EP0602071B1 - Dispersions aqueuses de nouveaux co-oligomeres amphiphiles pour l'appret graisseux resistant au lavage et au nettoyage des cuirs et des peaux, et leur utilisation - Google Patents

Dispersions aqueuses de nouveaux co-oligomeres amphiphiles pour l'appret graisseux resistant au lavage et au nettoyage des cuirs et des peaux, et leur utilisation Download PDF

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Publication number
EP0602071B1
EP0602071B1 EP92917518A EP92917518A EP0602071B1 EP 0602071 B1 EP0602071 B1 EP 0602071B1 EP 92917518 A EP92917518 A EP 92917518A EP 92917518 A EP92917518 A EP 92917518A EP 0602071 B1 EP0602071 B1 EP 0602071B1
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Prior art keywords
acid
leather
oligomers
aqueous
weight
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German (de)
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EP0602071A1 (fr
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Ludwig Schieferstein
Rudolf Zauns Huber
Joachim Conradi
Emil Ruscheinsky
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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 greasing of vegetable and / or mineral-tanned leather or fur skins is an essential process step in the finishing stages for the ready-to-use valuable material based on leather or fur.
  • the shape of the fat distribution in the skin substance and the extent to which the fat components are incorporated into the skin substance have a decisive influence on the properties and usability of the finished products.
  • the specific structure of the fatliquor - for example the extent of their lipophilic groups and any reactive groups present for reaction with suitable reactive components in the tanned leather - determine, among other things, the durability and effect of the greasing equipment in practical use of the leather and fur products.
  • EP 193 832 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 distinguishing feature of this process being that the leather or furs are subsequently retanned in treated aqueous liquor with impregnating and / or hydrophobizing fatliquoring agents containing sulfosuccinic acid monoester salts with C12 ⁇ 24 fatty residues and fixed after acidification by adding a chromium, zirconium and / or aluminum salt.
  • the sulfosuccinic acid monoester salts with impregnating fatliquors from the group consisting of oxidized or oxidized and partially sulfonated C18 ⁇ 26 hydrocarbons or C32 ⁇ 40 waxes, phosphoric acid mono-C12 ⁇ 24 alkyl esters, citric acid mono-C16 ⁇ 24 alkyl esters, sorbitan, Glycerol and / or pentaerythritol C16 ⁇ 24 fatty acid esters used.
  • amphiphilic agents have been described and recommended for the wet-end finishing of, in particular, mineral-tanned leathers and furskins, which represent certain selected co-oligomers of hydrophobic or oleophilic monomers on the one hand and hydrophilic monomer components on the other hand.
  • 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 finishing agents can simultaneously take on the function of retanning.
  • the amphiphilic agents can be finally fixed with mineral tannins in particular.
  • amphiphilic copolymers being formed from a predominant portion of at least one hydrophobic monomer and a minor portion of at least one copolymerizable hydrophilic monomer are.
  • 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 their mixtures.
  • the minor proportion of hydrophilic comonomers 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 the use of copolymers as agents for the hydrophobization of leather and fur skins by radical copolymerization of (a) C8 ⁇ 40-monoolefins with (b) ethylenically unsaturated C4 ⁇ 8-dicarboxylic acid anhydrides in the manner of a bulk polymerization at temperatures of 80 up 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 solutions .
  • EP 418 661 describes for the same purpose the use of copolymers which (a) 50 to 90% by weight C8 ⁇ 40-alkyl (meth) acrylates, vinyl esters of C8 ⁇ 40-carboxylic acids or their mixtures and (b ) 10 to 50 wt .-% monoethylenically unsaturated C3 ⁇ 12-carboxylic acids, monoethylenically unsaturated dicarboxylic acid anhydrides, half esters or half-amides of monoethylenically unsaturated C4 ⁇ 12-dicarboxylic acids, amides of C3 ⁇ 12-monocarboxylic acids or mixtures thereof and copolymerized and molecular weights from 500 to 30,000 own g / mole.
