EP1512759B1 - Composition pour le traitement de cuir - Google Patents

Composition pour le traitement de cuir Download PDF

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Publication number
EP1512759B1
EP1512759B1 EP03017794A EP03017794A EP1512759B1 EP 1512759 B1 EP1512759 B1 EP 1512759B1 EP 03017794 A EP03017794 A EP 03017794A EP 03017794 A EP03017794 A EP 03017794A EP 1512759 B1 EP1512759 B1 EP 1512759B1
Authority
EP
European Patent Office
Prior art keywords
alcohol
composition according
leather
mpa
weight
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.)
Expired - Lifetime
Application number
EP03017794A
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German (de)
English (en)
Other versions
EP1512759A1 (fr
Inventor
Michael Dr. Breitsamer
Ottmar Götz
Manfred Dr. Palissa
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.)
Dystar Textilfarben GmbH and Co Deutschland KG
Original Assignee
Dystar Textilfarben GmbH and Co Deutschland KG
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.)
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Publication date
Application filed by Dystar Textilfarben GmbH and Co Deutschland KG filed Critical Dystar Textilfarben GmbH and Co Deutschland KG
Priority to DE50309326T priority Critical patent/DE50309326D1/de
Priority to AT03017794T priority patent/ATE388246T1/de
Priority to EP03017794A priority patent/EP1512759B1/fr
Publication of EP1512759A1 publication Critical patent/EP1512759A1/fr
Application granted granted Critical
Publication of EP1512759B1 publication Critical patent/EP1512759B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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

