EP0412389A1 - Utilisation de copolymères à base d'oléfines à longue chaîne et d'anhydrides d'acides carboxyliques à insaturation éthylénique pour l'imperméabilisation du cuir et des fourrures - Google Patents
Utilisation de copolymères à base d'oléfines à longue chaîne et d'anhydrides d'acides carboxyliques à insaturation éthylénique pour l'imperméabilisation du cuir et des fourrures Download PDFInfo
- Publication number
- EP0412389A1 EP0412389A1 EP90114574A EP90114574A EP0412389A1 EP 0412389 A1 EP0412389 A1 EP 0412389A1 EP 90114574 A EP90114574 A EP 90114574A EP 90114574 A EP90114574 A EP 90114574A EP 0412389 A1 EP0412389 A1 EP 0412389A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copolymers
- carboxyl groups
- solvolysis
- leather
- carried out
- 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
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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
Definitions
- the invention has for its object to provide an improved agent for the waterproofing of leather and fur.
- the copolymers are known for example from DE-05 3 730 885. They are obtained in the manner of bulk polymerization by copolymerizing the monomers of group (a) with the monomers of group (b) at temperatures from 80 to 300 ° C.
- Suitable monoolefins with 8 to 40 carbon atoms are, for example, n-octene-1, 2, 4, 4-trimethylpentene-1, 2,4,4-trimethylpentene-2, diisobutene, which is technically an isomer mixture of approx. 80% by weight 2 , 4,4-trimethylpentene-1 and approx.
- 2,4,4-trimethylpentene-2 is present, 4,4-dimethylhexene-1, decene-1, dodecene-1, tetradecene-1, hexadecene-1 , Octadecen-1, C20-olefin-1, C22-olefin-1, C24-olefin-1, C20- to C24-olefin-1, C24- to C28-olefin-1, C30-olefin-1, C35-olefin -1 and C40-olefin-1.
- the olefins or mixtures of olefins are commercial products.
- cyclic olefins such as cyclooctene are also suitable.
- the olefins may contain small amounts of inert organic hydrocarbons, e.g. up to about 5% by weight.
- the olefins are usually used in the commercially available quality. You do not need to be subjected to any special cleaning.
- the preferred olefins are C16 to C30 olefins.
- Component (b) of the copolymers are monoethylenically unsaturated C4 to C8 dicarboxylic anhydrides, e.g. Maleic anhydride, itaconic anhydride, mesaconic anhydride, citraconic anhydride, methylene malonic anhydride and mixtures with one another. Of the anhydrides mentioned, maleic anhydride is preferably used.
- the copolymers contain 40 to 60 mol% of monoolefins and 60 to 40 mol% of the dicarboxylic acid anhydrides mentioned and have a molar mass of 500 to 20,000, preferably 800 to 10,000 g / mol.
- Monomers (a) and (b) are obtainable by polymerizing the monomers (a) and (b) in a molar ratio of 1.1: 1 to 1: 1.
- Monomers (a) and (b) are preferably polymerized in a molar ratio of 1: 1 or only a 1% by weight excess of monomers of component (a) is used.
- the monomers of groups (a) and (b) form alternating copolymers which, at high molecular weights, contain the monomers (a) and (b) in copolymerized form in each case at 50 mol%.
- the bulk polymerization is carried out at temperatures from 80 to 300, preferably from 120 to 200 ° C., the lowest polymerization temperature to be chosen preferably being at least about 20 ° C. above the glass transition temperature of the polymer formed.
- the polymerization conditions are chosen. Polymerization at high temperatures results in copolymers low molecular weights, while polymers with higher molecular weights are formed at lower polymerization temperatures.
- the amount of the polymerization initiator also has an influence on the molecular weight. In general, 0.01 to 5% by weight, based on the monomers used in the polymerization, of polymerization initiators which form free radicals is required.
- the monomers (a) and (b) can be copolymerized at temperatures above 200 ° C. even in the absence of polymerization initiators. This means that the use of initiators is not absolutely necessary, because the monomers (a) and (b) polymerize radically at temperatures above 200 ° C. even in the absence of initiators.