  • the copolymers are in at least partially neutralized form in aqueous solution or in aqueous dispersion for the intended use.
  • the invention is based on the object of providing a new class of amphiphilic co-oligomers which can be used in an improved manner in the finishing steps of pre-tanned leather and fur skins, which are particularly suitable for impregnating and permeating the skin substance on the one hand, set the desired fatliquoring and possibly also certain hydrophobization effects, but on the other hand can also replace the otherwise usual retanning at the same time.
  • the invention seeks to make it possible to provide grease that is at least largely resistant to cleaning, so that appropriately equipped leathers and skins can be accessed by aqueous surfactant washing and / or chemical cleaning without suffering any substantial loss in value.
  • the invention provides for the use of the co-oligomer class described below, if desired also in a mixture with other greasing and / or hydrophobicizing, in particular known mixture components before, in one embodiment both the class of the amphiphilic co-oligomers selected according to the invention and the optionally additionally used auxiliary substances of the type specified above can be fixed in the skin material by post-treatment with in particular mineral tanning agents.
  • the invention relates to the use of the aqueous dispersions of these amphiphilic agents, in particular for finishing mineral-tanned leather and / or fur skins, the amphiphilic agents of the invention described above also being able to take on or exercise a retanning function in the course of this treatment.
  • the invention relates to aqueous dispersions of the amphiphilic co-oligomers from the previously defined components (a) and (b) and optionally (c), the molar ratios of (a) :( b) in these co-oligomers Range from about 1: 1 to 2: 1.
  • the optional component (s) (c) are present in smaller amounts by weight, based on the sum of (a) + (b).
  • the aqueous dispersions are adjusted to pH values in the range from neutral to weakly basic and are present in particular as a water-dilutable aqueous pasty mass with valuable content of the co-oligomer in the range from about 30 to 50% by weight.
  • the basic element of the invention is the use of the co-oligomers from half-esters of maleic acid with selected oleophilic alcohols - component (a) - and acrylic acid and / or methacrylic acid - component (b), hereinafter also referred to simply as (meth) acrylic acid - as main components.
  • these co-oligomers can have minor amounts either of comonomers with a hydrophilic character and / or of comonomers with an oleophilic character.
  • These optional additional components of the co-oligomer molecule are collectively referred to as components of type (c).
  • Preferred embodiments for co-oligomers of the definition according to the invention provide that at least approximately equal amounts of (a) to (b) are used to build up the co-oligomer molecule, but it is preferred that the component (a) is molar in the Use excess over component (b). This ensures that a possible large proportion of fatty and / or hydrophobizing lipophilic molecule components are introduced into the wet-end leather to be finished, but on the other hand there is a sufficiently large number of free carboxyl groups in the co-oligomer molecule, which are both from the components of (a) and from Components to (b) result.
  • this creates the possibility of specifically setting greasing effects in the fiber structure of the leather or fur, but at the same time there is a large number of reactive free carboxyl groups available for interaction with the skin substance and / or auxiliary agents that are already present or have to be added subsequently - in particular mineral tanning agents.
  • the desired combination of the majority of equipment effects is thus made controllably accessible.
  • the auxiliary substance can be fixed in the skin structure in such a way that cleaning by washing and / or chemical cleaning agents becomes accessible when the greased soft leather structure is retained.
  • This component is formed by half esters of maleic acid with lipophilic or oleophilic alcohols, and in addition to or instead of the alcohols, their alkylene oxide adducts also have a limited and, in a manner known per se, the chain length of the alcohols adapted number of alkylene oxide residues can be used. Details on this can be found, for example, in EP 193 832 cited at the outset.
  • the latter components with a maximum of 6 alkylene oxide groups and preferably with up to to derivatize to 4 alkylene oxide groups.