Definitions

  • the present invention relates to a composition for the treatment of leather, a process for its preparation and its use for the hydrophobing and / or softening of leather.
  • Water-soluble hydrophobicizing fatliquor formulations contain the hydrophobizing components in a water phase emulsified or dispersed. Many of the emulsifiers used for this purpose counteract due to their hydrophilic parts of the molecule water repellency, resulting in insufficient hydrophobing of the leather.
  • silicone oils without or with functional groups, such as OH, carboxy and amino groups and halogen-substituted polymers, such as fluorocarbon compounds used.
  • functional groups such as OH, carboxy and amino groups
  • halogen-substituted polymers such as fluorocarbon compounds used.
  • fatty polyacrylates are used today. These cause a hydrophobic and simultaneously softening effect. Their effect is enhanced by additional use of silicone oils or functional silicone oils in the leather treatment agent (EP 1 087 021 A1 ). Disadvantage of this fatliquoring agent is that the leather produced therewith are much too soft, cause the typical "rubbery" handle acrylate-based fatliquor and thus can not or only partially used for certain applications, such as for permanent shoe upper leather.
  • the reaction product from the reaction of phosphating agent with the abovementioned OH components siloxane and furthermore alcohol and / or alcohol polyglycol ether is used, ie there is a phosphoric acid ester mixture in the composition according to the invention.
  • a phosphating agent is understood to mean any agent that is capable of forming phosphoric acid esters with the OH components.
  • the phosphating agent is P 2 O 5 , with which the phosphating reaction can be carried out in a particularly favorable, simple and rapid manner.
  • the phosphoric acid esters are in particular derived from the ortho-phosphoric acid. It can be mono-, di- and tri-esters.
  • the OH components used for the reaction with the phosphating agent are a mixture containing the siloxanes described in more detail above and also either a C 10 -C 40 alcohol or a C 10 -C 40 alcohol polyglycol ether or both a C 10 -C 40 alcohol and a C10-C40 alcohol polyglycol ether.
  • the phosphoric acid ester mixture of the composition according to the invention can, as described above, be prepared by phosphating a mixture of the abovementioned OH components. But it is also possible to use in the composition according to the invention in each case separately prepared with the respective OH components phosphoric acid ester.
  • the ⁇ , ⁇ -dihydroxypoly-C 1 -C 4 -alkylsiloxane is the compound ⁇ , ⁇ -dihydroxypolydimethylsiloxane, with which a composition according to the invention which is particularly advantageous in terms of its properties, in particular with regard to hydrophobing and plasticizing, is obtained.
  • the viscosity of the siloxane is 500 mPas. Siloxanes having this viscosity give particularly advantageous compositions according to the invention, in particular with regard to the hydrophobizing effect and the softening properties.
  • a plurality of mutually different C 10 -C 40 alcohols can be used in the phosphatization reaction.
  • they may be primary alcohols.
  • the alcohols are (i) unsaturated, in particular monounsaturated, C 12 -C 20 -fatty alcohols, in particular cetyl alcohol and oleyl alcohol, or mixtures of 2 or more of these, for example a mixture of cetyl alcohol and oleyl alcohol in the ratio 1: 1, (ii) branched or unbranched saturated C20-C40 alcohols, for example C30-C38 Guerbet alcohol, and (iii) saturated C10-C18 alcohols or mixtures of 2 or 3 of the alcohols (i) to (iii).
  • the C 10 -C 40 alcohol polyglycol ethers are preferably those derived from the C 10 -C 40 alcohols described in more detail above, in particular the alcohols (i), (ii) and (iii).
  • the alcohol polyglycol ethers used in the composition of the invention have units derived from alkylene oxide of 0.5 to 10 mol.
  • alkylene oxides ethylene oxide, propylene oxide and mixtures thereof can be used.
  • the preparation of the phosphoric acid ester mixture used in the composition according to the invention can be carried out by initially charging the abovementioned OH components in a reaction vessel. If one of the OH components is solid, it may be necessary to melt it. Optionally, the mixture of the submitted OH components can be heated to about 40 ° C.
  • the phosphating agent for example P 2 O 5 , is introduced into this mixture.
  • the phosphating reaction is exothermic, the reaction temperature can rise to 80 ° C to 85 ° C. If it rises to over 85 ° C, it is favorable to carry out a cooling.
  • the phosphating reaction can be carried out under a protective gas atmosphere, such as N 2 .
  • the reaction temperature for the phosphating may be 70 ° C to 80 ° C.
  • the reaction can be carried out with stirring. Conveniently, the reaction is stopped after completion of the phosphoric acid ester formation. This can be the case after about 5 to 6 hours.
  • the phosphating agent P 2 O 5 is favorably used based on the OH groups of the OH components in a molar ratio of 1: 2 to 1: 3 (n P 2 O 5 : n OH groups). As a result, as complete as possible conversion of the phosphating agent is achieved.
  • the amount of siloxane is desirably from 50% to 60% by weight, based on the mixture of OH components used in the phosphating reaction.
  • the remainder to 100% by weight, based on the mixture of the OH components used in the phosphating reaction, can then be formed by the C 10 -C 40 alcohol and / or C 10 -C 40 alcohol polyglycol ether.
  • the above mixture of the OH components A, B, C and D it may contain 30% by weight to 40% by weight of A, 5% by weight to 10% by weight of B, 2% by weight. % to 4 wt .-% C and 50 wt .-% to 60 wt .-% D, wherein the amounts are based on the mixture of the OH components.
  • mineral oil preferably mineral oil is used.
  • mineral oil the common mineral oils used for the leather grease can be used. These are mineral oils with predominantly paraffinic content (paraffinic mineral oils) with a viscosity of 15 mm 2 / s to 20 mm 2 / s at 40 ° C.
  • mineral oils with predominantly paraffinic content (paraffinic mineral oils) with a viscosity of 15 mm 2 / s to 20 mm 2 / s at 40 ° C.
  • other, for example naphthenic, mineral oils with other viscosities for example naphthenic, mineral oils with other viscosities.
  • synthetic oils or waxes such as paraffin oil, alkylbenzenes, paraffin waxes, polyethylene waxes but also native oils or waxes, such as wool fat, beeswax, fish oil, rapeseed oil and lecithin can be used for the composition according to the invention.
  • An emulsifier may furthermore be present in the composition according to the invention.
  • the emulsifier serves to stabilize the composition according to the invention and to improve its optical and performance properties.
  • those emulsifiers are used which do not impair the hydrophobizing effect of the composition according to the invention.
  • emulsifiers examples include those in the EP 0 213 480 A2 described salts of an ⁇ -amino acid having 2 to 6 carbon atoms and with the Akyl radical of a saturated or unsaturated fatty acid having 9 to 20 carbon atoms on the amine nitrogen, which may optionally be additionally substituted by methyl, wherein as salts alkali metal salts, in particular of sodium or of potassium, ammonium salts or salts of a mono-, di- or trialkanolamine having 2 to 4 carbon atoms in the alkanol radical, in particular mono-, di- or triethanolamine.
  • N-oleoyl sarcoside, N-stearyl sarcoside, N-lauryl sarcoside and their salts have proven particularly useful.
  • Nonionic surfactants can be used if they do not adversely affect the hydrophobic effect. These are, for example, nonionic emulsifiers (eg fatty alcohol ethoxylates) with an HLB value preferably of 3-9. It is also possible to use sorbitan esters and esters of other polyols. All surfactants from the group of anionic surfactants can also be used if they provide the required performance properties and do not impair the hydrophobic effect.
  • the amount of the emulsifier in the composition according to the invention is 0 to 5 wt .-%, preferably about 2.5 wt .-%.
  • composition according to the invention may further comprise conventional adjusting agents, in particular glycols, e.g. in an amount of from 1% to 2% by weight, based on the composition of the invention, and a biocide and / or fungicide, each e.g. in an amount of about 0.1% by weight, based on the composition of the invention.
  • conventional adjusting agents in particular glycols, e.g. in an amount of from 1% to 2% by weight, based on the composition of the invention, and a biocide and / or fungicide, each e.g. in an amount of about 0.1% by weight, based on the composition of the invention.
  • composition of the invention may be water, which also acts as an adjusting agent.
  • water causes the composition of the invention can be used immediately by the user. Distilled water or deionized water may conveniently be used as the water, thereby advantageously avoiding precipitation reactions in the composition according to the invention.
  • the composition according to the invention has a whole series of advantages.
  • the composition according to the invention is a water-emulsifiable leather treatment agent which is distinguished by an excellent hydrophobizing effect and also an excellent softening effect of leather. It is a multifunctional composition that can simultaneously achieve the hydrophobing and softening of leather.
  • the disadvantageous properties of the acrylate-based hydrophobicizing fatliquoring agent to be plasticized do not include the composition according to the invention. There is a reproducible good water repellency exercised on the leather produced, with no additional, used in the tannery aids.
  • the composition according to the invention does not adversely affect the subsequent leather treatment steps.
  • the hygienic properties of the leather produced with the composition according to the invention are outstanding.
  • the composition of the invention can be used without further use of organic solvents, whereby it proves to be advantageous in terms of toxicological and environmental aspects.
  • the composition of the invention can be easily applied to the leather in an aqueous liquor.
  • the present invention further provides a process for the preparation of the composition according to the invention, wherein the phosphoric acid ester mixture a), the Mineral oil b) and optionally the other ingredients, such as emulsifier, adjuster, biocide and fungicide are mixed and then water is added to this mixture.
  • the addition of water can be done with stirring.
  • the pH of the composition according to the invention can be adjusted to a value between 7 and 9 with a base, preferably sodium hydroxide solution or potassium hydroxide solution.
  • a base preferably sodium hydroxide solution or potassium hydroxide solution.
  • the addition of adjusting agents, such as glycols, z. B. butyglycol, fungicide and biocide can also be done only after the addition of water.
  • the composition according to the invention is ideally suited for softening and hydrophobing leather. Due to the multifunctionality of the composition according to the invention, softening and hydrophobing can be achieved simultaneously.
  • the composition according to the invention can be used in the same way as the previously used fatliquoring agents and water repellents.
  • the amount of the composition according to the invention can be 8% by weight to 15% by weight, based on the shaved weight of the leather.
  • Example 1 Preparation of a Composition According to the Invention
  • Example 2 Treatment of pure chrome leather using the agent according to the invention
  • Drum speed approx. 30 rpm for small barrels
  • Example 3 Treatment of vegetable retanned leather using a composition of the invention
  • the leathers made according to Examples 2 and 3 were full, soft, had a comfortable grip, and had no negative rubbery feel. Furthermore, they show excellent hydrophobization.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Claims (10)