- Suitable polymerization initiators are, for example, di-tertiary-butyl peroxide, acetylcyclohexanesulfonyl peroxide, diacetyl peroxydicarbonate, di-2-ethylhexylperoxidicarbonat dicyclohexyl peroxydicarbonate, tertiary-butyl perneodecanoate, 2,2 'azobis (4-methoxy-2,4-dimethylvaleronitrile), tertiary-butyl perpivalate, tertiary-butyl -2-ethyl-hexanoate, tertiary butyl permaleinate, 2,2 'azobis (isobutyronitrile), bis (tertiary butyl peroxy) cyclohexane, tertiary butyl peroxyisopropyl carbonate, tertiary butyl peracetate, di-tertiary butyl per
- the initiators can be used alone or as a mixture with one another. In bulk polymerization, they are preferably introduced into the polymerization reactor separately or in the form of a solution or dispersion in the monoolefin.
- Redox coinitiators can of course also be used in the copolymerization, for example benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals such as copper, cobalt, iron, manganese, nickel and chromium.
- the use of redox coinitiators allows the polymerization to be carried out at a lower temperature.
- the amounts of redox coinitiators usually used are about 0.1 to 2000, preferably 0.1 to 1000 ppm, based on the amounts of monomers used.
- the monomer mixture is polymerized at the lower limit of the temperature range that is suitable for the polymerization and then polymerized out at a higher temperature, it is expedient to use at least two different initiators which decompose at different temperatures, so that a sufficient concentration is obtained in each temperature interval of radicals is available.
- regulators In order to produce low molecular weight polymers, it is often expedient to carry out the copolymerization in the presence of regulators.
- Conventional regulators can be used for this, such as, for example, C1 to C4 aldehydes, formic acid and compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tertiary butyl mercaptan, n-dodecyl mercaptan and tertiary dodecyl mercaptan.
- the polymerization regulators are generally used in amounts of 0.1 to 10% by weight, based on the monomers.
- the copolymerization is carried out in customary polymerization apparatus, for example a pressure-tight kettle which is provided with a stirrer, in pressure-tight kettle cascades or in a tubular reactor.
- customary polymerization apparatus for example a pressure-tight kettle which is provided with a stirrer, in pressure-tight kettle cascades or in a tubular reactor.
- the olefins and anhydrides are copolymerized in a molar ratio in the absence of solvents.
- the copolymerization can be carried out continuously or batchwise.
- the olefin or a mixture of different olefins can be placed in the reactor and heated to the desired polymerization temperature with stirring.
- the ethylenically unsaturated dicarboxylic anhydride is metered in.
- an initiator is used, it is metered into the reaction mixture, preferably separately or as a solution in an olefin which undergoes polymerization.
- the polymerization regulator is added to the polymerizing mixture either separately or also dissolved in an olefin.
- the acid anhydrides are preferably added to the reaction mixture in the form of a melt. The temperature of the melt is about 70 to 90 ° C. If the olefin is used in excess in the copolymerization, e.g. in a 10% excess, after completion of the copolymerization it can be removed from the reaction mixture without difficulty from the copolymer melt by means of distillation, preferably under reduced pressure. The copolymer melt is then expediently processed further directly.
- the copolymers thus produced are solvolysed after cooling to room temperature or preferably in the form of the melt, which has a temperature in the range from 80 to 180 ° C., preferably 90 to 150 ° C.
- the solvolysis of the anhydride groups of the copolymers consists in hydrolysis and subsequent neutralization. It is particularly advantageous to work in pressure-tight apparatus and to convert the anhydride groups into carboxyl groups directly by adding water to a melt of the copolymers obtainable in bulk polymerization and to neutralize at least 10% of the carboxyl groups of the hydrolyzed copolymers by subsequent addition of bases.
- hydrolysis and neutralization can also be carried out practically simultaneously by adding dilute aqueous bases to the copolymer melt.
- the amounts of water and neutralizing agent are chosen so that 10 to 60, preferably 20 to 55% by weight solids-containing dispersions or solutions are formed be put on the market. Preparation solutions are then prepared from this by dilution to solids contents of 0.5 to 50% by weight.