  • Lower degrees of alkoxylation are preferably associated with lower chain lengths; higher degrees of alkoxylation within the lower range mentioned can be longer Chain lengths must be assigned.
  • Corresponding EO radicals can in particular be suitable as alkylene oxide groups.
  • oleophilic maleic acid half-esters as component (a) are used which are free from such an alkylene oxide derivatization.
  • Half-esters of maleic acid with straight-chain and / or branched alcohols of oleophilic character which contain at least predominantly 8 to 10 or more carbon atoms in the molecule are particularly suitable here.
  • ester-forming fatty alcohols are corresponding components of natural origin, such as are obtained, for example, by reduction from fatty acids of natural origin in a manner known per se.
  • Saturated fatty alcohols in the range from C 12 to 18 can be of particular importance for the formation of the monomeric components to (a). By using or using these components, optimized greasy and water-repellent effects are obtained.
  • branched chain alcohols can also contain fewer than 12 carbon atoms in the molecule, corresponding components with at least 6 carbon atoms, preferably with at least 8 carbon atoms, being suitable.
  • An important branched chain alcohol that is related to its manufacture the maleic acid half ester according to (a) can be used is 2-ethylhexanol.
  • the amount of branched-chain, in particular shorter, alcohols used will always be comparatively limited.
  • no more than 20% by weight, preferably no more than 15 or even 10% by weight, of the alcohol residues present in (a) is formed by such branched-chain lower alcohols.
  • Quantity ratios of approximately 95% by weight of pronounced oleophilic long-chain fatty alcohols, in particular in the range C 12 to 18 with approximately 5% by weight of a branched-chain alcohol of the 2-ethylhexanol type have proven to be sufficient for practical work.
  • the components of (a) are obtained in a manner known per se from maleic anhydride by alcoholysis with the respectively selected hydrophobic fatty alcohol or alcohol mixture.
  • the preferred monomer component for (b) is acrylic acid, but mixtures of acrylic acid and methacrylic acid with, in particular, predominant amounts of acrylic acid can also be particularly considered here.
  • co-oligomerization is expediently carried out in such a way that the resulting co-oligomers are obtained with average molecular weights (weight average) in the range from about 500 to 20,000.
  • Particularly suitable co-oligomers of the type described have corresponding average molecular weights in the range from about 1,000 to 10,000.
  • additional oleophilizing monomer components according to (c) and / or additional hydrophilizing monomer components according to (c) can also be used.
  • copolymerizable oleophilic monomer compounds - for example the (meth) acrylates of long-chain alcohols known from the prior art - can also be used.
  • further acid groups for example vinyl sulfonic acid and the like, the character of the fixability or the ability to retanning be enhanced.
  • the amphiphilic agents according to the invention contain the component (s) (c) which may also be used in comparatively small amounts by weight, based on the sum of (a) + (b).
  • component (s) (c) which may also be used in comparatively small amounts by weight, based on the sum of (a) + (b).
  • co-oligomers of the type described which additionally contain oleophilic components (c).
  • their content is not more than 45% by weight and in particular less than 30% by weight of the co-oligomer.
  • co-oligomers are used which have been prepared without adding such oleophilic components to (c). If additional greasing and / or hydrophobizing additional effects are desired here, then in the sense of the teaching according to the invention, mixture components are also used, which will be dealt with separately below.
  • the co-oligomers from (a) and (b) and, if appropriate, (c) are prepared according to the invention by aqueous emulsion copolymerization.
  • the individual procedure is expediently carried out as follows: the separately prepared maleic acid half-ester is finely emulsified in slightly preheated water, if necessary, after melting. Alkalization with NaOH in particular ensures a weakly acidic to neutral pH at best. Preferred pH values are in the range from about 4.5 to 7, in particular 6 to 7.
  • an aqueous solution of component (s) becomes (b) - in particular Acrylic acid - metered in and simultaneous pH regulation ensures compliance with the specified weakly acidic pH value at best.
