fettung und Fixierung unter Zuhilfenahme von Carboxylgruppen enthaltenden Copolymeren zeichnet sich dadurch aus, daß man im Anschluß an die Gerbung und ggf. Färbung im gleichen Bad nacheinander als Fettungsmittel (A) oxidierte oder oxidierte und teilsulfierte langkettige Kohlenwasserstoffe oder Wachse und als Imprägniermittel (B) Copolymere aus 60 - 95 Mol-% (Meth)Acrylsäure und 5 - 40 Mol-% eines Esters, Amids oder Nitrils der (Meth)Acrylsäure mit einem Molgewicht von 800 - 10.000 in Salzform einsetzt, danach absäuert, fixiert und fertigstellt.The process for the production of waterproof leather and furs by tanning, retanning, dyeing, greasing and fixing with the aid of copolymers containing carboxyl groups is characterized in that, after the tanning and, if appropriate, dyeing in the same bath, one after the other oxidizes as fatliquor (A) or oxidized and partially sulfonated long-chain hydrocarbons or waxes and as impregnating agent (B) copolymers of 60-95 mol% (meth) acrylic acid and 5-40 mol% of an ester, amide or nitrile of (meth) acrylic acid with a molecular weight of 800 - 10,000 used in salt form, then acidified, fixed and finished.
Description
Zur Herstellung wasserdichter Leder und Pelze kommen insbesondere drei Verfahrensprinzipien in Betracht.
- (l) Imprägnierung durch Einlagerung wasserunlöslicher Substanzen, z. B. feste Fette, Wachse oder spezielle Polymere,
- (2) Imprägnierung durch Einlagerung wasserquellender Substanzen, die bei Wasseraufnahme hochviskose Emulsionen bilden und die Faserzwischenräume des Leders verstopfen, z. B. spezielle Emulgatoren vom W/O-Typ,
- (3) Behandlung mit hydrophobierend wirkenden Substanzen, z.B. Aluminium- und Chromkomplexe, Silikone oder organische Fluor-Verbindungen.
- (l) Impregnation by storing water-insoluble substances, e.g. B. solid fats, waxes or special polymers,
- (2) Impregnation by embedding water-swelling substances that form highly viscous emulsions when water is absorbed and clog the interstices of the leather, e.g. B. special emulsifiers of the W / O type,
- (3) Treatment with substances having a hydrophobic effect, for example aluminum and chromium complexes, silicones or organic fluorine compounds.
In der Praxis hat sich eine Kombination der unter (2) und (3) genannten Maßnahme bewährt, wobei bevorzugt im Walkfaß in wäßriger Flotte gearbeitet wird. Dabei erfolgt eine Umwandlung der W/O-Emulgatoren in hydrophobierend wirkende Metallkomplexsalze durch eine Fixierung mit Chrom- bzw. Aluminuzmsalzen, die nach der Fettung durchgeführt wird, Die.ses Verfahren weist aber Nachteile auf, da die Fettung relativ hohe pH-Werte (über 6) erfordert, um ein oberflächliches Anfallen der Fette und damitIn practice, a combination of the measures mentioned under (2) and (3) has proven its worth, preference being given to working in an aqueous liquor in a drum. The W / O emulsifiers are converted into metal complex salts with a hydrophobic effect by fixing with chromium or aluminum salts, which is carried out after the greasing. This process has disadvantages, however, since the greasing has relatively high pH values (above 6) Requires a superficial accumulation of fats and thus
Verschmierungen zu vermeiden. Dies führt jedoch leicht zu einer gewissen Losnarbigkeit des Leders. Außerdem zeigen die in der Praxis erhaltenen Penetrometerwerte häufig sehr starke Schwankungen, so daß eine Nachbehandlung des Leders durch Gießen, Spritzen oder Plüschen notwendig werden kann.Avoid smearing. However, this easily leads to a certain loose grain of the leather. In addition, the penetrometer values obtained in practice often show very strong fluctuations, so that aftertreatment of the leather by casting, spraying or plushing may be necessary.
