WO1995033077A1 - Agents utilises pour nourrir des cuirs et des fourrures - Google Patents

Agents utilises pour nourrir des cuirs et des fourrures Download PDF

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Publication number
WO1995033077A1
WO1995033077A1 PCT/EP1995/001941 EP9501941W WO9533077A1 WO 1995033077 A1 WO1995033077 A1 WO 1995033077A1 EP 9501941 W EP9501941 W EP 9501941W WO 9533077 A1 WO9533077 A1 WO 9533077A1
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WO
WIPO (PCT)
Prior art keywords
leather
agents
acid
fatty acid
products
Prior art date
Application number
PCT/EP1995/001941
Other languages
German (de)
English (en)
Inventor
Ramon Segura
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to JP8500254A priority Critical patent/JPH10501010A/ja
Priority to EP95920858A priority patent/EP0763139B1/fr
Priority to DE59509641T priority patent/DE59509641D1/de
Publication of WO1995033077A1 publication Critical patent/WO1995033077A1/fr

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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 invention relates to fatliquoring agents for leather and furs containing selected anionic surfactants and their use for the preparation of the agents.
  • greasing agents are the most important tools to shape the character of leather.
  • the effect of the fatliquoring agents comes about through fiber-insulating lubrication and through hydrophobization.
  • 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.
  • 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".
  • Fatty spew is formed mainly on chromgegerb ⁇ th leathers for short or prolonged storage as a white, often bloom-the only individual sites or the whole leather surface covered.
  • the rash is reindeer on leakage of solid fats from the leather Maschinenzuun ⁇ . It can be caused by the per se in leather existing natural fat or fatty substances that have been incorporated only in the course of greasing of the leather.
  • 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 have different tendencies to form fat rashes, the tendency to rash generally declines with a longer lifespan [cf. J.In. Soc. eat .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 position of the fat mixture of natural fat and lickerfat present in the leather are decisive for the extent and the 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 fatty spew develop holes and small crystals initially formed in the depth, the felting glands channels gradually than larger fatty crystals all the hair hole filling area over the leather upper ⁇ addition swell and ver ⁇ to a dense crystal film in the hair ⁇ . All fats stearic or palmitic derivatives ent ⁇ hold, crystalline fatty spew can cause, with Increasing concentration increases the risk of rash [Ledertechn.Rundsch. 1 (1949)].
  • neutral fats i.e. substances suitable for leather greasing which do not contain any ionic groups in the molecule, e.g. Fats, waxes and hydrocarbons to form fat rashes.
  • a class of fatliquoring agents commonly used in this regard is halogenated compounds such as chlorinated hydrocarbons.
  • halogenated compounds such as chlorinated hydrocarbons.
  • Anionic surfactants are usually used for leather greasing.
  • EP-B 0247509 Sudleyhausen
  • sulfuric acid or oleum with unsaturated, alkoxylated and optionally epoxidized fats and oils are known.
  • sulfuric acid or gaseous sulfur Trioxide is also particularly suitable for the hydrophilization of fatty substances by sulfitation, ie the attachment of hydrogen sulfite to unsaturated compounds.
  • 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 area 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, for example, a more pleasant grip and less tendency towards greasy deposits.
  • the feedstocks should also have better color quality and advantages in handling, in particular with regard to look at the production of liquid, low-viscosity products.
  • the invention relates to agents for greasing leather and furs with a content of 1 to 30% by weight of sulfonation products of unsaturated fatty acid lower alkyl esters in the form of their alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium salts.
  • sulfonation products of unsaturated fatty acid alkyl esters according to the invention are not only completely biodegradable, but have proposals in comparison with other known anionic fatliquors a significantly lower tendency to form Fettaus ⁇ was found. Moreover, they give leathers also improved Schmalzig- or suppleness, an integrally ⁇ take grip and increased water repellency.
  • the sulfation products are also highly concentrated and of low viscosity and can therefore be easily incorporated into liquid, aqueous formulations. In contrast to sulfated ester oils, for example, they are also characterized by an improved color quality. Sulfation products
  • Sulfation products of unsaturated fatty acid lower alkyl esters are known substances which can be obtained by the relevant methods of preparative organic chemistry.
  • One method of making them is, for example, to use unsaturated fatty acid lower alkyl esters such as e.g. to implement technical oleic acid esters with gaseous sulfur trioxide and then to neutralize the crude sulfonation product with an aqueous base and at the same time to hydrolyze cyclic intermediates such as sultones [DE-Al 3803912 (Henkel)].
  • the sulfonation is an electrophilic addition of the SO 3 molecule to the double bond.
  • Mixtures of isomeric hydroxy and alkene sulfonates are formed in the course of neutralization or hydrolysis. An overview of this is provided by A. Behler et al. in C.R. CESIO, elttensidkongress Paris, Vol.II, p.14 (1988).
  • the sulfonation products are prepared by adding oleum to the unsaturated esters mentioned. Mixtures of sulfates and sulfonates are obtained.
  • Sulfation products of unsaturated fatty acid lower alkyl esters of the formula (I) are preferably used,