  • an initiator for the radical reaction in particular hydrogen peroxide, is metered in.
  • a neutral to weakly alkaline pH is set in the aqueous reaction medium.
  • paste-like masses can be produced whose content of co-oligomers is valuable For example, it is in the range from about 30 to 45% by weight and the unreacted constituents only contain amounts significantly below 1% by weight, preferably below 0.5% by weight.
  • Preferred pH values for the storage-stable product are in the range around pH 7 to 8.
  • the 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, in the production of which in the stage of the aqueous co-oligomerization emulsifiers have been used which, when introduced into mineral-tanned leather and / or furs in particular, cause additional greasing or hydrophobization and preferably at the same time can be fixed via acidic groups in the tanned leather or fur.
  • An important example of compounds of this type 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.
  • auxiliaries of this type do not have to have been used as mixture components in the course of the co-oligomerization; they can also be used as the aqueous mixture of valuable substances used according to the invention Mix components are added afterwards.
  • connection types of this type are examples of connection types of this type:
  • Sulfosuccinic acid half-esters of long-chain fatty alcohols with in particular 12 to 24 C atoms and / or their alkylene oxide adducts with preferably up to 6 alkylene oxide residues corresponding sulfosuccinic acid half-esters of fatty acid mono- and / or diglycerides or their alkylene oxide adducts with preferably up to 6 alkylene oxide residues with a further preferred chain length of Fatty acid (s) in the range C12 ⁇ 24, long-chain sulfofatty acids, in particular corresponding alpha-sulfofatty acids with preferably 12 to 24, in particular 16 to 18, carbon atoms, the hydrocarbon radicals usually being saturated in the case of these alpha-substituted sulfofatty acids, and internal sulfofatty acids of olefinically 1- and / or polyunsaturated carboxylic acids such as oleic acid, linoleic acid, linolenic acid
  • the co-oligomers of (a) and (b) and optionally (c) defined according to the invention are combined with impregnating and / or hydrophobizing fatliquors, the sulfosuccinic acid monoester salts with C12 ⁇ 24 fat residues in combination with other impregnating fatliquoring agents, selected in particular from the group of oxidized or oxidized and partially sulfonated C18 ⁇ 26 hydrocarbons or C32 ⁇ 40 waxes.
  • additional impregnating fatliquors are phosphoric acid mono-C12 ⁇ 24 alkyl esters, partial esters of polycarboxylic acids, such as citric acid mono-C16 ⁇ 24 alkyl esters, partial esters of polyalcohols, such as sorbitan, glycerol or pentaerythritol C16 ⁇ 26 ⁇ fatty acid esters.
  • the amount of the co-oligomers of (a) and (b) defined according to the invention and, if appropriate, is (c) 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 wet-end leather to be finished, based on the co-oligomers according to the invention.
  • the co-oligomer dispersions 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 treatment. They may have been stained before treatment. Coloring can also only be carried out after the treatment according to the invention.
  • the leather to be impregnated in the wet state is advantageously mixed with the dispersions in an aqueous liquor at pH values of about 4 to 10, preferably at pH 5 to 8, and at temperatures of about 20 to 60 ° C., preferably 30 to 50 ° C. treated in several stages if necessary for a period of up to a few hours.
  • the treatment takes place, for example, by drumming in a barrel.
  • the required amount of co-oligomer dispersion is usually 0.1 to 30% by weight, in particular 1 to 20% by weight, based on the shaved weight of the leather or the wet weight of the fur skins.
  • the liquor length is usually 10 to 1,000%, preferably 30 to 150%, and 50 to 500% for fur skins.
  • 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 being particularly preferred here.
  • maleic anhydride (Examples 1 and 2) is also used, this component is first added in portions at such a rate that the internal temperature of the reaction mixture remains below approx. 55 ° C. (time required approx. 20 minutes; possibly weak external cooling). After the maleic anhydride has completely dissolved, the maleic acid half-ester, if necessary melted, is added. The template is then neutralized by adding NaOH cookies in portions to a pH of approximately 7.0. The internal temperature rises to a maximum of 80 ° C.
