EP0745142A1 - Nouveaux agents de graissage du cuir et leur utilisation - Google Patents

Nouveaux agents de graissage du cuir et leur utilisation

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Publication number
EP0745142A1
EP0745142A1 EP95908919A EP95908919A EP0745142A1 EP 0745142 A1 EP0745142 A1 EP 0745142A1 EP 95908919 A EP95908919 A EP 95908919A EP 95908919 A EP95908919 A EP 95908919A EP 0745142 A1 EP0745142 A1 EP 0745142A1
Authority
EP
European Patent Office
Prior art keywords
partial esters
acid
leather
acids
partial
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.)
Withdrawn
Application number
EP95908919A
Other languages
German (de)
English (en)
Inventor
Wolfgang Ritter
Rudolf Zauns-Huber
Emil Ruscheinsky
Stefanie Ortanderl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0745142A1 publication Critical patent/EP0745142A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/47—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/49—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/28—Aminocarboxylic acids

Definitions

  • the invention relates to the use of water-dispersible and / or water-emulsifiable partial esters of cyclic polycarboxylic acids or their (partial) anhydrides and onofunctional alcohols with a fat character as amphiphilic agents for greasing equipment and optionally retanning leather and furs.
  • the greasing of vegetable and / or mineral-tanned leather or fur skins is an essential process step in the finishing of the ready-to-use material.
  • the shape of the fat distribution in the skin substance and the extent to which the fat components are incorporated in the skin substance have a decisive influence on the properties and the usability of the finished products.
  • the specific structure of the lipid agents - for example the extent of their lipophilic Groups and any reactive groups present for reaction with suitable reactive components in the tanned leather - determine, inter alia, the durability and effect of the greasing equipment in practical use of the leather and fur products.
  • Impregnation by storing water-swellable compounds which form highly viscous emulsions when water is absorbed and clog the interstices of the leather for example special emulsifiers of the W / O type,
  • EP 193832 relates to a process for the production of waterproof leather or furs using sulfosuccinic acid monoesters in combination with impregnating and / or hydrophobic greasing agents, the characteristic of this process being that the leather or furs are subsequently retanned treated in an aqueous liquor with impregnating and / or hydrophobizing fatliquoring agents which contain sulfosuccinic acid monoester salts with c 12-24 "' re t-t ⁇ es t- en , and after acidification by adding a chromium, zirconium and / The sulfosuccinic acid monoester salts with impregnating fatliquoring agents from the group consisting of oxidized or oxidized and partially sulfated Ci8_
  • aphiphilic agents have been described for the greasy finishing of, in particular, mineral-tanned leathers and furs, which represent certain selected co-oligomers of, on the one hand, hydrophobic or oleophilic monomers and, on the other hand, hydrophilic monomer components.
  • Amphiphilic agents of this type can be worked into the leather or skins to be finished in the form of aqueous dispersions, emulsions and / or solutions after completion of the main tanning, for example by being rolled in.
  • these amphiphilic agents can simultaneously take on the function of retanning.
  • the amphiphilic agents can be finally fixed with mineral tannins in particular.
  • EP 372 746 describes corresponding agents and their use, the amphiphilic copolymers consisting of a predominant proportion of at least one hydrophobic monomer and a minor proportion of at least one copoly- mer. merizable 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 alkylcarboxylic acids and mixtures thereof.
  • the hydrophilic comonomers present in a smaller proportion are ethylenically unsaturated water-soluble acids or hydrophilic basic comonomers.
  • the molecular weight (weight average) of the copolymers is in the range from 2,000 to 100,000.
  • EP 412 389 describes as agents for hydrophobizing leather and fur the use of copolymers which are obtained by radical copolymerization of (a) C8-40 monoolefins with (b) ethylenically unsaturated C4_8 dicarboxylic acid anhydrides in the manner of a substance polymerization at temperatures from 80 to 300 ° C. to copolymers with molar masses 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 during the solvolysis in aqueous medium with bases and which have been prepared in the form of aqueous dispersions or solutions.
  • EP 418 661 describes the use of copolymers which (a) 50 to 90% by weight C8__40-Alkl (meth) acrylates, vinyl esters of Cg_4o-carboxylic acids or their mixtures and (b) 10 to 50% by weight of onoethylenically unsaturated C3_i2-carboxylic acids, monoethylenically unsaturated dicarboxylic acid anhydrides, half-esters or half-amides of monoethylenically unsaturated C4_i2-dicarboxylic acids, amides of C3_i2-monocarboxylic acids or mixtures thereof contain in copolymerized form and have molecular weights of 500 to 30,000 g / mol.
  • the copolymers are present in at least partially neutralized form in aqueous solution or in aqueous dispersion for the stated purpose.