- the copolymers obtainable by bulk polymerization can also be solvolysed by adding primary and / or secondary amines.
- the solvolysis is carried out with amounts of amines such that 10 to 50% of the total carboxyl groups formed from the copolymerized monomers (b) are amidated upon complete hydrolysis. After the formation of half-amide groups in the copolymer, neutralization takes place. It is carried out so far that at least 10% of the carboxyl groups of the copolymer obtained in bulk polymerization are neutralized.
- Solvolysis can also be carried out with aminocarboxylic acids and salts of aminocarboxylic acids, preferably the alkali metal salts.
- Alkali metal salts of ⁇ -aminocarboxylic acids are particularly preferably used, the alkali metal salts of sarcosine being particularly advantageous.
- the solvolysis using salts of aminocarboxylic acids is advantageously carried out in an aqueous medium.
- the solvolysis is carried out with such amounts of aminocarboxylates that 10 to 50% of the total carboxyl groups formed from the copolymerized monomers (b) are amidated upon complete hydrolysis. After the formation of half-amide groups in the copolymer, neutralization takes place. It is carried out so far that at least 10% of the carboxyl groups of the copolymer obtained in bulk polymerization are neutralized.
- Solvolysis can also be carried out by adding alcohols to a melt of the copolymers obtainable in bulk polymerization.
- the amounts of alcohol used are such that 10 to 50% of the total carboxyl groups formed from the copolymerized dicarboxylic acid units are esterified. This is followed by neutralization, in which at least 10% of the total carboxyl groups resulting from the copolymer containing anhydride groups are neutralized.
- Suitable neutralizing agents are, for example, ammonia, amines, alkali metal and alkaline earth metal bases, for example sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide, calcium hydroxide, barium hydroxide and all amines which are also used to amidate the copolymers.
- Neutralization is preferably carried out by adding aqueous sodium hydroxide solution to the copolymer.
- the neutralization of the copolymers containing anhydride groups is carried out at least to such a degree that copolymers which are dispersible in water are obtained.
- This degree of neutralization is at least 10% of the total from the anhydride groups emerging carboxyl groups.
- the degree of neutralization is also dependent on the chain length of the olefin of component (a) used in each case.
- a copolymer of a C30-olefin and maleic anhydride is neutralized to at least 75%, for example, a copolymer of a C20 / C20-olefin and maleic anhydride at a degree of neutralization of 50% from this copolymer resulting carboxyl groups is already readily dispersible in water.
- a degree of neutralization of 20% of the carboxyl groups formed from the copolymerized maleic anhydride is sufficient for dispersing the copolymer in water.
- Ammonia and primary and secondary amines can be used to form the amide.
- the amide formation is preferably carried out in the absence of water by reaction of the anhydride groups of the copolymer with ammonia or the amines.
- the primary and secondary amines in question can have 1 to 40, preferably 3 to 30, carbon atoms.
- Suitable amines are, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, hexylamine, cyclohexylamine, methylcyclohexylamine, 2-ethylhexylamine, n-octylamine, isotridecylamine, tallow fatty amine, stearylamine, oleylamine, dimethylamine, diethylamine Propylamine, di-isopropylamine, di-n-butylamine, di-isobutylamine, dihexylamine, di-cyclohexylamine, di-methylcyclohexylamine, di-2-ethylhexylamine, di-n-octylamine, di-isotridecylamine, di-tallow fatty amine, di-stearylamine, Di-oleylamine,
- Suitable alcohols can contain 1 to 40, preferably 3 to 30, carbon atoms.
- Primary, secondary and tertiary alcohols can be used. Both saturated aliphatic alcohols and unsaturated alcohols, such as oleyl alcohol, can be used.
- Monohydric, primary or secondary alcohols are preferably used, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol and isomers, n-hexanol and isomers, n-octanol and isomers, such as 2-ethylhexanol , Nonanols, decanols, dodecanols, tridecanols, cyclohexanol, tallow fatty alcohol, stearyl alcohol and the alcohols or alcohol mixtures with 9 to 19 carbon atoms that are easily accessible technically by oxosynthesis, such as C 9/11 oxo alcohol, C 13/15 oxo alcohol and Ziegleral alcohols , which are known under the name Alfol with 12 to 24 carbon atoms.