  1. Composition pour le traitement du cuir, comprenant
    a) 20% en poids à 30% en poids, par rapport à la composition, d'un mélange d'esters de l'acide phosphorique, pouvant être obtenu par transformation d'un agent de phosphatation avec un mélange, contenant de l'α,ω-dihydroxypoly-C1-C4-alkylsiloxane présentant une viscosité à 25°C de 200 mPa.s à 20 000 mPa.s et/ou de l'α,ω-dihydroxyalkylpoly-C1-C4-alkylsiloxane présentant une viscosité de 40 mPa·s à 300 mPa·s ainsi qu'en outre un alcool en C10-C40 et/ou un alcool en C10-C40 comprenant 0,5 à 10 moles d'unités dérivées d'un oxyde d'alkylène et
    b) 20% en poids à 35% en poids, par rapport à la composition, d'huile et/ou de cire.
  2. Composition selon la revendication 1, l'agent de phosphatation étant le P2O5.
  3. Composition selon l'une quelconque des revendications précédentes, où l'α,ω-dihydroxypoly-C1-C4-alkylsiloxane est le composé α,ω-dihydroxypolydiméthylsiloxane.
  4. Composition selon l'une quelconque des revendications précédentes, la viscosité de l'α,ω-dihydroxypoly-C1-C4-alkylsiloxane étant de 500 mPa.s.
  5. Composition selon l'une quelconque des revendications précédentes, l'alcool en C10-C40 étant choisi parmi un alcool gras insaturé en C12-C20, un alcool saturé, ramifié ou non ramifié en C20-C40, un alcool saturé en C10-C18 ou les mélanges de 2 de ceux-ci ou plus.
  6. Composition selon l'une quelconque des revendications précédentes, l'alcool en C10-C40 comprenant 0,5 à 10 moles d'unités dérivées d'un oxyde d'alkylène étant choisi parmi les alcools gras insaturés en C12-C20, un alcool saturé, ramifié ou insaturé en C20-C40, un alcool saturé en C10-C18, qui sont à chaque fois transformés avec 0,5 à 10 moles d'un oxyde d'alkylène, ou les mélanges de 2 de ceux-ci ou plus.
  7. Composition selon l'une quelconque des revendications précédentes, le mélange d'esters de l'acide phosphorique étant le produit de transformation d'un agent de phosphatation avec un mélange
    A d'un mélange d'alcools gras insaturés en C12-C20, de préférence un mélange alcool cétylique/oléylique dans un rapport 1:1, le cas échéant éthoxylé avec 0,5 à 10 moles d'oxyde d'éthylène, de préférence 3,5 moles d'oxyde d'éthylène ;
    B d'un alcool saturé, ramifié ou non ramifié en C20-C40, de préférence un alcool de Guerbet en C30-C38 ;
    C d'un alcool gras saturé présentant une longueur moyenne de chaîne de C10-C18, et
    D d'un α,ω-dihydroxypolydiméthylsiloxane présentant une viscosité à 25°C de 200 mPa.s à 20 000 mPa.s, de préférence de 500 mPa.s.
  8. Composition selon l'une quelconque des revendications précédentes, contenant en outre jusqu'à 5% en poids d'émulsifiant.
  9. Procédé pour la préparation d'une composition selon l'une quelconque des revendications 1 à 8, le mélange d'esters de l'acide phosphorique a) étant mélangé avec l'huile et/ou la cire b) et le cas échéant l'émulsifiant, puis de l'eau étant ajoutée.
  10. Utilisation de la composition selon l'une quelconque des revendications 1 à 8 pour hydrofuger et/ou assouplir le cuir.
EP03017794A 2003-08-04 2003-08-04 Composition pour le traitement de cuir Expired - Lifetime EP1512759B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE50309326T DE50309326D1 (de) 2003-08-04 2003-08-04 Zusammensetzung zur Behandlung von Leder
AT03017794T ATE388246T1 (de) 2003-08-04 2003-08-04 Zusammensetzung zur behandlung von leder
EP03017794A EP1512759B1 (fr) 2003-08-04 2003-08-04 Composition pour le traitement de cuir

