EP0739425B1 - Mittel zur fettenden ausrüstung von leder - Google Patents
Mittel zur fettenden ausrüstung von leder Download PDFInfo
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- EP0739425B1 EP0739425B1 EP95904545A EP95904545A EP0739425B1 EP 0739425 B1 EP0739425 B1 EP 0739425B1 EP 95904545 A EP95904545 A EP 95904545A EP 95904545 A EP95904545 A EP 95904545A EP 0739425 B1 EP0739425 B1 EP 0739425B1
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- Prior art keywords
- acid
- preparations
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- oligomers
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Classifications
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- 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 relates to agents for greasing leather.
- the leather treated with these agents is characterized by good Fastness to washing and cleaning as well as good water resistance.
- the Agents according to the invention are aqueous dispersions with a content based on special aminopropionic acid derivatives and co-oligomers of fat crotonates.
- the greasing of vegetable and / or mineral tanned leather respectively Fur skins is an essential process step in the Ready-to-use equipment.
- the form of fat distribution in the skin substance and the extent of the integration of the fat components in the skin substance affect the properties and the usability of the finished products is crucial. It exists extensive knowledge of possible interactions between the fat components on the one hand and the tanned, as well as residual tannins containing skin substance on the other hand.
- the special structure the fatliquor - for example the extent of their lipophilic Groups and any reactive groups present for the reaction with suitable reactive components in the tanned leather - determine among other things, the durability and effectiveness of the greasing equipment in the practical use of leather and fur products.
- EP 193 832 relates to a method for producing watertight Leather or furs using sulfosuccinic acid monoesters in combination with impregnating and / or hydrophobic Greasing agents.
- amphiphilic agents of this kind can in the form of aqueous dispersions, emulsions and / or solutions after completion of the main tanning in the leather to be finished or Skins are worked in - for example rolled in.
- these can Amphiphilic agents simultaneously take on the function of retanning.
- there can be a final fixation of the amphiphiles Means with in particular mineral tanning agents can be provided.
- amphiphilic copolymers from one predominant proportion of at least one hydrophobic monomer and one minor portion of at least one copolymerizable hydrophilic Monomers are formed.
- hydrophobic monomers long chain alkyl (meth) acrylates, long chain alkoxy or Alkylphenoxy (polyethylene oxide) - (meth) acrylates, primary alkenes, vinyl esters of long-chain alkyl carboxylic acids and their mixtures.
- the Hydrophilic comonomers present to a lesser extent are ethylenic unsaturated water-soluble acids or hydrophilic basic ones Comonomers.
- the weight average molecular weight of the copolymers is in the range of 2,000 to 100,000.
- EP 412 389 describes the use of copolymers as agents for hydrophobicizing leather and fur skins, which are obtained by radical copolymerization of (a) C 8-40 monoolefins with (b) ethylenically unsaturated C 4-8 dicarboxylic acid anhydrides in the manner of bulk polymerization at temperatures from 80 to 300 ° C to copolymers with molecular weights of 500 to 20,000 g / mol, subsequent solvolysis of the anhydride groups of the copolymers and at least partial neutralization of the carboxyl groups formed in the solvolysis have been prepared in an aqueous medium with bases and which are in the form of aqueous dispersions or There are solutions.
- EP 418 661 describes the use of copolymers which contain (a) 50 to 90% by weight of C 8-40 alkyl (meth) acrylates, vinyl esters of C 8-40 carboxylic acids or mixtures thereof and ( b) 10 to 50% by weight of monoethylenically unsaturated C 3-12 carboxylic acids, monoethylenically unsaturated dicarboxylic acid anhydrides, half esters or half amides of monoethylenically unsaturated C 4-12 dicarboxylic acids, amides of C 3-12 monocarboxylic acids or mixtures thereof, and copolymerized, and molecular weights possess from 500 to 30,000 g / mol.
- the copolymers are in at least partially neutralized form in aqueous solution or in aqueous dispersion for the intended use.
- aqueous dispersions of co-oligomers from the radically triggered aqueous emulsion copolymerization in weakly acidic to neutral pH range as amphiphiles Means for greasing and washable finishing of leather and Fur skins;
- the main components are half esters of maleic acid with oleophilic alcohols and / or their lower alkylene oxide adducts as well as acrylic acid and / or methacrylic acid; in addition can also minor amounts of other hydrophilic and / or oleophilic Co-monomers can be contained in the oligomer molecule.