  • Typical examples are sulfonation products of esters of methanol, ethanol, butanol, octanol and in particular 2-ethylhexanol with palmoleic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid, behenic acid and clupanodonic acid and their technical mixtures in the form of their sodium , Potassium and / or ammonium salts.
  • the sulfonation products can also contain technical fatty acid cuts with a predominantly unsaturated fraction such as rapeseed, sunflower and / or olive oil oleic acid as components.
  • Sulfation products of oleic acid 2-ethylhexyl ester, in particular based on olive oil fatty acid in the form of the sodium salt, are preferably used.
  • the sulfonation 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, oleum, chlorosulfonic acid and gaseous sulfur trioxide are suitable as sulfating agents.
  • the latter is usually diluted with an inert gas, preferably air or nitrogen, and in the form of a Gas mixture which contains the sulfonating agent in a concentration of 1 to 8, in particular 2 to 5,% by volume.
  • the molar ratio of ester to sulfating agent can be 1: 0.95 3 1: 1.3 and preferably 1: 1.0 to 1: 1.15 in the case of chlorosulfonic acid or sulfur trioxide. If sulfuric acid or oleum is used as the sulfonating agent, it is advantageous to use this in deficit, i.e. for example in a molar ratio of 1: 0.1 to 1: 0.95 and in particular 1: 0.25 to 1: 0.8.
  • the sulfonation is usually carried out at from 15 to 90 ° C.
  • it has proven to be optimal to carry out the reaction in a temperature range from 20 to 30 ° C.
  • the acidic sulfonation products obtained during the sulfonation 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-C2-4 ⁇ alkanolamines, for example mono- , Di- and triethanolamine and primary, secondary or tertiary C 4 alkylamines and glucamines into consideration.
  • the neutralization bases arrive preferably in the form of 5 to 55% by weight aqueous solutions are used, with 5 to 25 percent by weight aqueous Natriumhy ⁇ droxiditesen .-% being preferred.
  • the sulfonation may be bleached by the addition of hydrogen peroxide or triumhypochloritans Na ⁇ in a known manner by neutralization.
  • hydrogen peroxide or triumhypochloritans Na ⁇ in a known manner by neutralization.
  • 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 sulphonation according to the invention can be used alone, but preferably in admixture with other anionic, nonionic, amphoteric or zwitterionic surfactants, and - limited - and cationic surfactants used ⁇ the.
  • anionic surfactants are alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfo- nate, glycerol ether, o-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, ether sulfates Glycerin ⁇ , Hydroxymischethersulfate, monoglyceride (ether) - sulfates, fatty acid amide (ether) sulfates, mono- and Dialkylsulfo- succinate, mono- and dialkyl sulfosuccinamates, Sulfotriglyce- ride , Amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, acyl lac
  • nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, Fettklarepo- lyglycolester, FettTexreamidpolygylcolether, Fettaminpoly- glycol ethers, alkoxylated triglycerides, alk (en) yloligoglyko- side, fatty acid-N-alkyl glucamides, polyol fatty acid esters, sugar kerester, sorbitan esters and polysorbates.
  • non-ionic surfactants ⁇ polyglycol ether chains they may have a conventional, but preferably a narrow Ho ⁇ mologenverander.
  • amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, amino glycinates, imidazolinium betaines and sulfobetaines.
  • Typical examples of cationic surfactants with which the anionic sulfonation products are compatible and do not form sparingly soluble salts are esterquats, in particular those which have ethylene oxide units in the molecule.
  • the surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, reference is made to relevant reviews, for example J.Falbe (ed.), “Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.) , “Catalysts, surfactants and mineral oil additives", Thieme V erlag, Stuttgart, 1978, pp. 123-217.
  • the fatliquoring agents can contain other customary auxiliaries and additives.
  • the proportion of the sulfonation 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.
  • Sulphonation products of unsaturated fatty acid lower alkyl esters as a component of fatliquoring agents, give leathers and furs an improved lardiness and suppleness, a pleasant feel and increased hydrophobization.
  • a particular advantage lies in the fact that the sulfonation products are also highly concentrated and have a low viscosity and can accordingly be easily incorporated into liquid formulations. In comparison with other known anionic fatliquoring agents, they also show a significantly lower tendency to form fat rashes. When using the agents according to the invention, the colors are brilliant with good levelness.
  • Another object of the invention therefore relates to the use of the sulfonation products mentioned as anionic surfactants for greasing leather and furs.
  • oleic acid 2-ethylhexyl ester sulfonate / sulfate sodium salt 250 g (0.7 mol) of technical grade oleic acid 2-ethylhexyl ester (based on olive oil fatty acid with an oleic acid content of approx. 70% by weight) were placed in a 1-1-sulphonation reactor with jacket cooling and at a temperature of 31 to 33 ° C 44 g of oleum (20% by weight of SO3) were added in portions. The mixture was subjected to a post-reaction over a period of 90 min at 30 ° C. and then neutralized at about 55 ° C.
  • Anionic surfactant content 42.3% by weight
  • Anionic surfactant content 26.3% by weight Unsulfated parts 3.5% by weight sodium sulfate 1.1% by weight water 69.1% by weight Example 1 ;
  • Lecithin emulsion 3 ester sulfonate according to Hl 2 40 sulfited ester oil 3 40
  • Lecithin emulsion 2 45 ester sulfonate according to Hl 5 sulfited ester oil 4
  • Neutralisa water (40 ° C) 100 15 tion of sodium formate 0.5 sodium aluminum silicate 0.5
  • Examples 1 to 4 were repeated, but instead of the oleic acid 2-ethylhexyl ester sulfonate salt, a sulfated ester oil from the trade was used.
  • the resulting leather like ⁇ sen on a harder grip and less Schmalzmaschine. In addition, an uneven coloring was observed.