- oxosynthesis such as C 9/11 oxo alcohol, C 13/15 oxo alcohol and
- Alcohols with 4 to 24 carbon atoms such as n-butanol, isobutanol, amyl alcohol, 2-ethylhexanol, tridecanol, tallow fatty alcohol, stearyl alcohol, C 9/11 oxo alcohol, C 13/15 oxo alcohol, C 12/14, are preferably used -Alfols and C 16/18 -Alfols.
- the anhydride groups still present in the copolymer are hydrolysed.
- the hydrolysis of the remaining anhydride groups of the copolymer can also be carried out simultaneously with the partial neutralization still required, by adding an aqueous base to the partially amidated or esterified copolymer which still contains anhydride groups.
- the amount of water and bases is chosen so that the concentration of the copolymer dispersion or solution is preferably 20 to 55% by weight.
- the pH of the ready-to-use agents for waterproofing is in the range from about 4 to 10.
- the aqueous copolymer dispersions obtainable in this way are stable and stable in storage. They are outstandingly suitable for finishing leather and furs because they have a particularly pronounced hydrophobic effect and also have a greasy and retanning effect.
- the leather and fur material treated with these copolymer dispersions shows only a low level of water absorption and water permeability.
- the dispersions have a softening effect at the same time, so that in most cases no additional fatliquor based on natural or synthetic licker oils is required.
- the dispersions give the goods a high level and high tensile and tear strength, so that additional treatment with commercially available tanning agents, for example with vegetable tanning agents or synthetic organic tanning agents (synthetics) based on phenolsulfonic acid / phenol / formaldehyde condensation products, does not in most cases more is needed.
- commercially available tanning agents for example with vegetable tanning agents or synthetic organic tanning agents (synthetics) based on phenolsulfonic acid / phenol / formaldehyde condensation products
- aqueous dispersions to be used according to the invention contain no additional emulsifiers.
- Leather and furs, which have been treated with products containing emulsifiers, are known to have to undergo complex processes after treatment with these agents, e.g. Subsequent treatment with polyvalent metal salts are subjected in order to render the emulsifiers in the leather or in the fur skins ineffective.
- copolymer dispersions described above are suitable for the treatment of all customary tanned hides, in particular with mineral tanning agents, such as tanned hides containing chromium III salts.
- the tanned skins will be usually deacidified before treatment. They may have been stained before treatment. However, coloring can also be carried out only after the hydrophobization according to the invention has taken place.
- the tanned skins are expediently mixed with the aqueous dispersions in aqueous liquors, which can be obtained by diluting the copolymer dispersions with water, at pH values of 4 to 10, preferably 5 to 8 and temperatures of 20 to 60, preferably 30 to 50 ° C. during a period of 0.1 to 5, especially 0.5 to 2 hours, treated.
- This treatment is carried out, for example, by drumming in a barrel.
- the amount of copolymer dispersion required, based on the shaved weight of the leather or the wet weight of the fur skins is 0.1 to 30, preferably 1 to 20,% by weight.
- the fleet length i.e. the percentage weight ratio of the treatment liquor to the goods, based on the fold weight of the leather, the wet weight of the fur skins, is usually 10 to 1000, preferably 30 to 150%, for fur skins 50 to 500%.
- the pH of the treatment liquor is adjusted to a pH of 3 to 5, preferably 3.5 to 4, by adding acids, preferably using organic acids, such as formic acid.
- the treatment with the aqueous dispersions to be used according to the invention can be carried out before or after the retanning step or else in several stages, the aqueous dispersions being used in part before, during and after the retanning step.
- the aqueous dispersions to be used as hydrophobicizing agents can also be used together with conventional leather and fur finishing agents such as hydrophobic agents based on paraffin. In some cases, this improves the water repellent, oiling and retanning effects.
- the percentages in the examples are percentages by weight.
- the molecular weights of the copolymers were determined by gel permeation chromatography, using tetrahydrofuran as eluent and narrowly distributed fractions of polystyrene for calibration.