- the object of the present invention was to provide means for the above Field of application, i.e. for the greasing equipment of To provide leather.
- Fat crotonates are esters of crotonic acid (trans-2-butenoic acid) with C 10-40 fatty alcohols.
- the radical R 1 in the formula for the aminopropionic acid derivatives (I) is a saturated alkyl radical with predominantly 12 to 18 carbon atoms.
- the radical Y in the formula for the aminopropionic acid derivatives (I) is an alkylene group, in particular a group -CH 2 -CH 2 -, and the radical R 2 is a carboxyl group (-CO 2 H).
- the teaching according to the invention thus provides for the application area specified here the greasing equipment of leather and fur Combination of special aminopropionic acid derivatives with co-oligomers based on fat crotonates, their use as the main oleophilic component in amphiphilic dressings of the type concerned in The prior art has not been described so far.
- the agents according to the invention are for rapid and penetrating impregnating finish of leather and / or fur particularly suitable, so that genuine and cleanable leather and fur skins become accessible.
- the so obtained leather due to the hydrophobic properties of the invention Good water resistance.
- those fatty crotonate building blocks (a) are preferred which contain C 12-24 fatty alcohols as the alcohol component.
- Straight-chain fatty alcohols or their mixtures are preferred.
- the use of branched-chain fatty alcohols in the fat crotonate component (a) can also lead to interesting results in individual cases. For example, by using such branched-chain alcohols to a limited extent, the penetrability of the co-oligomer (II) into the fiber structure of the skin material to be treated can be promoted.
- branched alcohols with a shorter carbon number, suitable alcohols having at least 6 carbon atoms, preferably having at least 8 carbon atoms.
- An important branched chain alcohol that can be used in connection with the fatty crotonate building blocks (a) is 2-ethylhexanol.
- the amount of branched-chain, in particular shorter, alcohols to be used will always be comparatively small.
- no more than 50% by weight, preferably no more than 30 or no more than 20% by weight, of the alcohol residues present in (a) are formed by such branched-chain, in particular lower, alcohols.
- hydrophilic used in the amphiphilic co-oligomers (II) Components (b) can consist of the corresponding building blocks the co-oligomers of EP 372 746, EP 412 389 and Correspond to EP 418 661.
- the last-mentioned publication provides detailed information on suitable classes of substances and numerous special representatives.
- Particularly important building blocks (b) for the co-oligomers (II) are in According to the present invention, ethylenically unsaturated monocarboxylic acids and / or ethylenically unsaturated dicarboxylic acids and / or their anhydrides each with preferably up to 12 carbon atoms.
- the dicarboxylic acids can also at least partially in the form of their partial derivatives with a carboxyl group and a derivatized carboxylic acid group for example as dicarboxylic acid half esters.
- Particularly interesting representatives from the class of monoethylenically unsaturated C 3-12 monocarboxylic acids are, for example, acrylic acid, methacrylic acid and crotonic acid.
- Particularly suitable building blocks (b) can also be dicarboxylic acids or their derivatives, in particular their anhydrides. Typical representatives are maleic acid, fumaric acid, itaconic acid, glutaconic acid and corresponding anhydrides.
- Maleic anhydride is of particular importance. Fat crotonates (a) and maleic anhydride can be satisfactory Way with or without the use of auxiliary solvents to co-oligomers (II) implement an easily adjustable low molecular weight. It is particularly possible to use approximately the same molar amounts Maleic anhydride and fat crotonate with each other for implementation bring so that after solvolysis, especially hydrolysis of the maleic anhydride building blocks on the one hand, sufficiently high concentrations on carboxyl groups for fixing the oligomers in the skin or Fiber structure are available, on the other hand also reliably high levels of oleophilic and therefore greasy and water-repellent fat crotonate building block.
- hydrophilic building blocks (b) are also other copolymerizable, hydrophilic Connections can be used.
- Sulfoic acid groups in particular come into consideration here containing ethylenically unsaturated monomers.
- Known Representatives of this type are, in particular, corresponding aliphatic ones and / or aromatic sulfonic acids, such as styrene sulfonic acid also compounds such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid and the same.
- the block can (b) of the co-oligomer (II) wholly or partly from those of the copolymerization or co-oligomerization accessible sulfonic acid compounds be educated.
- Preferred ranges for the mixing ratios are about 35 to 80% by weight (a) to 65 to 20% by weight (b).
