EP0964935A1 - Utilisation des produits de sulfatation des diesters d'alkyleneglycol - Google Patents

Utilisation des produits de sulfatation des diesters d'alkyleneglycol

Info

Publication number
EP0964935A1
EP0964935A1 EP98913587A EP98913587A EP0964935A1 EP 0964935 A1 EP0964935 A1 EP 0964935A1 EP 98913587 A EP98913587 A EP 98913587A EP 98913587 A EP98913587 A EP 98913587A EP 0964935 A1 EP0964935 A1 EP 0964935A1
Authority
EP
European Patent Office
Prior art keywords
leather
products
agents
fats
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP98913587A
Other languages
German (de)
English (en)
Other versions
EP0964935B1 (fr
Inventor
Ramon Segura
José M. RUIZ
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.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co 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.)
Filing date
Publication date
Application filed by Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP0964935A1 publication Critical patent/EP0964935A1/fr
Application granted granted Critical
Publication of EP0964935B1 publication Critical patent/EP0964935B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 invention relates to the use of selected anionic surfactants for the production of fatliquoring agents for leather and furs.
  • greasing agents are the most important tools to shape the character of leather.
  • the effect of the fatliquor comes from a fiber-insulating lubrication and a hydrophobization.
  • the mutual friction is reduced and consequently the suppleness and stretchability of the fabric are improved.
  • This has a positive impact on the tear resistance of the leather, because in a stretchy material, many fibers align in the direction of tension when subjected to tensile stress and then offer greater resistance to tearing than the same fibers within a brittle material.
  • the water repellency also has tanning effects since it is associated with the displacement of water from the skin.
  • Vegetable and animal oils, fats and waxes are generally used as leather greasing agents, furthermore the hydrolysis, sulfation, oxidation and hardening products obtained from these substances by chemical conversion and finally mineral greasing agents; in detail:
  • Oils and fats refer to esters of glycerin and fatty acids that are solid or liquid at room temperature.
  • oils and fats refer to esters of glycerin and fatty acids that are solid or liquid at room temperature.
  • fatty acids are esterified with higher molecular weight alcohols instead of glycerin.
  • Waxes are beeswax, Chinese wax, caranuba wax, montan wax and wool fat; The most important resins include rosin, yeast oil and shellac.
  • Mineral greasing agents are also important for leather production. These hydrocarbons are similar to natural fats and oils in some properties, but cannot be saponified. These are fractions from petroleum distillation, which are called mineral oil in liquid form, petroleum jelly in pasty form and paraffin in solid form.
  • fatty spew undesirable stains are formed on the surface of the tanned and greased leather, which are referred to as "fatty spew".
  • Grease rashes occur primarily on chrome-tanned leather after shorter or longer storage as a white, often veil-like covering that only covers individual areas or the entire leather surface.
  • the rash is due to the release of solid fatty substances from the leather. It can be caused by the natural fat present in the leather itself or by fatty substances that were only incorporated in the course of the greasing of the leather. Fat mixtures used to grease leather tend to develop a rash if they contain a lot of free fatty acids. Free fatty acids generally have a higher melting point than their glycerides. The hydrolytic splitting of fatty substances during the storage of the leather increases the risk of fat rashes.
  • Soaps and licker greases are split in chrome leather, especially in insufficiently deacidified chrome leather, with the release of fatty acids. Sulphated oils and fats show a different tendency to form fat deposits, the tendency to deflect generally decreases with a longer lifespan [cf. J.In Soc.Leath.Trad.Chem. 47, 379 (1952)]. Fat rashes are more likely to occur the more the leather contains fat substances that tend to form rashes. The amount, composition and location of the fat mixture of natural fat and lickerfat present in the leather are decisive for the extent and composition of the rash. Loosely structured leather is less prone to rash than leather with a dense fiber structure.
  • Grease rashes are observed more often at low temperatures than at warmer outside temperatures.
  • the crystalline Greasy rashes develop in the hair holes and gland canals, initially forming small crystals in the depth, which gradually fill the entire hair hole as larger fat crystals, swell beyond the leather surface and become matted into a dense crystal film.
  • All fats containing stearin or palmitin derivatives can cause crystalline fat rashes, the risk of rash increases with increasing concentration [Ledertechn.Rundsch. 1 (1949)].
  • the so-called neutral fats ie substances suitable for leather greasing that do not contain any ionic groups in the molecule, for example fats, waxes and hydrocarbons, tend to form fat rashes.
  • Those neutral fats which represent stearin and / or palmitin derivatives, such as corresponding triglycerides or the free fatty acids, are particularly critical.
  • anionic fatliquoring agents are not without problems.
  • a major disadvantage is that a large number of these agents tend to form fat rashes when used.
  • biodegradability is not always satisfactory.
  • Sulphated oils are viscous in the range of high active substance contents and can therefore often only be metered with difficulty; after all, their color quality is often unsatisfactory.
  • the complex object of the invention was therefore to develop new greasing agents for leather and furs based on anionic surfactants, which are characterized by improved ecological and application properties, such as a more pleasant grip and less tendency to become greasy.
  • the feedstocks should also have a better color quality and handling advantages than the known sulfated or sulfited fatty substances, particularly with regard to the production of liquid, low-viscosity products.