Es ist weiterhin aus der DE-Anmeldung F 10 300.28a, 9 ein Verfahren zur Verbesserung der Eigenschaften von Leder,..insbesondere hinsichtlich der Wasseraufnahme und Wasserdurchlässigkeit bekannt, das dadurch gekennzeichnet ist, daß man wäßrige Lösungen oder Emulsionen von Salzen Carboxylgruppen enthaltender Polymerisate gegebenenfalls in Gegenwart von Fettungs- und Verdickungsmitteln, und/ oder von Puffersubstanzen in das Material einbringt und dieses gegebenenfalls einer Nachbehandlung unterwirft, um die Polymerisate in den unlöslichen Zustand zu überführen. Als Carboxylgruppen enthaltende Polymerisate werden u. a. Mischpolymerisate aus Acrylsäure oder Methacrylsäure und deren Estern genannt, wobei der Gehalt an Carboxylgruppen enthaltenden Komponenten zwischen 2,5 und 50 % schwankt. Es hat sich jedoch gezeigt, daß sehr hohe Mengen an Polymerisaten(>30 % bezogen auf Falzgewicht der Leder) eingelagert werden müssen, um eine ausreichende Imprägnierwirkung zu erhalten.It is also known from DE application F 10 300.28a, 9 a method for improving the properties of leather, .. in particular with regard to water absorption and water permeability, which is characterized in that aqueous solutions or emulsions of salts of carboxyl group-containing polymers are optionally used in the presence of fatliquoring and thickening agents, and / or of buffer substances in the material and this is optionally subjected to an aftertreatment in order to convert the polymers into the insoluble state. As polymers containing carboxyl groups u. a. Copolymers of acrylic acid or methacrylic acid and their esters mentioned, the content of components containing carboxyl groups fluctuating between 2.5 and 50%. However, it has been shown that very high amounts of polymers (> 30% based on the shaved weight of the leather) must be stored in order to obtain a sufficient impregnation effect.
Gegenstand der Erfindung ist demgegenüber ein Verfahren zur Herstellung wasserdichter Leder und Pelze durch Gerbung, Nachgerbung, Färbung, Fettung und Fixierung, unter Zuhilfenahme von Carboxylgruppen enthaltenden Copolymeren, dadurch gekennzeichnet, daß man im Anschluß an die Gerbung und gegebenenfalls Färbung im gleichen Bad nacheinander als Fettungsmittel (A) oxidierte oder oxidierte und teilsulfierte langkettige C18 - C26 - Kohlenwasserstoffe oder C32 - C40 - Wachse, und als Imprägnierungsmittel (B) Copolymere aus 60 - 95 Mol-% Acrylsäure und/oder Methacrylsäure und 5 - 40 Mol-% des Methyl-, Ethyl-, Propyl- oder Butylesters, Amids oder Nitrils der Acrylsäure oder Methacrylsäure mit einem Molgewicht von 800 - 10.000, in Form der Alkali-, Ammonium- oder Aminsalze einsetzt, und danach absäuert, fixiert und fertigstellt.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.
Bei der Durchführung des Verfahrens geht man von Rohhäuten oder Fellen aus, die in üblicher Weise gegerbt und nachgegerbt werden, wobei anorganische und/oder organische, natürliche oder synthetische Gerbstoffe, wie Chrom- oder Aluminiumsalze, oder Phenol-/Naphthalinkondensationsprodukte, oder pflanzliche Gerbstoffe, eingesetzt werden.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.