- amphiphilic co-oligomers can (II) also minor amounts of other copolymerizable Contain comonomers, which are in the above definition as building blocks (c) are designated.
- Any of the co-oligomerization can be suitable here accessible ethylenically unsaturated compounds as they are are described in the relevant prior art, cf. here for example EP 418 661 Al, column 3, 49 to column 4, 27. In the As a rule, these are comonomers that are neither pronounced Hydrophobing effect also have hydrophilizing groups in the Sense of the carboxyl groups or sulfonic acid groups of the invention have used components (b).
- Such comonomers (c) in the amphiphilic co-oligomers described according to the invention used their share is preferably no longer than about 30% by weight and in particular not more than about 15% by weight - % by weight - refers to the sum of (a), (b) and (c).
- co-oligomers (II) particularly preferred which are free from those according to the above Definition of optional building blocks (c), that is, the exclusive ones are built up from building blocks (a) and (b).
- These preferred Co-oligomers (II) contain building blocks (a) and (b) in mixing ratios from about 40 to 70% by weight (a) to 60 to 30 % By weight (b); the percentages by weight relate to the sum again of (a) and (b).
- the co-oligomers (II) based on the fat crotonates preferably have average molecular weights in the range from about 500 to 30,000 g / mole. Molar masses in the range can be particularly suitable from about 1,000 to 15,000 g / mol. It has been shown that within of these comparatively broad areas the lower values - average molecular weights or molecular weights in the range of about 1,000 to 4,000 or 5,000 g / mol and expediently in the range from about 1,000 to 3,000 g / mol - can be of particular importance.
- those co-oligomers (II) are within the scope of the invention
- Lessons preferred from the implementation of fat crotonates and maleic anhydride result and their maleic anhydride building blocks by hydrolysis and / or solvolysis with H-active components in the corresponding form with free carboxyl groups have been converted.
- solvolysis of maleic anhydride building blocks with H-active components alcohols are particularly suitable but also other compounds such as carboxylic acids, reactive hydrogen containing amino compounds and the like.
- Such targeted solvolysis can be influenced in a targeted manner a strengthening of the greasy or water-repellent Properties of the co-oligomers (II).
- the ratio from oleophilic to hydrophilic groups towards the water-repellent oleophilic elements are moved.
- co-oligomers (II) access to the co-oligomers (II) is also, for example possible in the following way: In a first process stage, the free crotonic acid and maleic anhydride with each other to the corresponding Implemented oligomer compound. Then is excluded of water and rapid discharge of the condensation water Esterification of the crotonic acid components with the desired fatty alcohols or fatty alcohol mixtures. Below then the hydrolysis or solvolysis of the anhydride rings carried out.
- the agents according to the invention are preferably weak acidic to weakly alkaline range.
- it may be appropriate to offer forms provide the aqueous phase by adding inorganic and / or organic bases on neutral to weakly alkaline pH values is set.
- Suitable for pH regulation all bases described in the relevant prior art.
- the alkali salts, in particular sodium, are preferred and / or potassium.
- ammonium salts or salts of alkanolamines such as diethanolamine are suitable representatives.
- Preferred pH values for products that are stable in storage can be in the range of pH 7 to 8.
- aqueous pasty masses can be produced be, the valuable content of components (I) and (II) for example is in the range of about 30 to about 75% by weight.
- Such pasty masses are mixed with water and / or aqueous active ingredients of the type described below at any time and to put it into practical use.
- the agents according to the invention are used together with selected emulsifiers which, when introduced into mineral-tanned leather and / or furs in particular, cause additional greasing or hydrophobicization and can preferably be fixed simultaneously via acidic groups in the tanned leather or fur.
- emulsifiers which, when introduced into mineral-tanned leather and / or furs in particular, cause additional greasing or hydrophobicization and can preferably be fixed simultaneously via acidic groups in the tanned leather or fur.
- emulsifiers are the water-emulsifiable sulfosuccinic acid half-esters mentioned at the outset, which are derived from long-chain fatty alcohols and / or their alkylene oxide adducts.
- An important example of the emulsifier class of the type concerned here are C 18 sulfosuccinic acid half esters. It has been shown that by using such emulsifier-like auxiliary components - which are known per se as finishing agents for
- the agents according to the invention can also contain greasing agents or hydrophobizing agents in the sense of the mixtures of materials from EP 193 832 cited at the beginning.