  • the invention relates to the use of sulfation products of alkylene glycol diesters of the formula (I)
  • R 1 CO stands for an unsaturated acyl radical with 16 to 22 carbon atoms and n for numbers from 2 to 4, in the form of their alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium salts for the preparation of leather greasing agents and furs.
  • the sulfation products of the alkylene glycol diesters according to the invention not only have excellent ecological properties, but also have a significantly lower tendency to form fat rashes in comparison with other known anionic fatliquoring agents.
  • they give leather an improved Schmalzig, Suppleness, a pleasant grip and increased hydrophobicity.
  • the sulfation products are also highly concentrated and of low viscosity and can therefore be easily incorporated into liquid, aqueous formulations.
  • sulfated ester oils they are also characterized by improved color quality, while, unlike sulfonated oleic acid esters, they are completely biodegradable even under anaerobic conditions.
  • alkylene glycol diesters Sulfation products of alkylene glycol diesters are known substances that can be obtained by the relevant methods of preparative organic chemistry.
  • the usual starting point for their preparation is alkylene glycols, preferably ethylene or propylene glycol, which are first esterified with unsaturated fatty acids. The diesters are then sulfated with sulfuric acid or oleum and neutralized with aqueous bases.
  • Typical examples are diesters of ethylene glycol, propylene glycol and / or butylene glycol with oleic acid, elaidic acid, Petra- selinic acid, linoleic acid, linoien acid, ricinoleic acid, gadoleic acid and / or erucic acid and their technical mixtures. Due to the manufacturing process, the diesters may still have a monoester content below 15% by weight. Sulfation products of propylene glycol dioleate in the form of the ammonium, sodium or potassium salt are preferably used.
  • the sulfation of the unsaturated fatty acid lower alkyl esters can be carried out in the manner known for saturated fatty acid lower alkyl esters [J. Falbe (ed.), "Surfactants in consumer products", Springer Verlag, Berlin-Heidelberg, 1987, p. 61], reactors which work according to the falling film principle, are preferred.
  • Sulfuric acid or preferably oleum are suitable as sulfonating agents.
  • the molar ratio of ester to sulfating agent can be 1: 0.1 to 1: 0.95 and in particular 1: 0.25 to 1: 0.8.
  • the sulfation is usually carried out at from 15 to 90.degree. With regard to the viscosity of the starting materials on the one hand and the color quality of the resulting sulfonation products on the other hand, it has proven to be optimal to carry out the reaction in a temperature range from 20 to 30 ° C.
  • the acidic sulfation products obtained in the sulfation are stirred into aqueous bases, neutralized and adjusted to a pH of 6.5 to 8.5.
  • bases for the neutralization come alkali metal hydroxides such as sodium, potassium and lithium hydroxide, alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, mono-, di- and tri-C2-alkanolamines, for example mono-, di- and Triethanolamine as well as primary, secondary or tertiary Cu alkyl amines and glucamines into consideration.
  • the neutralization bases are preferably used in the form of 5 to 55% by weight aqueous solutions, with 5 to 25% by weight aqueous sodium hydride solutions being preferred.
  • the sulfation products can be bleached in a manner known per se by adding hydrogen peroxide or sodium hypochlorite solution. Based on the solids content in the solution of the sulfation products, 0.2 to 2% by weight of hydrogen peroxide, calculated as a 100% substance, or corresponding amounts of sodium hypochlorite are used.
  • the pH of the solutions can be adjusted using suitable buffering agents, e.g. B. be kept constant with sodium phosphate or citric acid. To stabilize against bacterial attack, conservation is also recommended, e.g. B. with formaldehyde solution, p-hydroxybenzoate, sorbic acid or other known preservatives.
  • the sulfonation products according to the invention can be used alone, but preferably in a mixture with other anionic, nonionic, amphoteric or zwitterionic surfactants and - to a limited extent - also cationic surfactants.
  • anionic surfactants are alkylbenzenesulfonates, droxymischethersulfate alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether, ⁇ - methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, Glycerol ether, hybrid, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates , Mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, acyl lactylates, alkyl
  • anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polygylcol ethers, fatty amine polyglycol ethers, alk-oxylated triglycerides, alk (en) yl oligoglycosides, fatty acid-N-alkyl glucamides and polyol fatty acid orbitates, sugar esters, polyol fatty acid orbital esters.
  • nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amidobetaines, aminoprapionates, aminogiycinates, imidazoiinium betaines and sulfobetaines.
  • Typical examples of cationic surfactants with which the anionic sulfonation products are compatible and do not form poorly soluble salts are ester quats, in particular those which have ethylene oxide units in the molecule. The surfactants mentioned are exclusively known compounds.
  • the fatliquoring agents can contain other common auxiliaries and additives.
  • the proportion of the sulfation products in the agents according to the invention is usually 15 to 90 and preferably 20 to 80% by weight, based on the agents.
  • the agents are dosed in such a way that 1 kg of leather or fur (calculated as the shaved weight) accounts for 20 to 1000, preferably 30 to 80 g of the agent. Examples
  • the organic value phase was adjusted to a pH of 7.5.
  • the product contained 42.3% by weight of anionic surfactant, 42.0% by weight of unsulfated components, 3.8% by weight of sodium sulfate and ad 100% by weight of water.
  • the anionic surfactant content (WAS) and the unsulfated content (US) were determined according to the DGF standard methods, Stuttgart 1950-1984, H-III-10 and G-II-6b.