- the treated leather was tested for water absorption and water permeability using the Bally penetrometer in accordance with measurement method IUP 10 of the International Union of Leather Chemist Associations, Commission for Physical Leather Testing, cf. the leather, volume 12, 36 to 40 (1961).
- the reaction mixture is stirred after 2 hours at 110 ° C. in order to convert the anhydride groups of the copolymer into the corresponding half-amide groups.
- the reaction mixture is then cooled to 90 ° C. with stirring and, separately from one another, 480 g of a 50% strength aqueous sodium hydroxide solution and 8680 g of water, which has a temperature of 90 ° C., are added over the course of half an hour and the mixture is heated for a further 2 Hrs at 90 ° C.
- a dispersion which is viscous at room temperature and has a solids content of 25.4% is obtained.
- the molar mass of the non-solvolysed copolymer was 4800 g / mol, 50 mol% of the total carboxyl groups resulting from the anhydride groups were present as the amide group and 50 mol% were neutralized.
- the leather was then dyed with 1% by weight of a conventional anionic aniline dye. Then it was adjusted to a pH of 3.8 with formic acid. It was then washed, mechanically stretched and dried.
- the leather obtained was very soft, supple, well filled, evenly colored and had excellent dynamic water resistance.
- the test with the Bally penetrometer showed a value of 20.9% by weight for the water absorption after 15 hours at 15% compression and showed no water penetration during this period.
- the leather thus obtained was very soft and easy to grip and had a high dynamic water resistance.
- the test with the Bally penetrometer showed a value of 23.7% by weight for the water absorption after 15 hours at 15% compression and showed no water penetration during this period.
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- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3926167 | 1989-08-08 | ||
DE3926167A DE3926167A1 (de) | 1989-08-08 | 1989-08-08 | Verwendung von copolymerisaten auf basis von langkettigen olefinen und ethylenisch ungesaettigten dicarbonsaeureanhydriden zum hydrophobieren von leder und pelzfellen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0412389A1 true EP0412389A1 (fr) | 1991-02-13 |
EP0412389B1 EP0412389B1 (fr) | 1994-11-30 |
Family
ID=6386714
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90114574A Revoked EP0412389B1 (fr) | 1989-08-08 | 1990-07-30 | Utilisation de copolymères à base d'oléfines à longue chaîne et d'anhydrides d'acides carboxyliques à insaturation éthylénique pour l'imperméabilisation du cuir et des fourrures |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0412389B1 (fr) |
JP (1) | JPH0376800A (fr) |
KR (1) | KR910004817A (fr) |
AT (1) | ATE114727T1 (fr) |
AU (1) | AU628205B2 (fr) |
CA (1) | CA2021758A1 (fr) |
DE (2) | DE3926167A1 (fr) |
ES (1) | ES2064554T3 (fr) |
NZ (1) | NZ234781A (fr) |
PT (1) | PT94915B (fr) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0542033A2 (fr) * | 1991-11-14 | 1993-05-19 | BASF Aktiengesellschaft | Utilisation de préparations de pigments pour la fabrication de pâtes, d'encres d'imprimerie et de peintures |
DE4214011C1 (de) * | 1992-04-29 | 1993-11-04 | Muenzing Chemie Gmbh | Copolymerisate |
US5266165A (en) * | 1991-10-05 | 1993-11-30 | Basf Aktiengesellschaft | Paper sizing using copolymers of long-chain olefins and maleic anhydride in the form of the semiamides with morpholine |