Nach Beendigung der Nachgerbung und gutem Spülen erfolgt gegebenenfalls die Färbung und anschließend die Fettung. Als Fettungsmittel (A) werden erfindungsgemäß oxidierte oder oxidierte und teilsulfierte langkettige C18 - C26 - Kohlenwasserstoffe oder C32 - C40 - Wachse in einer Menge von 3 - 8 Gew.-%, bezogen auf das Falzgewicht des Leders, eingesetzt. Die Produkte weisen Säurezahlen von 5 - 100 und gegebenenfalls SO3-Gehalte von 0,2 - 2,0 Gew.-% auf. Beispiele für besonders geeignete Fettungsmittel sind sulfoxidierter C20 - C22-Paraffingatsch mit einem SO3-Gehalt von 0,2 - 0,5 Gew.-% und Säurezahlen von 5 - 15, oxidierte und sulfierte C24 - C26 - Polyethylene oder Paraffine mit einem S03-Gehalt von 0,3 - 0,8 Gew.-% und Säurezahlen von 5 - 20, sowie oxidiertes C22 - C 26 - Paraffin mit Säurezahlen von 60 - 70. Die Produkte werden vorzugsweise in Form ihrer Alkali-, Ammonium- oder Aminsalze angewendet. Die Fettungsmittel werden vorzugsweise in Kombination mit speziellen W/0-Emulgatoren wie C12 - C18 - Monoalkylphosphorsäureester, C16 - C20 - Alkenylbernsteinsäuren, Fettsäuresarcoside, Zitronensäure-Fettalkoholmonoester, ferner Fettsäuremonoethanolamid-Ethersulfaten oder Fettsäuren, in Form der Alkali-, Ammonium- oder Aminsalze eingesetzt.After retanning and good rinsing, the coloring and then the greasing may take place. 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. Examples of particularly suitable fatliquors are 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 .
Nach einer Laufzeit von 45 - 60 Minuten wird unter Zusatz des Copolymerisats (B) während 30 Minuten in der gleichen Flotte bei einem pH von 5 - 6 weiterbehandelt. Als Copolymere dienen vorzugsweise solche aus 70 - 85 Mol-% Acrylsäure und/oder Methacrylsäure mit 15 - 30 Mol-% des Methyl-, Ethyl-, Propyl- oder Butylesters oder Amids oder Nitrils der Acrylsäure oder Methacrylsäure in Form der Alkali-, Ammonium- oder Aminsalze. Das Molgewicht der Copolymeren beträgt 800 - 10.000. Bezogen auf das Falzgewicht des Leders werden - 0,5 - 3 Gew.-% an Copolymeren eingesetzt. Beispiele für geeignete Copolymere sind Produkte auf Basis 75 Mol-% Acrylsäure und 25 Mol-% Acrylsäureethylester, Na-Salz, 85 Mol-% Acrylsäure und 15 Mol-% Acrylnitril, Ammoniumsalz und 70 Mol-% Acrylsäure und 30 Mol-% Acrylamid, Na-Salz.After a running time of 45-60 minutes, the treatment with the addition of the copolymer (B) is continued for 30 minutes in the same liquor at a pH of 5-6. Such 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. Examples of 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.
Im Anschluß an diese Behandlung wird nachgesäuert, beispielsweise mit Ameisensäure oder Essigsäure und durch Zugabe von 2 - 4 Gew.-% eines Chrom- und/oder Aluminiumgerbstoffes fixiert und in üblicher Weise fertiggestellt. Man erhält weiche Leder oder Pelze mit guter Narbenfestigkeit. Die Wasserfestigkeit (Wasserdurchtritt und Wasseraufnahme) ist wesentlich verbessert. Die erzielten Ergebnisse sind von einer bemerkenswerten Gleichmäßigkeit und Reproduzierbarkeit.Following this treatment, acidification is carried out, for example with formic acid or acetic acid, and the mixture is fixed by adding 2-4% by weight of a chromium and / or aluminum tanning agent and finished in the customary manner. You get soft leather or furs with good grain resistance. The water resistance (water penetration and water absorption) is significantly improved. The results obtained are of remarkable uniformity and reproducibility.