- the mixtures according to the invention of components (I) and (II) combined with impregnating and / or hydrophobizing fatliquoring agents, such as sulfosuccinic acid monoester salts with C 12-24 fat residues, in combination with other impregnating fatliquoring agents are selected in particular from the group of oxidized or oxidized and partially sulfated C 18-26 hydrocarbons or C 32-40 waxes.
- additional impregnating fatliquors are phosphoric acid mono-C 12-24 alkyl esters, partial esters of polycarboxylic acids such as citric acid mono-C 16-24 alkyl esters, partial esters of polyalcohols such as sorbitan, glycerol or pentaerythritol C 16-24 fatty acid esters .
- a particularly suitable class of emulsifiers which can also be used in the context of the teaching according to the invention, are the N-acylamino acids known from the finishing of leather and furs with fatty substances, in particular fatty acid sarcosides, for example N-oleoyl sarcosine, as used, for example, as emulsifiers for introducing silicone oils in leather and furs are described in detail in EP-B-0 213 480.
- Suitable emulsifiers are accordingly, in particular, salts of N- (C 9-20 -acyl) -amino acids, corresponding salts of an amino acid having 2 to 6 C atoms, which with the acyl residue of a saturated or unsaturated fatty acid having 9 to 20 C atoms Amine nitrogen, which is optionally additionally substituted by methyl, is of particular importance.
- Suitable salts of these emulsifiers are in particular alkali, ammonium or alkanolamine salts.
- N- (C 9-20 -acyl) amino acids those with 2 to 4 C atoms and with the amino group in the alpha position to the carboxyl group are particularly preferred, which are also substituted on the amine nitrogen atom by a methyl group.
- the fatty acid sarcosides of saturated or unsaturated fatty acids with 9 to 20, preferably 16 to 18, carbon atoms have a particularly superior effect.
- the preferred sarcoside is the oleic acid sarcoside.
- N-stearoyl sarcosine, N-lauroyl sarcosine and N-isononanoyl sarcosine are particularly suitable, in each case in the form of their alkali metal salts, ammonium salts or the salts of mono-, di- or trialkanolamines with in particular 2 to 4 C- Atoms in the alkanol residue.
- the amount is Components (I) and (II) compulsory according to the invention preferably at least about 35% by weight of the material mixture and in particular at least about 50% by weight. However, it may be useful at least about 70 to 80 wt .-% of the total to be equipped A mixture of valuable materials to be introduced into leather or fur skins to be provided on the basis of components (I) and (II).
- the dispersions of the invention are suitable for the treatment of all usual tanned hides, especially appropriate material, that has been tanned with mineral tannins.
- the tanned Skins are usually deacidified before treatment. You can have been stained before treatment. A coloring can but also only after the treatment carried out according to the invention be made.
- the treatment takes place, for example by walking in a FaB.
- the amount of the invention Dispersions are usually 0.1 to 30 wt .-%, in particular 1 to 20% by weight based on the shaved weight of the leather or the wet weight of the fur skins.
- the fleet length is usually 10 to 1,000%, preferably 30 to 150%, for fur skins 50 to 500%.
- the addition of organic is particularly suitable Acids, preferably formic acid.
- Preferred pH values are in the range from 3 to 5, preferably in the range from about 3.5 to 4.
- fixation with mineral tanning agents in particular downstream, whereby the use of aluminum salts, but also from other multivalent mineral salts, e.g. Chromium or zirconium salts can be particularly preferred.
- the aminopropionic acid derivatives (I) can be prepared by methods known per se, e.g. B. by addition of acrylic or methacrylic acid to primary Alkylamines and subsequent implementation of the resulting N-alkylaminopropionic acids with carboxylic acid anhydrides, carboxylic acid chlorides, Sulfonic acid chlorides, isocyanates, halocarboxylic acids or acrylic or methacrylic acids (see e.g. the above-cited DE-A-37 17 961).