US5268437A (en) * | 1992-01-22 | 1993-12-07 | Rohm And Haas Company | High temperature aqueous polymerization process |
EP0574351A1 (fr) * | 1992-06-09 | 1993-12-15 | Ciba-Geigy Ag | Procédé pour l'après-traitement de cuir tanné et de fourrures |
EP0583973A2 (fr) * | 1992-08-18 | 1994-02-23 | Ciba Specialty Chemicals Water Treatments Limited | Composition d'imprégnation pour cuir |
WO1994010346A1 (fr) * | 1992-10-29 | 1994-05-11 | Chemische Fabrik Stockhausen Gmbh | Procede permettant d'assouplir et de nourrir des cuirs et des fourrures |
WO1995020056A1 (fr) * | 1994-01-25 | 1995-07-27 | Basf Aktiengesellschaft | Solutions ou dispersions aqueuses de copolymeres |
EP0682044A1 (fr) * | 1994-05-10 | 1995-11-15 | Hoechst Aktiengesellschaft | Copolymères à base d'anhydrides dicarboxyliques, d'oléfines à longue chaine et de fluoro-oléfines |
US5489389A (en) * | 1992-07-14 | 1996-02-06 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
US5501707A (en) * | 1991-09-03 | 1996-03-26 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous dispersions of new amphiphilic co-oligomers for the washing- and cleaning-resistant oiling of leather and skins and their use |
US5567343A (en) * | 1992-07-14 | 1996-10-22 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
US5683611A (en) * | 1994-01-12 | 1997-11-04 | Henkel Kommanditgesellschaft Auf Aktien | Preparations for the oiling of leather |
WO1998010103A1 (fr) * | 1996-09-09 | 1998-03-12 | Stockhausen Gmbh & Co. Kg | Nouveaux produits pour le traitement du cuir, leur procede de fabrication et leur utilisation dans la fabrication de cuirs a faible exsudation |
US5728313A (en) * | 1994-02-18 | 1998-03-17 | Henkel Corporation | Leather oiling compositions and their use |
US6200640B1 (en) | 1996-04-01 | 2001-03-13 | Basf Aktiengesellschaft | Polymer composition and process for treating leather and fur skins |
US6336942B1 (en) | 1995-03-12 | 2002-01-08 | Basf Aktiengesellschaft | Processes of treating leather and skins employing polymer compositions |
WO2003044233A1 (fr) * | 2001-10-16 | 2003-05-30 | Buckman Laboratories International, Inc. | Formulation d'impermeabilisation du cuir et articles en cuir impermeabilises avec ladite formulation |
WO2011050980A2 (fr) | 2009-10-30 | 2011-05-05 | FLN FEUERLöSCHGERäTE NEURUPPIN VERTRIEBS GMBH | Composition destinée à la production d'agents extincteurs en mousse |
DE102012201167A1 (de) | 2012-01-27 | 2013-08-01 | Evonik Industries Ag | Mischungszusammensetzung enthaltend aminofunktionelle Siloxane, hydrophobePartikel und hochmolekulare Silicone sowie dessen Verwendung zur Lederbehandlung |
US9029310B2 (en) | 2008-07-07 | 2015-05-12 | Basf Se | Enzyme composition comprising enzyme containing polymer particles |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4139090A1 (de) * | 1991-11-28 | 1993-06-03 | Stockhausen Chem Fab Gmbh | Verwendung von copolymerisaten mit polysiloxan-einheiten zur behandlung von leder und pelzen |
DE4205839A1 (de) * | 1992-02-26 | 1993-09-02 | Basf Ag | Verwendung von umsetzungsprodukten von homo- oder copolymerisaten auf basis monoethylenisch ungesaettigter dicarbonsaeureanhydride mit aminen oder alkoholen zum fetten und fuellen von leder oder pelzfellen |
DE4242039A1 (de) * | 1992-12-12 | 1994-06-16 | Stockhausen Chem Fab Gmbh | Copolymerisate und ihre Verwendung zur Behandlung von Leder |
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 |
DE502004001687D1 (de) * | 2004-07-13 | 2006-11-16 | Zschimmer & Schwarz Gmbh & Co | Mittel zur hydrophobierenden Ausrüstung von Leder |