In üblicher Weise, jedoch ohne Emulgatorzusätze geäscherte, entkälkte, gebeizte und gepickelte Rindblößen werden chromgegerbt und auf ca. 2,8 mm gefalzt. Nach Waschen mit 200 % Wasser von 25°C wird gegen Brom- - kresolgrün durchneutralisiert.In the usual way, but without emulsifier additives, 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.
Die Nachgerbung erfolgt mit
- 3 Gew.-% eines Hilfsgerbstoffes auf Basis Phenol-/ Naphthalinkondensationsprodukt
- 6 Gew.-% Mimosa
- 6 Gew.-% Quebracho
- 6 Gew.-% Kastanie bis zur Durchgerbung durch den Lederquerschnitt. Nach gutem Spülen werden die Leder mit
- 3 Gew.-% eines 25 %igen basischen Aluminiumgerbstoffs
behandelt.
- 3% by weight of an auxiliary tanning agent based on a phenol / naphthalene condensation product
- 6 wt% mimosa
- 6 wt% quebracho
- 6% by weight chestnut until tanned through the leather cross-section. After a good rinse, the leathers are washed
- 3% by weight of a 25% basic aluminum tanning agent
treated.
Die Färbung und Fettung erfolgt nach folgender Arbeitsweise
Alle Prozentangaben beziehen sich auf das Falzgewicht des Leders.All percentages refer to the fold weight of the leather.
Nach Ausspülen und üblicher Fertigstellung erhält man weiche Leder mit deutlich verzögertem Wasserdurchtritt und geringer Wasseraufnahme (Probe A).After rinsing and completion, you get soft leather with significantly delayed water penetration and low water absorption (sample A).
Ein entsprechender Vergleichsversuch ohne Copolymerisatzusatz (Probe B) ergab hinsichtlich der Wasserfestigkeit wesentlich ungünstigere Werte.
Rindoberleder wurden nach der gleichen Arbeitsweise wie im Beispiel 1 gearbeitet, jedoch wird die Fettung mit
- 5 Gew.-% sulfoxidiertem Paraffingatsch C20 - C22, 0,2 - 0,5 Gew.-% SO3, Säurezahl 5 - 15, Ammoniumsalz
- 1.4 Gew.-% C12 - C18 - Monoalkylphosphorsäureester, Na-Salz
durchgeführt.Cowhide leather was worked in the same way as in example 1, but the greasing is with
- 5% by weight of sulfoxidized paraffin gum C20 - C22, 0.2 - 0.5% by weight SO 3 , acid number 5 - 15, ammonium salt
- 1.4% by weight of C12 - C18 - monoalkyl phosphoric acid ester, Na salt
carried out.
Nach Fertigstellung erhält man weiche Leder, die ebenfalls im Falle A ein wesentlich besseres Verhalten gegenüber Wasser als im Falle B aufweisen.
Rindoberleder wurden nach der gleichen Arbeitsweise wie im Beispiel 1 gearbeitet, jedoch wird die Fettung mit
- 6,4 Gew.-% eines Gemisches aus
oxidiertem und sulfiertem
C24 - C26 - Paraffin,
0,3 - 0,8 Gew.-% SO3, Säurezahl 5 - 20, Ammoniumsalz,
C12 - C18 - Monoalkylphosphorsäureester, Na-Salz,
C16 - C18 - Alkenylbernsteinsäure, Ammoniumsalz,
im Gewichtsverhältnis von 6,2 : 2,8 : 1,3
durchgeführt.Cowhide leather was worked in the same way as in example 1, but the greasing is with
- 6.4% by weight of a mixture
oxidized and sulfated
C24 - C26 - paraffin,
0.3-0.8% by weight SO 3 , acid number 5-20, ammonium salt,
C12 - C18 - monoalkyl phosphoric acid ester, sodium salt,
C16 - C18 - alkenyl succinic acid, ammonium salt,
in a weight ratio of 6.2: 2.8: 1.3
carried out.
Nach Fertigstellung erhält man weiche Leder mit ausgezeichnetem Verhalten gegenüber Wasser im Falle A.