  • the reactor contents are then heated to 90 ° C.
  • feed solutions were previously prepared separately from this reaction template: feed solution 1: acrylic acid / water (demineralized); Feed resolution 2: ammonium peroxydisulfate / water (demineralized); Inlet resolution 3: 35% by weight hydrogen peroxide After the temperature inside the reactor has reached 90 ° C., the addition of the feed solutions and the starter is started.
  • feed solution 1 acrylic acid / water (demineralized);
  • Feed resolution 2 ammonium peroxydisulfate / water (demineralized); Inlet resolution 3: 35% by weight hydrogen peroxide
  • Allowance 1 28 parts by weight of 35% hydrogen peroxide Allowance 1 is added evenly over a period of 5 hours. At the same time, feed solutions 2 and 3 are added evenly over a period of 6 hours at an internal temperature of 100 ° C - this can cause slight reflux.
  • reaction mixture is then reheated at 100 ° C. for 1 hour.
  • a pH of about 7 is set by carefully adding aqueous 20% sodium hydroxide solution.
  • chrome leather samples are treated with the oligomers according to the invention under the working conditions of Examples 7 to 11 below.
  • Examples 7 to 11 which are summarized in a table, the products of the definition according to the invention from Examples 1, 4 and 5 are used as oligomers of the invention.
  • soft, supple and well-filled leathers are obtained, which have a pleasant grip and are characterized by high grain resistance.
  • the samples can be subjected to both aqueous-surfactant washing (30 ° C) and chemical cleaning without causing lasting damage to the product properties. Even after repeated repetitive cleaning steps of the specified type, no lasting stiffening of the leather material can be determined.

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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)
  • Detergent Compositions (AREA)

Claims (15)

  1. Utilisation de dispersions aqueuses de co-oligomères à partir de copolymérisation en émulsion aqueuse démarrée par voie radicalaire, dans une zone de pH ajustée de faiblement acide à neutre de :
    a) hémi-esters d'acide maléique avec des alcools oléophiles et/ou leurs produits d'addition d'oxyde d'alcoylène inférieurs et,
    b) d'acide acrylique et/ou d'acide méthacrylique
    comme constituants principaux, qui aussi en supplément peuvent renfermer,
    c) quantités inférieures d'autres co-monomères hydrophiles et/ou oléophiles dans la molécule d'oligomère,
    comme agent amphiphile en vue de l'apprêtage du cuir et des peaux de fourrure qui doivent être graissées, résistant au lavage et résistant au nettoyage chimique.
  2. Mode d'exécution selon la revendication 1, caractérisé en ce que les dispersions aqueuses de l'agent amphiphile sont mises en oeuvre pour l'apprêtage de cuirs et/ou de peaux tannés avec des produits minéraux et peuvent être ici aussi en même temps utilisées comme agent en vue du tannage final.
  3. Mode d'exécution selon les revendications 1 et 2, caractérisé en ce que l'on travaille avec des co-oligomères, qui possèdent des rapports molaires de (a):(b) dans la zone de 1:1 à 2:1.
  4. Mode d'exécution selon les revendications 1 à 3, caractérisé en ce que l'on met en oeuvre des co-oligomères qui renferment comme composant (a) un hémi-ester d'acide maléique avec des alcools à chaîne droite et/ou ramifiés de caractère oléophile, qui au moins d'une façon prépondérante possèdent dans la molécule de 8 à 10 ou plus d'atomes de carbone, de préférence de 12 à 14 atomes de C et le cas échéant sont dérivés avec jusqu'à 6 groupes d'oxyde d'alcoylène inférieurs, en particulier 1 à 4 groupes OE.