  • DE-A 41 29244 by the applicant relates to the use of aqueous dispersions of co-oligomers from the free radical dissolved aqueous emulsion copolymerization in the weakly acidic to neutral pH range of
  • (c) may contain minor amounts of further hydrophilic and / or oleophilic comonomers in the oligomer molecule,
  • (c) may contain minor amounts of further copolymerizable comonomers
  • the teaching according to the invention intends to use a class of amphiphilic agents for the field of application of the greasing finish of leather and furs which can be predetermined precisely with regard to the molecular size and the molar masses and thus enable an optimization of the interaction with the tanned skin substance.
  • the substance class selected according to the invention and described below also enables fine-tuning of the respective functional portions of these amphiphilic agents. This ensures the optimization of the multifaceted and sometimes contradictory requirements such as high penetration ability in the innermost areas of the tanned skin substance, but at the same time secure fixation of the lubricant after the entry, controllable appearance of the leather greasing up to the long-lasting waterproofness without simultaneous Formation of a greasy surface.
  • the invention relates in a first embodiment to the use of water-dispersible and / or water-emulsifiable partial esters of cyclic polycarboxylic acids or their (partial) anhydrides and monofunctional alcohols with a fat character as amphiphilic agents for greasing and possibly retanning leather and fur skins.
  • teaching of the invention can be particularly important for the finishing of mineral-tanned leather and / or fur skins, the amphiphilic agents of the invention described above also being able to take on a resilient function in the course of this treatment.
  • the invention relates to aqueous dispersions of partial esters of cyclic polycarboxylic acids or their (partial) anhydrides and monofunctional alcohols with a fat character, which are adjusted to pH values in the range from weakly acidic to weakly basic and are present as water-dilutable compositions with valuable substance contents of at least about 20% by weight, in particular with valuable substance contents in the range from about 30 to 70% by weight.
  • the main element of the teaching according to the invention is the use of selected partial esters composed of cyclic polycarboxylic acids of the type described below and, on the other hand, monofunctional alcohols with a fat character, these partial esters being capable of binding to the skin substance or of fixing with in particular mineral tanning agents in the skin substance due to their content of non-esterified carboxyl groups, but on the other hand in the same molecule by type and Have quantity of predeterminable hydrocarbon residues with a fat character as alcohol residues forming esters.
  • the partial esters are formed or prepared in a manner known per se, for example the cyclic polycarboxylic acids as such with the alcohol-forming alcohol components in stoichiometric deficit can be brought to reaction.
  • the cyclic polycarboxylic acids described in detail below for the synthesis of the amphiphilic agents according to the invention can often be produced at least partially in the form of their anhydrides and are referred to in the description of the invention as "(partial) anhydrides".
  • the anhydride ring of the o-shaped dicarboxylic acid residues present in the polycarboxylic acid molecule can then be opened by a ring opening known per se with a monofunctional alcohol compound with a fat character, and the amphiphilic character of the partial esters according to the invention can thus be formed.
  • An important embodiment of the invention uses partial esters with a fat character which are derived from at least 3-functional cyclic polycarboxylic acids or their (partial) anhydrides.
  • the teaching according to the invention provides here that on average at least one carboxyl group per polycarboxylic acid molecule is esterified with the fatty alcohol. If desired, the ratio of ester groups to carboxyl groups can also be shifted in the direction of higher proportions of the ester groups while simultaneously reducing free carboxyl groups. Even with the average ratio of 2 ester groups to a free car boxyl group ensures that the partial esters are sufficiently integrated into the structure of the tanned skin structure.
  • suitable 5-membered and / or especially the cyclic 6-membered ring systems are suitable as cyclic polycarboxylic acids, which - based on the free polycarboxylic acid - have at least 3 , preferably have at least 4 free carboxyl groups in the molecule. At least some of these carboxyl groups can be directly ring-shaped, but these acid groups can also be bonded to the ring as substituents via bridge members.
  • 6-membered ring systems which can be saturated or olefinically unsaturated, but in particular also aromatic in nature, are suitable as the polycarboxylic acid component, in particular for reasons of large-scale accessibility, but also taking into account the adjustable richness characteristics. This can be understood using two characteristic examples:
  • Aromatic polycarboxylic acids with at least 3, preferably with 4 to 6, carboxyl groups on the Co ring system are, for example, synthesis components which are commercially available as trimellitic acid or as pyromellitic acid or their (partial) anhydrides.