Rindoberleder wurden nach gleicher Arbeitsweise wie im Beispiel 1 gearbeitet, jedoch wird die Fettung mit
- 6,4 Gew.-% eines Gemisches aus
oxidiertem C22 - C26 - Paraffin, Säurezahl 60 - 70,
C12 - C18 - Monoalkylphosphorsäureester, Na-Salz,
C16 - C18 Fettsäuremonoethanolamid-2-EO-sulfat, Ammoniumsalz
im Verhältnis 4,5 : 1,5 : 0,4
durchgeführt.Cowhide leather was worked according to the same procedure as in Example 1, but the greasing is with
- 6.4% by weight of a mixture
oxidized C22 - C26 paraffin, acid number 60 - 70,
C12 - C18 - monoalkyl phosphoric acid ester, sodium salt,
C16 - C18 fatty acid monoethanolamide 2-EO sulfate, ammonium salt
in the ratio 4.5: 1.5: 0.4
carried out.
Nach Fertigstellung erhält man weiche Leder mit gutem Verhalten gegenüber Wasser im Falle A
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT84101000T ATE23366T1 (en) | 1983-02-08 | 1984-02-01 | PROCESS FOR THE MANUFACTURE OF WATERPROOF LEATHER AND FUR. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833304120 DE3304120A1 (en) | 1983-02-08 | 1983-02-08 | METHOD FOR PRODUCING WATERPROOF LEATHER AND FURS |
| DE3304120 | 1983-02-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0118023A1 true EP0118023A1 (en) | 1984-09-12 |
| EP0118023B1 EP0118023B1 (en) | 1986-11-05 |
Family
ID=6190223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84101000A Expired EP0118023B1 (en) | 1983-02-08 | 1984-02-01 | Process for water-proofing leather and furs |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4527992A (en) |
| EP (1) | EP0118023B1 (en) |
| AT (1) | ATE23366T1 (en) |
| BR (1) | BR8400513A (en) |
| CA (1) | CA1207954A (en) |
| DE (2) | DE3304120A1 (en) |
| ES (1) | ES8501446A1 (en) |
| FI (1) | FI840131A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0278267A1 (en) * | 1987-01-26 | 1988-08-17 | Chemische Fabrik Stockhausen GmbH | Retanning process |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TNSN89128A1 (en) * | 1988-12-02 | 1991-02-04 | Rohn And Haas Company Independance Mall West | LEATHER TREATMENT WITH SELECTED AMPHIPHITE COPOLYMERS |
| US5330537A (en) * | 1990-06-07 | 1994-07-19 | Rohm And Haas Company | Leather treatment selected amphiphilic copolymer |
| DE4139090A1 (en) * | 1991-11-28 | 1993-06-03 | Stockhausen Chem Fab Gmbh | USE OF COPOLYMERS WITH POLYSILOXANE UNITS FOR THE TREATMENT OF LEATHER AND FURS |
| DE4227974C2 (en) * | 1992-08-26 | 1996-04-18 | Stockhausen Chem Fab Gmbh | Copolymers containing alkoxy groups, processes for their preparation and their use for retanning leather |
| US5417723A (en) * | 1993-03-25 | 1995-05-23 | Bayer Aktiengesellschaft | Use of ester urethanes for retanning |
| DE4334796A1 (en) * | 1993-10-13 | 1995-04-20 | Bayer Ag | Softening and hydrophobic retanning agents |
| DE4402029A1 (en) * | 1994-01-25 | 1995-07-27 | Basf Ag | Aqueous solutions or dispersions of copolymers |
| DE4439990A1 (en) * | 1994-11-09 | 1996-05-15 | Bayer Ag | Leather tanning agents and agents for dyes |
| DE19516961A1 (en) * | 1995-05-12 | 1996-11-28 | Stockhausen Chem Fab Gmbh | Process for waterproofing leather at low pH values and leather produced therewith |
| 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 |
| US7160480B2 (en) * | 2005-02-22 | 2007-01-09 | E. I. Du Pont De Nemours And Company | Leather treated with fluorochemicals |