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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)
- Cosmetics (AREA)
Description
- der Rest R1 eine gesättigte oder ungesättigte, geradkettige oder verzweigte Alkyl- oder Alkoxyalkylgruppe mit 8 bis 22 C-Atomen,
- der Rest R2 eine Alkylgruppe mit 1 bis 18 C-Atomen, einen gesättigten oder ungesättigten Carboxyalkylrest mit 3 bis 4 C-Atomen, einen Carboxyphenylrest oder einen Carboxylrest
- der Rest R3 Wasserstoff oder eine Methylgruppe,
- der Rest X Wasserstoff, Alkalimetall, Erdalkalimetall, Ammonium, Alkylammonium oder Alkanolammonium und
- der Rest Y eine Gruppe -CO-, -SO2-, -CONH oder eine Alkylengruppe mit bis zu drei C-Atomen
Restmonomere: | |
C16-Crotonat | 5,1 % |
C18-Crotonat | 6,3 % |
Maleinsäureanhydrid | < 0,1 % |
Molekulargewichte: | |
Mw | 2.100 g/Mol |
Mn | 1.200 g/Mol |
Feststoffgehalte | 40,2 Gew.-% |
Restmonomere: | |
C16-Crotonat | 3,9 % |
C18-Crotonat | 4,3 % |
Maleinsäureanhydrid | < 0,01 % |
Molekulargewichte: | |
Mw | 2.000 g/Mol |
Mn | 1.350 g/Mol |
Feststoffgehalt | 30,1 Gew.-% |
Restmonomere: | |
C16-Crotonat | 5,6 % |
C18-Crotonat | 6,1 % |
Maleinsäureanhydrid | < 0,1 % |
Molekulargewichte: | |
Mw | 2.100 g/Mol |
Mn | 1.300 g/Mol |
Feststoffgehalt | 34,4 Gew.-% |
Restmonomere: | |
Stenol 1618 | 4,7 % |
Maleinsäureanhydrid | 0,15 % |
Crotonsäure | 0,05 % |
Molekulargewichte: | |
Mw | 10.600 g/Mol |
Mn | 1.000 g/Mol |
Feststoffgehalt | 40,1 Gew.-% |
Claims (19)
- Mittel zur fettenden Ausrüstung von Leder in Form einer wäßrigen Dispersion, dadurch gekennzeichnet, daß sie enthalteni) mindestens ein Aminopropionsäurederivat der allgemeinen Formel (I) worinder Rest R1 eine gesättigte oder ungesättigte, geradkettige oder verzweigte Alkyl- oder Alkoxyalkylgruppe mit 8 bis 22 C-Atomen,der Rest R2 eine Alkylgruppe mit 1 bis 18 C-Atomen, einen gesättigten oder ungesättigten Carboxyalkylrest mit 3 bis 4 C-Atomen, einen Carboxyphenylrest oder einen Carboxylrestder Rest R3 Wasserstoff oder eine Methylgruppe,der Rest X Wasserstoff, Alkalimetall, Erdalkalimetall, Ammonium, Alkylammonium oder Alkanolammonium undder Rest Y eine Gruppe -CO-, -SO2-, -CONH oder eine Alkylengruppe mit bis zu drei C-Atomenii) mindestens ein wasserdispergierbares und/oder wasseremulgierbares Co-Oligomer (II) ausa) Fettcrotonaten undb) radikalisch copolymerisierbaren hydrophilen ethylenisch ungesättigen Säuren und/oder deren Anhydriden, die auchc) untergeordnete Mengen weiterer copolymerisierbarer Comonomere enthalten können.
- Mittel nach Anspruch 1, wobei der Rest R1 der Aminopropionsäurederivate (I) ein gesättigter Alkylrest mit überwiegend 12 bis 18 C-Atomen ist.
- Mittel nach Anspruch 1 oder 2, wobei der Rest Y des Aminopropionsäurederivates (I) eine Alkylengruppe, insbesondere eine Gruppe -CH2-CH2, ist und der Rest R2 eine Carboxylgruppe (-CO2H).
- Mittel nach einem der Ansprüche 1 bis 3, wobei man Co-Oligomere (II) verwendet, die als Bausteine (a) Ester beziehungsweise Estergemische aus Crotonsäure und C12-24-Fettalkoholen enthalten.
- Mittel nach einem der Ansprüche 1 bis 4, wobei man Co-Oligomere (II) verwendet, die als Bausteine (b) ethylenisch ungesättigte Monocarbonsäuren, ethylenisch ungesättigte Dicarbonsäuren und/oder deren Anhydride mit bevorzugt jeweils bis zu 12 C-Atomen enthalten, wobei die Dicarbonsäuren auch wenigstens anteilsweise in Form ihrer Partialderivate mit einer Carboxylgruppe und einer derivatisierten Carbonsäuregruppe, zum Beispiel als Dicarbonsäure-Halbester, vorliegen können.