  • the partial esters of these acids described in accordance with the invention can be produced in a particularly simple manner by opening the corresponding anhydride rings of adjacent carboxyl groups with the alcohol component of pronounced fat character.
  • trimellitic anhydride can be reacted with one mole of a fatty alcohol or pyromellitic acid dianhydride with one or with 2 moles of a fatty alcohol.
  • the corresponding partial esters with amphiphilic properties are created in the sense of the teaching according to the invention.
  • cyclic polycarboxylic acids are also easily accessible on a large industrial scale in another way, in which case at least partly natural product-based chemicals can be used.
  • the known Diels-Alder reaction of monoolefinically unsaturated mono- and / or polycarboxylic acids or their anhydrides with conjugated di-olefinically unsaturated components gives, in a manner known per se, onoolefinically unsaturated 6-ring systems which belong to the group of cyclic polycarbonates defined according to the invention assign acids.
  • the fatty acid mixtures derived from oils of vegetable and / or animal origin are generally characterized by high contents of polyunsaturated fatty acids, the representatives having at least 2 olefinic double bonds in conjugation with one another suitable reactants for the known Diels-Alder Addition with another olefinically unsaturated molecule.
  • a typical and industrially accessible example of such conjuen fatty acids is ricinic acid, which can be a preferred reactant for the formation of the cyclic polycarboxylic acids and the amphiphilic partial esters derived therefrom.
  • a polycarboxylic acid with a mono-olefinically unsaturated 6-ring is formed as the core of the polycarbonate acid formed.
  • Suitable Diels-Alder reactants with the polyolefinically unsaturated component in the sense of the optimization according to the invention are, in particular, olefinically unsaturated polycarboxylic acids, preferably corresponding dicarboxylic acids such as maleic acid and / or that Maleic anhydride (MAH).
  • ricinic acid and MAH can be converted in a manner known per se to give the partial anhydride of a 3-functional carboxylic acid which, by further reaction with the monofunctional alcohol of pronounced fat character, becomes an amphiphilic working medium in the sense of the teaching according to the invention.
  • the presentation given here with the aid of concrete compounds or reactants on the history of the origin of cyclic polycarboxylic acids can be modified analogously in a variety of ways. Polycarboxylic acids with a cyclic backbone are always obtained, which can be used as an ester-forming reactant for the preparation of the amphiphilic agents in the sense according to the invention.
  • the term monofunctional alcohol with fat character encompasses corresponding compounds of natural and synthetic origin.
  • fatty alcohols of natural origin are obtained by reducing the associated fatty acids and are generally characterized by straight-chain nature.
  • important embodiments of the invention provide for the use or at least the concomitant use of branched-chain alcohols, which can then be of synthetic origin in particular.
  • the alcohol components can be saturated, but if desired they can also be olefinically unsaturated.
  • a typical example of an olefinic fatty alcohol of natural origin is oleyl alcohol, which in the context of the teaching according to the invention for the formation of partial esters with amphiphiles. Character can be used.
  • Preferred alcohol components for partial ester formation contain 10 to 40 carbon atoms in the molecule, esters based on Ci2-24 -
  • r ett alcohols can be of particular importance.
  • the use of branched-chain fatty alcohols for ester formation can lead to interesting results in individual cases.
  • the use of branched-chain alcohols to a limited extent can promote the ability of the amphiphilic agents to penetrate the fiber structure of the skin material to be treated.
  • branched alcohols with a shorter carbon number, suitable components having at least 6 carbon atoms, preferably having at least 8 carbon atoms.
  • An important branched chain alcohol of synthetic origin is 2-ethylhexanol.
  • the amount of the branched-chain, in particular shorter, alcohols to be used will be comparatively limited.
  • no more than 50% by weight, preferably no more than 30 or no more than 20% by weight, of the total alcohol residues used are formed by such branched-chain, in particular lower, alcohols.
  • Particularly important representatives for the ester-forming alcohol components can be found in the range C12..I8 . which in a preferred embodiment can make up at least about 90 to 95% by weight of the ester-forming alcohol residues.
  • onofunctional alcohols with a pronounced fat character are not only to be understood as the corresponding alcohols in the narrower sense, but also from this derived monofunctional alcoholic derivatives.
  • Two characteristic examples of this are the following: It is known to react fatty alcohols with lower alkylene oxides, in particular ethylene oxide and / or propylene oxide, with the formation of corresponding alcohol alkoxylates. Of particular importance here is alcohol ethoxylates with an average of a maximum of about 6 EO units per fatty alcohol haulmolecule, where corresponding compounds with 1 to 4 EO units per fatty alcohol molecule can be particularly important.