  5. Mode d'exécution selon les revendications 1 à 4, caractérisé en ce que l'on utilise des agents amphiphiles qui possèdent dans les co-oligomères comme composant(s) (a) un hémi-ester d'acide maléique, provenant de la réaction d'anhydride maléique avec un mélange à base d'alcools gras à chaîne droite ayant au moins 8 atomes de carbone, de préférence des alcools gras en C₁₂ à C₁₈, et des quantités inférieures d'alcools ramifiés tandis que ces alcools ramifiés peuvent contenir aussi moins de 12 atomes de C dans la molécule et qu'en outre le(s) composant(s) (a) sont soumis de préférence avec l'acide acrylique, comme composant (b), à la co-oligomérisation aqueuse.
  6. Mode d'exécution selon les revendications 1 à 5, caractérisé en ce que l'on utilise des agents amphiphiles dont le composant (a) est formé d'un mélange d'hémiesters d'acide maléique avec des alcools gras d'origine naturelle ayant au moins 12 atomes de carbone et des alcools à chaîne ramifiée ayant au moins 6 atomes de carbone, de préférence au moins 8 atomes de carbone, les alcools à chaîne ramifiée représentant de préférence pas plus de 15 % en poids et en particulier pas plus de 10 % en poids des restes d'alcools présents au total dans (a).
  7. Mode d'exécution selon les revendications 1 à 6, caractérisé en ce que l'on utilise des agents amphiphiles, dont la teneur en composants oléophiles (c) représente jusqu'à 45 % en poids, de préférence moins de 30 % en poids du co-oligomère, tandis que dans un mode d'exécution important on met en oeuvre des co-oligomères qui ont été préparés sans addition de composants oléophiles (c).
  8. Mode d'exécution selon les revendications 1 à 7, caractérisé en ce que l'on utilise des dispersions aqueuses de co-oligomères ayant des poids moléculaires moyens dans la zone de 500 à 20 000 de préférence d'environ 1 000 à 10 000.
  9. Mode d'exécution selon les revendications 1 à 8, caractérisé en ce que l'on met en oeuvre des dispersions aqueuses des agents amphiphiles qui ont été préparées comme suit :
    - introduction d'une émulsion aqueuse, ajustée de faiblement acide à neutre, d'hémi-esters d'acide maléique, démarrage de la réaction radicalaire par addition lente d'acide acrylique et/ou d'acide méthacrylique et si désiré du ou des composant(s) à (c) sous régulation continue ou par intervalles, de la valeur du pH dans une zone indiquée et ajustement final d'une valeur de pH de neutre à faiblement alcaline dans le produit terminé.
  10. Mode d'exécution selon les revendications 1 à 9, caractérisé en ce que l'on utilise des agents amphiphiles pour une production desquels dans le stade de la co-oligomérisation en milieu aqueux on a utilisé des agents émulsionnants qui entraînent un graissage supplémentaire lors de l'incorporation dans le cuir et/ou les peaux tannés en particulier par des minéraux et qui peuvent être fixés de préférence en même temps par l'intermédiaire de groupes acides dans le cuir ou dans les peaux tannés.
  11. Mode d'exécution selon les revendications 1 à 10, caractérisé en ce que les co-oligomères après incorporation dans le cuir et/ou les peaux de fourrure à apprêter, y ont été fixés par un traitement ultérieur avec en particulier des agents tannants minéraux.
  12. Dispersions aqueuses de co-oligomères amphiphiles à base de :
    a) hémi-esters d'acide maléique avec des alcools oléophiles et/ou leurs produits d'addition avec un oxyde d'alcoylène inférieurs,
    b) acide acrylique et/ou méthacrylique, ainsi que le cas échéant,
    c) d'autres co-monomères hydrophiles et/ou oléophiles,
    qui renferment des rapports molaires de (a):(b) dans la zone de 1:1 à 2:1 et le(s) composant(s) (c) éventuellement présent(s) en quantités de poids plus faibles, rapportés à la somme de (a)+(b), sont ajustées à des valeurs de pH dans la zone allant de neutre à faiblement basique et sont formées en particulier en tant que masse aqueuse, pâteuse diluable à l'eau avec des teneurs en substance valable dans la zone allant d'environ 30 à 50 % en poids.