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP03017794A EP1512759B1 (fr) 2003-08-04 2003-08-04 Composition pour le traitement de cuir

Publications (2)

Publication Number Publication Date
EP1512759A1 EP1512759A1 (fr) 2005-03-09
EP1512759B1 true EP1512759B1 (fr) 2008-03-05

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Family Applications (1)

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EP03017794A Expired - Lifetime EP1512759B1 (fr) 2003-08-04 2003-08-04 Composition pour le traitement de cuir

Country Status (3)

Country Link
EP (1) EP1512759B1 (fr)
AT (1) ATE388246T1 (fr)
DE (1) DE50309326D1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102190606B (zh) * 2010-03-19 2014-03-12 广州市浪奇实业股份有限公司 一种新型磺化油脂的制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2043422C1 (ru) * 1993-07-30 1995-09-10 Научно-производственное объединение "Центральный научно-исследовательский институт кожевенно-обувной промышленности" Состав для жирования кож
JPH0948855A (ja) * 1995-08-07 1997-02-18 Kao Corp リン酸トリエステル変性オルガノ（ポリ）シロキサン、その製造法、並びにそれを含有する化粧料及び外用剤
EP1087021B1 (fr) * 1999-09-18 2003-08-06 Trumpler GmbH & Co. Chemische Fabrik Agent de traitement du cuir

Also Published As

Publication number Publication date
ATE388246T1 (de) 2008-03-15
EP1512759A1 (fr) 2005-03-09
DE50309326D1 (de) 2008-04-17

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