  • Alkoxylated, in particular low ethoxylated fatty alcohols in the sense of this definition are also suitable reactants for the reaction with the cyclic polycarboxylic acids, or their anhydrides, for the formation of the amphiphilic agents in the sense of the invention.
  • Another characteristic example of the modification of the partial esters according to the invention is the use of fatty alcohols which are extended with lower hydroxycarboxylic acid chains.
  • the extent of the chain extension must be restricted so that the pronounced fat character of the alcohol component is retained.
  • this modification of the fatty alcohol component enables the control of important material properties in the leather or fur treated according to the invention.
  • the softness of the leather finished with the amphiphilic agents according to the invention can be significantly increased if partial esters of the type described are used, in which long-chain alcohols of natural and / or synthetic origin which are at least partially ester-forming with lactide residues are extended be used.
  • hydroxycarboxylic acids for the formation of corresponding fatty alcohol derivatives are in particular the corresponding representatives with up to 6, preferably with up to 4, carbon atoms, the oxalic acid and / or lactic acid being particularly important for chain extension on the fatty alcohol molecule.
  • Preferred average degrees of oligomerization for the introduced hydroxycarboxylic acid residues are from 1 to 8, preferably from 1 to 5 and in particular 1 to 3.
  • the cyclic partial esters ultimately used are expediently in the form of aqueous dispersions and / or emulsions which have preferably been adjusted to a weakly acidic to weakly alkaline range.
  • aqueous dispersions and / or emulsions which have preferably been adjusted to a weakly acidic to weakly alkaline range.
  • All bases described in the relevant state of the art are suitable for pH regulation, cf. also here the information of the prior art cited at the beginning.
  • the alkali salts, particularly sodium and / or potassium, are particularly preferred.
  • ammonium salts or salts of alkanolins, such as diethanolamine are also suitable representatives.
  • Preferred pH values for storage-stable products can be in the range around pH 7 to 8.
  • the partial ester value of which is, for example, in the range from at least about 20% by weight, preferably from about 30 to 70 or 75% by weight.
  • Such pasty masses are to be mixed with water and / or aqueous active substance mixtures of the type described below at any time and put to practical use.
  • amphiphilic agents of the type described are used together with selected emulsifiers which, when introduced into in particular tanned leather and / or skins, cause additional greasing or hydrophobization and, at the same time, preferably via acidic groups in the tanned leather or fur can be fixed.
  • emulsifiers which, when introduced into in particular tanned leather and / or skins, cause additional greasing or hydrophobization and, at the same time, preferably via acidic groups in the tanned leather or fur can be fixed.
  • emulsifiers which, when introduced into in particular tanned leather and / or skins, cause additional greasing or hydrophobization and, at the same time, preferably via acidic groups in the tanned leather or fur can be fixed.
  • water-emulsifiable sulfosuccinic acid half-esters mentioned at the outset, which are derived from long-chain fatty alcohols and / or their alkylene oxide adducts
  • Ci2-24 ⁇ long-chain sulfofatty acids more particularly alpha-sulfofatty acids ent speaking with preferably 12 to 24, more particularly sondere 16 to 18 C atoms, where in the case of alpha-sulfofatty acids th substitutability the hydrocarbon radicals are usually saturated ge, and internal sulfo fatty acids of olefinically 1- and / or polyunsaturated carboxylic acids such as oleic acid, linoleic acid, linolenic acid and the like.
  • fatliquoring or hydrophobicizing agents in the sense of the mixtures of materials from EP 193832 cited at the beginning can also be used.
  • the partial esters of cyclic polycarboxylic acids defined in accordance with the invention are combined with impregnating and / or hydrophobizing fatliquoring agents, such as sulfosuccinic acid monoester salts with Ci2-24 ⁇ ' : re'ttresten ' " > n combination with other im ⁇ fatliquoring agents selected, selected in particular from the group of oxidized or oxidized and partially sulfated Ci8-26 ⁇ Ko - 1 ⁇ oleic acids or C32-40 waxes.
  • fatliquoring agents such as sulfosuccinic acid monoester salts with Ci2-24 ⁇ ' : re'ttresten ' " > n combination with other im ⁇ fatliquoring agents selected, selected in particular from the group of oxidized or oxidized and partially
  • a particularly suitable class of emulsifier which can also be used in the context of the teaching according to the invention, are the N-acylamino acids known from finishing leather and furs with fatty substances, in particular fatty acid sarcosides, e.g. N-oleoyl sarcosine, as described in detail, for example, as emulsifiers for introducing silicone oils into leather and furs in EP-B1-0213480.