  13. Dispersions aqueuses de co-oligomères selon la revendication 12, caractérisées en ce qu'elles renferment en supplément des agents de graissage à bas poids moléculaire pour l'apprêtage du cuir, qui contiennent un reste hydrocarboné oléophile ayant de préférence au moins 8 à 10 atomes de carbone conjointement avec au moins un groupe acide dans la molécule et de préférence sont rangés dans les classes suivantes :
    - hémi-esters d'acide sulfosuccinique d'alcools gras avec en particulier de 12 à 24 atomes de C et/ou leurs produits d'addition avec de l'oxyde d'alcoylène ayant de préférence jusqu'à 6 restes d'oxyde d'alcoylène,
    - hémi-esters d'acide sulfosuccinique de mono et/ou diglycérides d'acide gras ou de leurs produits d'addition avec de l'oxyde d'alcoylène avec de préférence jusqu'à 6 restes d'oxyde d'alcoylène pour une longueur de chaîne préférée de(s) acide(s) gras dans la zone de C₁₂ à C₂₄,
    - des acides gras sulfonés à longue chaîne, en particulier des acides gras alpha sulfonés de la zone de C₁₂ à C₂₄,
    - des sulfonates placés à l'intérieur, d'acides gras non saturés oléfiniquement une ou plusieurs fois ayant au moins 12 et de préférence de 16 à 24 atomes de carbone.
  14. Dispersions aqueuses de co-oligomères selon les revendications 12 et 13, caractérisées en ce qu'elles renferment, incorporés en supplément, d'autres agents de graissage du cuir à action imprégnante et/ou hydrophobisante, étant un mélange de principes actifs préféré de ce type est constitué des composants suivants :
    - hémi-esters d'acide sulfosuccinique avec des restes gras en C₁₂ à C₂₄ en combinaison avec des composés choisis dans le groupe des hydrocarbures en C₁₈ à C₂₆ oxydés ou oxydés et partiellement sulfonatés ou bien des cires en C₃₂ à C₄₀, des mono-alcoylesters en C₁₂ à C₂₄ d'acide phosphorique, des esters partiels d'acides polycarboxyliques, comme des mono-alcoylester en C₁₈ à C₂₄ d'acide citrique, des esters partiels de polyalcools comme les esters d'acide gras en C₁₈ à C₂₄ de sorbitanne, de glycérine ou de pentaérythrite.
  15. Dispersions aqueuses de co-oligomères selon les revendications 12 à 14, caractérisées en ce que les co-oligomères conformes à l'invention à base des composants (a) et (b) représentent au moins environ 35 % en poids, de préférence au moins la quantité prépondérante des substances de valeur destinées à imprégner et/ou à rendre hydrophobe dans les mélanges de substances de valeurs correspondantes des dispersions aqueuses.