- Mittel nach einem der Ansprüche 1 bis 5, wobei man Co-Oligomere (II) verwendet, die als Bausteine (b) wenigstens anteilsweise Reste copolymerisierbarer aliphatischer und/oder aromatischer Sulfonsäuren enthalten, wobei die Bausteine (b) auch ausschließlich durch solche Sulfonsäuren gebildet sein können.
- Mittel nach einem der Ansprüche 1 bis 6, wobei man Co-Oligomere (II) verwendet, in denen die Bausteine (a) und (b) in Gewichtsverhältnissen - bezogen auf die Summe von (a) und (b) - von 30 bis 90 Teilen, vorzugsweise 35 bis 80 Teilen (a) auf 70 bis 10 Teile, vorzugsweise 65 bis 20 Teile (b) vorliegen, wobei weiterhin im Falle der Mitverwendung von Comonomeren gemäß (c) deren Anteile bevorzugt nicht mehr als 30 Gew.-%, vorzugsweise nicht mehr als 15 Gew.-% - Gew.-% hier bezogen auf die Summe von (a), (b) und (c) - beträgt.
- Mittel nach einem der Ansprüchen 1 bis 7, wobei man Co-Oligomere (II) aus der radikalischen Copolymerisation von Fettcrotonaten mit Acrylsäure, Methacrylsäure, Maleinsäureanhydrid, Maleinsäure, Crotonsäure und/oder Fumarsäure einsetzt.
- Mittel nach einem der Ansprüche 1 bis 8, wobei man Co-Oligomere (II) verwendet, bei deren Herstellung keine Kettenüberträger beziehungsweise Molgewichtsregler mitverwendet worden sind.
- Mittel nach einem der Ansprüche 1 bis 9, wobei man Co-Oligomere (II) mit mittleren Molekulargewichten (Molmassen) von 500 bis 30.000 g/Mol, vorzugsweise von etwa 1.000 bis 15.000 g/Mol einsetzt, wobei die Verwendung der Co-Oligomeren niedrigen Molgewichtes mit beispielsweise Molmassen im Bereich von etwa 1.000 bis 4.000 g/Mol besonders bevorzugt sein kann.
- Mittel nach einem der Ansprüche 1 bis 10, wobei man Co-Oligomere (II) aus Fettcrotonat und Maleinsäureanhydrid einsetzt, deren Maleinsäureanhydrid-Anteil durch Hydrolyse und/oder Solvolyse mit H-aktiven Komponenten zum Maleinsäure-Rest beziehungsweise Maleinsäure-Derivatrest umgewandelt worden ist.
- Mittel nach einem der Ansprüche 1 bis 11, wobei man Co-Oligomere (II) einsetzt, die durch Co-Oligomerisation von Crotonsäure und Maleinsäureanhydrid, anschließende Veresterung der Crotonsäureanteile mit Fettalkoholen und gewünschtenfalls nachfolgende Hydrolyse beziehungsweise Solvolyse der Anhydridringe hergestellt worden sind.
- Mittel nach einem der Ansprüche 1 bis 12, wobei die Mittel auf einen schwach sauren bis schwach alkalischen pH-Bereich eingestellt worden sind.
- Verwendung der Mittel nach einem der Ansprüche 1 bis 13, wobei man die Verbindungen (I) und die Co-Oligomeren (II) zusammen mit Emulgatoren verwendet, die beim Eintrag in insbesondere mineralgegerbte Leder und/oder Felle eine zusätzliche Fettung bewirken und bevorzugt gleichzeitig über saure Gruppen im gegerbten Leder beziehungsweise Fell fixiert werden können, zur fettenden Ausrüstung von feder.
- Verwendung der Mittel nach einem der Ansprüche 1 bis 14, wobei man die Verbindungen (I) und die Co-Oligomeren (II) nach ihrem Eintrag in die auszurüstenden Leder und/oder Pelzfelle darin durch eine Nachbehandlung mit insbesondere Mineralgerbstoffen fixiert, zur fettenden Ausrüstung von feder.