DE102005029627A1 (de) * | 2005-06-23 | 2007-01-04 | Basf Ag | Verfahren zur Herstellung von Leder |
JP2008012958A (ja) * | 2006-07-03 | 2008-01-24 | Fujikura Parachute Co Ltd | 耐g服 |
JP5941806B2 (ja) * | 2012-09-27 | 2016-06-29 | 花王株式会社 | 重合体組成物の製造方法 |
JP6199125B2 (ja) * | 2013-09-05 | 2017-09-20 | 花王株式会社 | 水性スラリー |
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DE2629748C2 (de) * | 1976-07-02 | 1979-06-07 | Zschimmer & Schwarz Chemische Fabriken, 5420 Lahnstein | Verwendung von Copolymerisaten aus Monoolefinen und Maleinsäureanhydrid zum Füllen und Fetten von Leder und Pelzfellen |
DE3730885A1 (de) * | 1987-09-15 | 1989-03-23 | Basf Ag | Kraftstoffe fuer ottomotoren |
Family Cites Families (1)
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ATE74620T1 (de) * | 1987-09-15 | 1992-04-15 | Basf Ag | Kraftstoffe fuer ottomotoren. |
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1989
- 1989-08-08 DE DE3926167A patent/DE3926167A1/de not_active Withdrawn
-
1990
- 1990-07-23 CA CA002021758A patent/CA2021758A1/fr not_active Abandoned
- 1990-07-30 DE DE59007823T patent/DE59007823D1/de not_active Revoked
- 1990-07-30 EP EP90114574A patent/EP0412389B1/fr not_active Revoked
- 1990-07-30 ES ES90114574T patent/ES2064554T3/es not_active Expired - Lifetime
- 1990-07-30 AT AT90114574T patent/ATE114727T1/de not_active IP Right Cessation
- 1990-08-06 PT PT94915A patent/PT94915B/pt not_active IP Right Cessation
- 1990-08-06 NZ NZ234781A patent/NZ234781A/xx unknown
- 1990-08-07 AU AU60227/90A patent/AU628205B2/en not_active Ceased
- 1990-08-07 JP JP2207708A patent/JPH0376800A/ja active Pending
- 1990-08-08 KR KR1019900012136A patent/KR910004817A/ko active IP Right Grant
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2629748C2 (de) * | 1976-07-02 | 1979-06-07 | Zschimmer & Schwarz Chemische Fabriken, 5420 Lahnstein | Verwendung von Copolymerisaten aus Monoolefinen und Maleinsäureanhydrid zum Füllen und Fetten von Leder und Pelzfellen |
DE3730885A1 (de) * | 1987-09-15 | 1989-03-23 | Basf Ag | Kraftstoffe fuer ottomotoren |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0542033A3 (en) * | 1991-11-14 | 1993-06-02 | Basf Aktiengesellschaft | Use of pigment preparations for the manufacture of pastes, printing inks and paints |
EP0542033A2 (fr) * | 1991-11-14 | 1993-05-19 | BASF Aktiengesellschaft | Utilisation de préparations de pigments pour la fabrication de pâtes, d'encres d'imprimerie et de peintures |
US5352729A (en) * | 1991-11-14 | 1994-10-04 | Basf Aktiengesellschaft | Use of pigment formulations for the preparation of pastes, printing inks and coatings |
US5412026A (en) * | 1992-01-22 | 1995-05-02 | Rohm And Haas Company | High temperature aqueous polymerization process |
US5268437A (en) * | 1992-01-22 | 1993-12-07 | Rohm And Haas Company | High temperature aqueous polymerization process |
DE4214011C1 (de) * | 1992-04-29 | 1993-11-04 | Muenzing Chemie Gmbh | Copolymerisate |
EP0574351A1 (fr) * | 1992-06-09 | 1993-12-15 | Ciba-Geigy Ag | Procédé pour l'après-traitement de cuir tanné et de fourrures |
US5558675A (en) * | 1992-06-09 | 1996-09-24 | Ciba-Geigy Corporation | Process for aftertreating tanned leather and pelts |
US5741434A (en) * | 1992-07-14 | 1998-04-21 | Henkel Kommanditgesellschaft Auf Aktien | Leather oiling preparations and their use |
US5489389A (en) * | 1992-07-14 | 1996-02-06 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