EP92917518A 1991-09-03 1992-08-24 Dispersions aqueuses de nouveaux co-oligomeres amphiphiles pour l'appret graisseux resistant au lavage et au nettoyage des cuirs et des peaux, et leur utilisation Expired - Lifetime EP0602071B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4129244A DE4129244A1 (de) 1991-09-03 1991-09-03 Waessrige dispersionen von neuen amphiphilen co-oligomeren fuer die wasch- und reinigungsbestaendige fettende ausruestung von leder und pelzfellen sowie ihre verwendung
DE4129244 1991-09-03
PCT/EP1992/001938 WO1993005188A1 (fr) 1991-09-03 1992-08-24 Dispersions aqueuses de nouveaux co-oligomeres amphiphiles pour l'appret graisseux resistant au lavage et au nettoyage des cuirs et des peaux, et leur utilisation

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EP0602071A1 EP0602071A1 (fr) 1994-06-22
EP0602071B1 true EP0602071B1 (fr) 1995-03-01

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US (1) US5501707A (fr)
EP (1) EP0602071B1 (fr)
JP (1) JP3295080B2 (fr)
AT (1) ATE119208T1 (fr)
DE (2) DE4129244A1 (fr)
ES (1) ES2070009T3 (fr)
MX (1) MX9205019A (fr)
WO (1) WO1993005188A1 (fr)

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DE4400507A1 (de) * 1994-01-12 1995-07-13 Henkel Kgaa Mittel zur fettenden Ausrüstung von Leder
DE4402029A1 (de) * 1994-01-25 1995-07-27 Basf Ag Wäßrige Lösungen oder Dispersionen von Copolymerisaten
DE4405205A1 (de) * 1994-02-18 1995-08-24 Henkel Kgaa Neue Lederfettungsmittel und ihre Verwendung
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
DE19516963A1 (de) * 1995-05-12 1996-11-14 Stockhausen Chem Fab Gmbh Verfahren zur Behandlung von Häuten, Fellen, Ledern und Pelzen mit Tensiden zur Verbesserung der Hydrophobierwirkung und zur Angleichung qualitativ unterschiedlichen wet-blue-Materials
DE19609789A1 (de) * 1996-03-13 1997-09-18 Henkel Kgaa Verfahren zur Herstellung von Co-Oligomeren und deren Verwendung zur fettenden Ausrüstung von Leder
DE19612986A1 (de) 1996-04-01 1997-10-02 Basf Ag Verwendung von Copolymerisaten auf Basis ethylenisch ungesättigter Dicarbonsäuren oder Dicarbonsäureanhydride, niederer Olefine und hydrophober Comonomerer zum Nachgerben, Fetten oder Hydrophobieren von Leder und Pelzfellen
DE19625984C2 (de) * 1996-06-28 1999-07-29 Stockhausen Chem Fab Gmbh Wäßrige Polymerdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung in der Lederherstellung
DE19636494C2 (de) * 1996-09-09 2000-11-16 Stockhausen Chem Fab Gmbh Restmonomerarme, aminfreie Polymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung bei der Herstellung foggingarmer Leder
DE19942681B4 (de) * 1999-09-07 2006-04-27 Dr. Th. Böhme KG Chem. Fabrik GmbH & Co Copolymer zur Behandlung von Leder und Pelzfellen
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US8742047B2 (en) 2009-08-28 2014-06-03 3M Innovative Properties Company Polymerizable ionic liquid comprising multifunctional cation and antistatic coatings
JP5800812B2 (ja) 2009-08-28 2015-10-28 スリーエム イノベイティブ プロパティズ カンパニー 重合性イオン液体混合物を含む組成物及び物品並びに硬化方法
EP2515827A2 (fr) 2009-12-22 2012-10-31 3M Innovative Properties Company Compositions dentaires durcissables et articles contenant des liquides ioniques polymérisables
DE102012201167A1 (de) 2012-01-27 2013-08-01 Evonik Industries Ag Mischungszusammensetzung enthaltend aminofunktionelle Siloxane, hydrophobePartikel und hochmolekulare Silicone sowie dessen Verwendung zur Lederbehandlung
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US5501707A (en) 1996-03-26
DE4129244A1 (de) 1993-03-04
DE59201561D1 (de) 1995-04-06
MX9205019A (es) 1993-04-01
ES2070009T3 (es) 1995-05-16
ATE119208T1 (de) 1995-03-15
JPH06510083A (ja) 1994-11-10
WO1993005188A1 (fr) 1993-03-18
JP3295080B2 (ja) 2002-06-24
EP0602071A1 (fr) 1994-06-22

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