| US20060188729A1 (en) * | 2005-02-22 | 2006-08-24 | Kai-Volker Schubert | Washable leather with repellency |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE896697C (en) * | 1941-10-11 | 1953-11-16 | Basf Ag | Leather fatliquor |
| DE971898C (en) * | 1943-02-02 | 1959-04-09 | Roehm & Haas G M B H | Emulsifier for emulsions of mineral, vegetable and animal fats for leather finishing |
| DE1800244B1 (en) * | 1968-10-01 | 1970-04-02 | Roehm & Haas Gmbh Chem Fab | Process for the simultaneous greasing and impregnation of leather |
| DE2538280A1 (en) * | 1975-08-28 | 1977-03-03 | Zschimmer & Schwarz Chemische | Softeners prodn. for leather etc. from waste from polyalkylene mfr. - by sulphation and neutralisation is economical and avoids pollution |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2061618A (en) * | 1936-11-24 | Sulphonated hydrocarbon | ||
| DE30028C (en) * | J. LESSING in Lippstadt | Kober for packing and storing eggs, fruit and the like. • | ||
| US2118308A (en) * | 1936-08-08 | 1938-05-24 | American Cyanamid & Chem Corp | Leather lubrication |
| 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 (en) * | 1979-07-26 | 1981-02-19 | Roehm Gmbh | IMPROVED METHOD FOR PRODUCING LEATHER |
| DE3013912A1 (en) * | 1980-04-11 | 1981-10-29 | Röhm GmbH, 6100 Darmstadt | POLYMER PRODUCTS FOR TREATING BLOSSOMS AND LEATHER |
-
1983
- 1983-02-08 DE DE19833304120 patent/DE3304120A1/en 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/en not_active Expired
- 1984-01-13 FI FI840131A patent/FI840131A/en not_active Application Discontinuation
- 1984-02-01 DE DE8484101000T patent/DE3461200D1/en not_active Expired
- 1984-02-01 AT AT84101000T patent/ATE23366T1/en not_active IP Right Cessation
- 1984-02-01 EP EP84101000A patent/EP0118023B1/en not_active Expired
- 1984-02-07 BR BR8400513A patent/BR8400513A/en unknown
- 1984-02-08 ES ES529550A patent/ES8501446A1/en not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE896697C (en) * | 1941-10-11 | 1953-11-16 | Basf Ag | Leather fatliquor |
| DE971898C (en) * | 1943-02-02 | 1959-04-09 | Roehm & Haas G M B H | Emulsifier for emulsions of mineral, vegetable and animal fats for leather finishing |
| DE1800244B1 (en) * | 1968-10-01 | 1970-04-02 | Roehm & Haas Gmbh Chem Fab | Process for the simultaneous greasing and impregnation of leather |
| DE2538280A1 (en) * | 1975-08-28 | 1977-03-03 | Zschimmer & Schwarz Chemische | Softeners prodn. for leather etc. from waste from polyalkylene mfr. - by sulphation and neutralisation is economical and avoids pollution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0278267A1 (en) * | 1987-01-26 | 1988-08-17 | Chemische Fabrik Stockhausen GmbH | Retanning process |
Also Published As
| Publication number | Publication date |
|---|---|
| US4527992A (en) | 1985-07-09 |
| FI840131A (en) | 1984-08-09 |
| ATE23366T1 (en) | 1986-11-15 |
| EP0118023B1 (en) | 1986-11-05 |
| DE3304120A1 (en) | 1984-08-09 |
| CA1207954A (en) | 1986-07-22 |
| DE3461200D1 (en) | 1986-12-11 |
| ES529550A0 (en) | 1984-11-16 |
| ES8501446A1 (en) | 1984-11-16 |
| FI840131A0 (en) | 1984-01-13 |
| BR8400513A (en) | 1984-09-11 |
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