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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)
  • Lubricants (AREA)

Abstract

L'invention concerne de nouveaux agents utilisés pour nourrir des cuirs et des fourrures, qui contiennent, comme tensioactifs anioniques, des produits de sulfitage d'esters d'alkyle inférieur d'acide gras non saturés. Ces agents confèrent aux cuirs davantage de souplesse et les rendent plus imperméables. Ils se caractérisent en ce qu'ils ont moins tendance à former des sécrétions grasses et qu'ils sont d'une tolérabilité écotoxycologique avantageuse.
PCT/EP1995/001941 1994-05-31 1995-05-22 Agents utilises pour nourrir des cuirs et des fourrures WO1995033077A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP8500254A JPH10501010A (ja) 1994-05-31 1995-05-22 レザーまたはスキン用オイリング組成物
EP95920858A EP0763139B1 (fr) 1994-05-31 1995-05-22 Agents utilises pour nourrir des cuirs et des fourrures
DE59509641T DE59509641D1 (de) 1994-05-31 1995-05-22 Mittel zur fettung von ledern und pelzen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4418942A DE4418942A1 (de) 1994-05-31 1994-05-31 Mittel zur Fettung von Ledern und Pelzen
DEP4418942.7 1994-05-31

Publications (1)

Publication Number Publication Date
WO1995033077A1 true WO1995033077A1 (fr) 1995-12-07

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ID=6519396

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/001941 WO1995033077A1 (fr) 1994-05-31 1995-05-22 Agents utilises pour nourrir des cuirs et des fourrures

Country Status (6)

Country Link
EP (1) EP0763139B1 (fr)
JP (1) JPH10501010A (fr)
DE (2) DE4418942A1 (fr)
ES (1) ES2164768T3 (fr)
PT (1) PT763139E (fr)
WO (1) WO1995033077A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2162548A1 (es) * 1998-02-06 2001-12-16 Henkel Kgaa Derivados del acido maleico sulfitados

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19709180A1 (de) * 1997-03-06 1998-09-10 Henkel Kgaa Verwendung von Sulfatierungsprodukten von Alkylenglycoldiestern

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0178557A1 (fr) * 1984-10-12 1986-04-23 Henkel Kommanditgesellschaft auf Aktien Procédé pour la fabrication d'agents de graissage pour cuir et fourrures
EP0247490A1 (fr) * 1986-05-26 1987-12-02 Henkel Kommanditgesellschaft auf Aktien Matières grasses sulfitées
EP0353704A1 (fr) * 1988-08-02 1990-02-07 Chemische Fabrik Stockhausen GmbH Dérivés liquides ou coulants de graisses naturelles ou d'huiles, procédé de leur préparation et utilisation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0178557A1 (fr) * 1984-10-12 1986-04-23 Henkel Kommanditgesellschaft auf Aktien Procédé pour la fabrication d'agents de graissage pour cuir et fourrures
EP0247490A1 (fr) * 1986-05-26 1987-12-02 Henkel Kommanditgesellschaft auf Aktien Matières grasses sulfitées
EP0353704A1 (fr) * 1988-08-02 1990-02-07 Chemische Fabrik Stockhausen GmbH Dérivés liquides ou coulants de graisses naturelles ou d'huiles, procédé de leur préparation et utilisation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2162548A1 (es) * 1998-02-06 2001-12-16 Henkel Kgaa Derivados del acido maleico sulfitados

Also Published As

Publication number Publication date
DE59509641D1 (de) 2001-10-31
ES2164768T3 (es) 2002-03-01
PT763139E (pt) 2002-03-28
DE4418942A1 (de) 1995-12-07
EP0763139B1 (fr) 2001-09-26
EP0763139A1 (fr) 1997-03-19
JPH10501010A (ja) 1998-01-27

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