- Mittel nach einem der Ansprüche 1 bis 13, die zusätzlich Emulgatoren und/oder niedermolekulare Fettungsmittel für die Lederzurichtung enthalten, die einen oleophilen Kohlenwasserstoffrest mit bevorzugt wenigstens 8 bis 10 C-Atomen, gegebenenfalls zusammen mit wenigstens einer Säuregruppe im Molekül enthalten und bevorzugt den nachfolgenden Klassen zugeordnet sind:Sulfobernsteinsäure-Halbester langkettiger Fettalkohole mit insbesondere 12 bis 24 C-Atomen und/oder deren Alkylenoxidaddukte mit bevorzugt bis zu 6 Alkylenoxidresten,Sulfobernsteinsäure-Halbester von Fettsäuremono- und/oder - diglyceriden beziehungsweise deren Alkylenoxidaddukten mit bevorzugt bis zu 6 Alkylenoxidresten bei bevorzugter Kettenlänge der Fettsäure(n) im Bereich C12-24,langkettige Sulfofettsäuren, insbesondere alpha-Sulfofettsäuren des Bereichs von C12-24,innenständige Sulfonate olefinisch 1- und/oder mehrfach ungesättigter Fettsäuren mit wenigstens 12, vorzugsweise 16 bis 24 C-Atomen,Salze einer Aminosäure mit 2 bis 6 C-Atomen und mit dem Acylrest einer gesättigten oder ungesättigten Fettsäure mit 9 bis 20 C-Atomen am Aminstickstoffatom, das gegebenenfalls zusätzlich durch Methyl substituiert ist, insbesondere Fettsäuresarkoside.
- Mittel nach einem der Ansprüche 1 bis 13 und 16, die zusätzlich weitere imprägnierende und/oder hydrophobierende Lederfettungsmittel eingemischt enthalten, wobei ein bevorzugtes Wirkstoffgemisch dieser Art auf den folgenden Komponenten aufgebaut ist:
Sulfobernsteinsäure-Halbester mit C12-24-Fettresten in Kombination mit Verbindungen aus der Gruppe oxidierte oder oxidierte und teilsulfierte C18-26-Kohlenwasserstoffe oder C32-40-Vachse, Phosphorsäuremono-C12-24-Alkylester, Partialester von Polycarbonsäuren, wie Citronensäuremono-C18-24-Alkylester, Partialester von Polyalkoholen, wie Sorbitan-, Glycerin- oder Pentaerythrit-C18-24-fettsäureester. - Mittel nach einem der Ansprüche 1 bis 13, 16 und 17, wobei die Summer der Komponenten (I) und (II) wenigstens etwa 35 Gew.-%, vorzugsweise wenigstens den überwiegenden Anteil der imprägnierenden und/oder hydrophobierenden Wertstoffe in den entsprechenden Wertstoffgemischen der wäßrigen Dispersionen ausmacht.
- Verwendung von Mischungen enthaltendi) mindestens ein Aminopropionsäurederivat der allgemeinen Formel (I) worinder Rest R1 eine gesättigte oder ungesättigte, geradkettige oder verzweigte Alkyl- oder Alkoxyalkylgruppe mit 8 bis 22 C-Atomen,der Rest R2 eine Alkylgruppe mit 1 bis 18 C-Atomen, einen gesättigten oder ungesättigten Carboxyalkylrest mit 3 bis 4 C-Atomen, einen Carboxyphenylrest oder einen Carboxylrestder Rest R3 Wasserstoff oder eine Methylgruppe,der Rest X Wasserstoff, Alkalimetall, Erdalkalimetall, Ammonium, Alkylammonium oder Alkanolammonium undder Rest Y eine Gruppe -CO-, -SO2-, -CONH oder eine Alkylengruppe mit bis zu drei C-Atomenii) mindestens ein wasserdispergierbares und/oder wasseremulgierbares Co-Oligomer (II) ausa) Fettcrotonaten undb) radikalisch copolymerisierbaren hydrophilen ethylenisch ungesättigen Säuren und/oder deren Anhydriden, die auchc) untergeordnete Mengen weiterer copolymerisierbarer Comonomere enthalten können,
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4400507 | 1994-01-12 | ||
DE4400507A DE4400507A1 (de) | 1994-01-12 | 1994-01-12 | Mittel zur fettenden Ausrüstung von Leder |
PCT/EP1995/000011 WO1995019451A1 (de) | 1994-01-12 | 1995-01-03 | Mittel zur fettenden ausrüstung von leder |
US08/679,475 US5683611A (en) | 1994-01-12 | 1996-07-12 | Preparations for the oiling of leather |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0739425A1 EP0739425A1 (de) | 1996-10-30 |