  • Suitable emulsifiers are accordingly, in particular, salts of N- (Cg_20-acyl) amino acids, with corresponding salts of an amino acid having 2 to 6 C atoms and the acyl residue of a saturated or unsaturated fatty acid having 9 to 20 C atoms on the amine stick - Substance, which is optionally additionally substituted by methyl, is of particular importance.
  • Suitable salts of these emulsifiers are in particular alkali metal, ammonium or alkanols.
  • N- (Cg_20-acyl) amino acids those with 2 to 4 carbon 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 having 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 tri-alkanols, in particular 2 to 4 carbon atoms in the alkanol radical.
  • the amount of partial esters of cyclic polycarboxylic acids defined according to the invention is preferably at least about 35% by weight of the material mixture and in particular at least about 50% by weight - based on the same basis. It may be expedient to provide at least about 70 to 80% by weight of the mixture of valuable substances to be incorporated into the leather or fur skins to be finished, based on the partial esters according to the invention.
  • amphiphilic agents defined according to the invention are suitable for the treatment of all customary tanned skins, in particular corresponding material which has been tanned with mineral tanning agents.
  • the tanned hides are usually deacidified before the treatment. They may have been dyed before the treatment. Coloring can also only be carried out after the treatment according to the invention.
  • the impregnating leather with the dispersions in an aqueous liquor is expediently at a pH of about 4 to 10 and preferably at a pH of 5 to 8 and at a temperature of about 20 to 60 ° C., preferably 30 to 50 ° C., for a period of time treated up to several hours if necessary in several stages.
  • the treatment takes place, for example, by drumming in a barrel.
  • the required amount of partial ester dispersion is usually 0.1 to 30% by weight, in particular 1 to 20% by weight, based on the fold 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%, and 50 to 500% for furskins.
  • the pH of the treatment liquor is shifted into the slightly acidic range by adding acids.
  • Preferred pH values are in the range from 3 to 5, preferably in the range from about 3.5 to 4.
  • a fixation with, in particular, mineral tanning agents can be added, the use of aluminum salts, but also of other polyvalent mineral salts, being used here , e.g. Chromium or zirconium salts can be particularly preferred.
  • the acid number of the starting mixture is 111.5. When the reactants had completely converted, the acid number was reduced to half. The theoretical acid number is reached after a reaction time of 2 hours.
  • the xylene is removed from the reaction product by distillation.
  • the result is a highly viscous, cream-like mass which can be dispersed with about 3 times the amount of water at 80 ° C. After cooling, the dispersion becomes solid.
  • amphiphilic partial esters of pyromellitic acid are prepared with the following fatty alcohols or fatty alcohol derivatives:
  • Ci2 fatty alcohol commercial product “Lorol C12” from the applicant); stable solid dispersion Example 2
  • Example 1 is repeated, but now with the omission of the solvent xylene.
  • the reactants are introduced together and stirred intensively at 140 ° C.
  • reaction time being based in each case on the theoretical acid number being reached and being able to last up to about 6 hours:
  • a cyclic polycarboxylic acid or its partial anhydride in the sense of the definition according to the invention is produced as follows:
  • a rizine fatty acid of the trade with a particularly high content of conjugates :
  • reaction mixture is reacted with maleic anhydride (MA) in a molar ratio of 1: 1 in the presence of 0.03% by weight of sulfur as a catalyst.
  • MA maleic anhydride
  • MSA is added dropwise at 100 ° C. in the course of 30 minutes. Thereafter, the temperature, which was raised to about 150 ° C. by exotherm, is increased to 200 ° C. and held for 2 hours. In further batches, the reaction mixture is heated to 220 ° C. for a further 2 hours in a subsequent reaction phase.
  • the polycarboxylic anhydride obtained is subsequently reacted with the fatty alcohols and fatty alcohol derivatives named in Examples 1 and 2, but now in a molar ratio of 1: 1.
  • the response time is usually around 3 hours. Solvent-free work is carried out so that the end of the reaction is determined by the (approximate) achievement of the theoretical acid number of the reaction product.
  • cowhide leather is used as the material to be finished, the following individual work instructions apply:
  • Ausoanqsmaterial cowhide wetblue, folded seam thickness approx. 1.8 mm% information on seam weight initial pH value approx. 3.9
  • the samples were air-conditioned for 24 hours at 23 ° C and 50% relative air humidity (IUP-3 / DIN 53303)
  • washing tests are carried out using the beef furniture leather equipped according to the invention and the results are determined on the material samples examined. The following applies in particular: After the leather had been air-conditioned (DIN 53303), test specimens were punched out in a size of 10 ⁇ 10 cm, after which they were measured and weighed.
  • the leathers are then chemically cleaned (Böwe) with perchlorethylene, dried and dried.