Landscapes

  • 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)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne l'utilisation des produits de sulfatation des diesters d'alkylèneglycol pour fabriquer des nouveaux produits destinés à nourrir le cuir et les fourrures. Ces produits donnent au cuir une plus grande souplesse et une plus grande imperméabilité. Ils sont caractérisés par une tendance réduite à former des réponses graisseuses et par une meilleure compatibilité écotoxicologique.
EP98913587A 1997-03-06 1998-02-25 Utilisation des produits de sulfatation des diesters d'alkyleneglycol Expired - Lifetime EP0964935B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1997109180 DE19709180A1 (de) 1997-03-06 1997-03-06 Verwendung von Sulfatierungsprodukten von Alkylenglycoldiestern
DE19709180 1997-03-06
PCT/EP1998/001061 WO1998039489A1 (fr) 1997-03-06 1998-02-25 Utilisation des produits de sulfatation des diesters d'alkyleneglycol

Publications (2)

Publication Number Publication Date
EP0964935A1 true EP0964935A1 (fr) 1999-12-22
EP0964935B1 EP0964935B1 (fr) 2002-01-09

Family

ID=7822451

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98913587A Expired - Lifetime EP0964935B1 (fr) 1997-03-06 1998-02-25 Utilisation des produits de sulfatation des diesters d'alkyleneglycol

Country Status (5)

Country Link
EP (1) EP0964935B1 (fr)
DE (1) DE19709180A1 (fr)
ES (1) ES2170488T3 (fr)
PT (1) PT964935E (fr)
WO (1) WO1998039489A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10242401A1 (de) * 2002-09-12 2004-03-25 Basf Ag Fettungsmittel auf der Basis von Mischungen modifizierter, nativer Öle mit alkoxylierten Alkanolen, ihre Verwendung bei der Herstellung und/oder Behandlung von Leder und Häuten, sowie Verfahren zur Herstellung und/oder Behandlung von Leder und Häuten mit diesen Fettungsmitteln
CN102978301A (zh) * 2012-12-28 2013-03-20 陕西科技大学 原位法制备季铵盐插层蒙脱土改性菜籽油阻燃型纳米复合加脂剂的方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3617657C2 (de) * 1986-05-26 1994-08-18 Stockhausen Chem Fab Gmbh Bei Raumtemperatur flüssige Derivate von natürlichen Fetten oder Ölen, Verfahren zu deren Herstellung, und ihre Verwendung
DE4141532A1 (de) * 1991-12-17 1993-06-24 Henkel Kgaa Verfahren zur herstellung hydrophilisierter triglyceride
DE4223704A1 (de) * 1992-07-18 1994-01-20 Henkel Kgaa Verwendung nichtionischer organischer Dialkylverbindungen zur Verhinderung von Fettausschlag auf Leder
DE4418942A1 (de) * 1994-05-31 1995-12-07 Henkel Kgaa Mittel zur Fettung von Ledern und Pelzen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9839489A1 *

Also Published As

Publication number Publication date
EP0964935B1 (fr) 2002-01-09
ES2170488T3 (es) 2002-08-01
PT964935E (pt) 2002-06-28
DE19709180A1 (de) 1998-09-10
WO1998039489A1 (fr) 1998-09-11

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