US5567343A (en) * | 1992-07-14 | 1996-10-22 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
EP0583973A2 (fr) * | 1992-08-18 | 1994-02-23 | Ciba Specialty Chemicals Water Treatments Limited | Composition d'imprégnation pour cuir |
EP0583973A3 (fr) * | 1992-08-18 | 1994-04-27 | Allied Colloids Ltd | |
WO1994010346A1 (fr) * | 1992-10-29 | 1994-05-11 | Chemische Fabrik Stockhausen Gmbh | Procede permettant d'assouplir et de nourrir des cuirs et des fourrures |
US5683611A (en) * | 1994-01-12 | 1997-11-04 | Henkel Kommanditgesellschaft Auf Aktien | Preparations for the oiling of leather |
WO1995020056A1 (fr) * | 1994-01-25 | 1995-07-27 | Basf Aktiengesellschaft | Solutions ou dispersions aqueuses de copolymeres |
US5728313A (en) * | 1994-02-18 | 1998-03-17 | Henkel Corporation | Leather oiling compositions and their use |
AU701756B2 (en) * | 1994-05-10 | 1999-02-04 | Clariant Gmbh | Copolymers based on ethylenically unsaturated dicarboxylic anhydrides, long-chain olefins and fluoroolefins |
EP0682044A1 (fr) * | 1994-05-10 | 1995-11-15 | Hoechst Aktiengesellschaft | Copolymères à base d'anhydrides dicarboxyliques, d'oléfines à longue chaine et de fluoro-oléfines |
US5534604A (en) * | 1994-05-10 | 1996-07-09 | Hoechst | Copolymers based on ethylenically unsaturated dicarboxylic anhydrides, long-chain olefins and fluoroolefins |
US6336942B1 (en) | 1995-03-12 | 2002-01-08 | Basf Aktiengesellschaft | Processes of treating leather and skins employing polymer compositions |
US6200640B1 (en) | 1996-04-01 | 2001-03-13 | Basf Aktiengesellschaft | Polymer composition and process for treating leather and fur skins |
WO1998010103A1 (fr) * | 1996-09-09 | 1998-03-12 | Stockhausen Gmbh & Co. Kg | Nouveaux produits pour le traitement du cuir, leur procede de fabrication et leur utilisation dans la fabrication de cuirs a faible exsudation |
WO2003044233A1 (fr) * | 2001-10-16 | 2003-05-30 | Buckman Laboratories International, Inc. | Formulation d'impermeabilisation du cuir et articles en cuir impermeabilises avec ladite formulation |
US6753369B2 (en) | 2001-10-16 | 2004-06-22 | Buckman Laboratories International, Inc. | Leather waterproofing formulation and leather goods waterproofed therewith |
US9029310B2 (en) | 2008-07-07 | 2015-05-12 | Basf Se | Enzyme composition comprising enzyme containing polymer particles |
WO2011050980A2 (fr) | 2009-10-30 | 2011-05-05 | FLN FEUERLöSCHGERäTE NEURUPPIN VERTRIEBS GMBH | Composition destinée à la production d'agents extincteurs en mousse |
DE102012201167A1 (de) | 2012-01-27 | 2013-08-01 | Evonik Industries Ag | Mischungszusammensetzung enthaltend aminofunktionelle Siloxane, hydrophobePartikel und hochmolekulare Silicone sowie dessen Verwendung zur Lederbehandlung |
WO2013110413A1 (fr) | 2012-01-27 | 2013-08-01 | Evonik Industries Ag | Composition de mélange contenant des siloxanes à fonction amino, des particules hydrophobes et du silicone à poids moléculaire élevé ainsi que leur utilisation aux fins de traitement du cuir |
Also Published As
Publication number | Publication date |
---|---|
NZ234781A (en) | 1991-10-25 |
CA2021758A1 (fr) | 1991-02-09 |
ATE114727T1 (de) | 1994-12-15 |
PT94915A (pt) | 1991-04-18 |
AU628205B2 (en) | 1992-09-10 |
DE3926167A1 (de) | 1991-02-14 |
DE59007823D1 (de) | 1995-01-12 |
PT94915B (pt) | 1997-05-28 |
ES2064554T3 (es) | 1995-02-01 |
AU6022790A (en) | 1991-02-14 |
JPH0376800A (ja) | 1991-04-02 |
EP0412389B1 (fr) | 1994-11-30 |
KR910004817A (ko) | 1991-03-29 |
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