Abstract

On utilise des esters partiels dispersibles et/ou émulsifiables dans l'eau extraits d'acides polycarboxyliques cycliques, ou leurs anhydres partiels et alcools monofonctionnels à caractère gras, comme agents amphiphiles d'apprêt graissant et le cas échéant de retannage de cuirs et de peaux. L'invention concerne en outre des dispersions aqueuses de ces esters partiels amphiphiles à caractère gras se présentant sous forme de masses aqueuses pâteuses, diluables dans l'eau. Mélangées à ces esters partiels, ces dispersions peuvent contenir d'autres émulsifiants et produits de graissage ou d'imperméabilisation des cuirs et des peaux connus en soi.
EP95908919A 1994-02-18 1995-02-09 Nouveaux agents de graissage du cuir et leur utilisation Withdrawn EP0745142A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4405205 1994-02-18
DE4405205A DE4405205A1 (de) 1994-02-18 1994-02-18 Neue Lederfettungsmittel und ihre Verwendung
PCT/EP1995/000463 WO1995022628A1 (fr) 1994-02-18 1995-02-09 Nouveaux agents de graissage du cuir et leur utilisation

Publications (1)

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EP0745142A1 true EP0745142A1 (fr) 1996-12-04

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EP95908919A Withdrawn EP0745142A1 (fr) 1994-02-18 1995-02-09 Nouveaux agents de graissage du cuir et leur utilisation

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US (1) US5728313A (fr)
EP (1) EP0745142A1 (fr)
DE (1) DE4405205A1 (fr)
WO (1) WO1995022628A1 (fr)

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US5853427A (en) * 1995-07-12 1998-12-29 The United States Of America As Represented By The Secretary Of Agriculture Use of polymerizable oil for leather fatliquor
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WO1995022628A1 (fr) 1995-08-24
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