EP0739425B1 true EP0739425B1 (de) | 1998-04-29 |
Family
ID=25932935
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95904545A Expired - Lifetime EP0739425B1 (de) | 1994-01-12 | 1995-01-03 | Mittel zur fettenden ausrüstung von leder |
Country Status (9)
Country | Link |
---|---|
US (1) | US5683611A (de) |
EP (1) | EP0739425B1 (de) |
JP (1) | JPH09507520A (de) |
AT (1) | ATE165623T1 (de) |
BR (1) | BR9506479A (de) |
CA (1) | CA2181081A1 (de) |
DE (2) | DE4400507A1 (de) |
ES (1) | ES2115355T3 (de) |
WO (1) | WO1995019451A1 (de) |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1669347A1 (de) * | 1967-03-25 | 1971-05-06 | Henkel & Cie Gmbh | Verfahren zum Fetten von Leder |
DE3507241A1 (de) * | 1985-03-01 | 1986-09-04 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur herstellung wasserdichter leder oder pelze |
DE3529869A1 (de) * | 1985-08-21 | 1987-02-26 | Basf Ag | Verfahren zum hydrophobieren von leder und pelzen |
DE3717961C2 (de) * | 1986-10-27 | 1994-05-26 | Stockhausen Chem Fab Gmbh | Verfahren zur Herstellung von Gemischen von N,N-disubstituierten ß-Aminopropionsäurederivaten, bestimmte Gemische von N-Alkyl-N(2-carboxyethyl)sulfonamiden und N-Alkyl-N(2-carboxyethyl)harnstoffen und Verwendung der genannten Verbindungen |
EP0265818B1 (de) * | 1986-10-27 | 1994-09-28 | Chemische Fabrik Stockhausen GmbH | Verfahren zur Herstellung von N,N-disubstituierten Beta-Aminopropionsäuren und ihre Verwendung zur Hydrophobierung von Leder und Pelzen |
TNSN89128A1 (fr) * | 1988-12-02 | 1991-02-04 | Rohn And Haas Company Independance Mall West | Traitement du cuir avec des copolymeres amphiphites choisis |
DE3926167A1 (de) * | 1989-08-08 | 1991-02-14 | Basf Ag | Verwendung von copolymerisaten auf basis von langkettigen olefinen und ethylenisch ungesaettigten dicarbonsaeureanhydriden zum hydrophobieren von leder und pelzfellen |
DE3931039A1 (de) * | 1989-09-16 | 1991-03-28 | Basf Ag | Verwendung von copolymerisaten auf basis von langkettigen ungesaettigten estern und ethylenisch ungesaettigten carbonsaeuren zum hydrophobieren von leder und pelzfellen |
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 |
DE4223111A1 (de) * | 1992-07-14 | 1994-01-20 | Henkel Kgaa | Neue Lederfettungsmittel und ihre Verwendung |
-
1994
- 1994-01-12 DE DE4400507A patent/DE4400507A1/de not_active Withdrawn
-
1995
- 1995-01-03 WO PCT/EP1995/000011 patent/WO1995019451A1/de active IP Right Grant
- 1995-01-03 CA CA002181081A patent/CA2181081A1/en not_active Abandoned
- 1995-01-03 AT AT95904545T patent/ATE165623T1/de not_active IP Right Cessation
- 1995-01-03 DE DE59502052T patent/DE59502052D1/de not_active Expired - Fee Related
- 1995-01-03 ES ES95904545T patent/ES2115355T3/es not_active Expired - Lifetime
- 1995-01-03 EP EP95904545A patent/EP0739425B1/de not_active Expired - Lifetime
- 1995-01-03 BR BR9506479A patent/BR9506479A/pt not_active Application Discontinuation
- 1995-01-03 JP JP7518800A patent/JPH09507520A/ja active Pending
-
1996
- 1996-07-12 US US08/679,475 patent/US5683611A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE59502052D1 (de) | 1998-06-04 |
JPH09507520A (ja) | 1997-07-29 |
DE4400507A1 (de) | 1995-07-13 |
US5683611A (en) | 1997-11-04 |
ATE165623T1 (de) | 1998-05-15 |
BR9506479A (pt) | 1997-10-07 |
EP0739425A1 (de) | 1996-10-30 |
CA2181081A1 (en) | 1995-07-20 |
ES2115355T3 (es) | 1998-06-16 |
WO1995019451A1 (de) | 1995-07-20 |
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