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 greasing agents for leather and furs containing selected anionic Surfactants and their use in the preparation of the compositions.
• greasing agents are the most important tools to improve the character of leather shape.
• the effect of the greasing agents comes from a fiber-insulating lubrication and a Hydrophobization.
• the mutual friction is reduced and consequently improves the suppleness and stretchability of the fabric. That has positive effects the tensile strength of the leather, because many fibers are aligned in a stretchy material under tensile stress in the pulling direction and then subject the tearing to greater resistance contrary to the same fibers within a brittle material.
• hydrophobization tanning effects are also achieved, since they are displaced with water from the Skin is connected.
• 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 rashes, the tendency to rash generally decreases with a longer lifespan [cf. J.Int.Soc.Leath.Trad.Chem. 47 , 379 (1952)].
• Grease 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 fat rashes develop in the hair holes and gland canals, whereby small crystals are initially formed in the depth, which gradually fill the entire hair hole as larger fat crystals, swell out over the leather surface and matted into a dense crystal film.
• halogenated compounds such as chlorinated hydrocarbons.
• Anionic surfactants are usually used for leather greasing.
• EP 0247509 B1 Stockhausen
• adducts of sulfuric acid or oleum with unsaturated, alkoxylated and optionally epoxidized fats and oils are known.
• the sulfilization ie the addition of hydrogen sulfite to unsaturated compounds
• the sulfilization is also particularly suitable for the hydrophilization of fatty substances.
• A. Kuenzel reports on the sulfitation of Dorschtran [Le der 8 , 5 (1957)] and M. Mikula on the sulfitation of unsaturated fatty acid butyl esters [Leder, Schuh, Lederwaren 21 , 282 (1986)] .
• From the German patent application DE-A1 4223704 (Henkel) also nonionic lubricants containing oleic acid esters and dialkyl ethers are known.
• EP 0247490 A1 which describes sulfited fatty substances.
• EP 0353704 A1 finally relates to sulfonation products of oxyalkylated fatty acid lower alkyl esters.
• anionic fatliquoring agents are not without problems.
• An essential one The disadvantage is that a large number of these agents are used to form fat rashes tend.
• biodegradability is not always satisfactory.
• Sulphated oils are viscous in the range of high active substance contents and can therefore often only be difficult dosing; after all, their color quality is often unsatisfactory.
• the complex object of the invention was therefore to find new greasing agents for leather and Develop furs based on anionic surfactants, which are characterized by improved ecological and application technology Properties such as more comfortable grip and less tendency to become greasy award.
• the feedstocks should also be compared to the known sulfated or sulfited fatty substances have a better color quality and advantages in handling, especially in terms of exhibit 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 C 1 -C 8 alkyl esters in the form of their alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium or glucammonium salts.
• the sulfonation products of the invention are more unsaturated Fatty acid lower alkyl esters are not only completely biodegradable, but in comparison with others known anionic fatliquoring agents have a significantly lower tendency to form fat rashes exhibit. In addition, they also give leathers an improved lard or Suppleness, a pleasant grip and increased hydrophobicity.
• the sulfonation products are also highly concentrated and low viscosity and can therefore be easily dissolved in liquid, aqueous Incorporate formulations. In contrast, for example, to sulfated ester oils, they draw Finally, it also has an improved color quality.
• Sulfation products of unsaturated fatty acid lower alkyl esters are known substances that can be obtained by the relevant methods of preparative organic chemistry.
• a process for their preparation consists, for example, in reacting unsaturated fatty acid lower alkyl esters such as technical oleic acid esters with gaseous sulfur trioxide and then neutralizing the crude sulfonation product with an aqueous base and at the same time hydrolyzing cyclic intermediates such as sultones [DE 3803912 A1 (Henkel)].
• 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 the neutralization or hydrolysis.
• the sulfonation products are prepared by adding oleum to the unsaturated esters mentioned. Mixtures of sulfates and sulfonates are obtained.
• R 1 CO-OR 2 Sulfation products of unsaturated fatty acid alkyl esters of the formula (I) are preferably used, R 1 CO-OR 2 in which R 1 CO represents an unsaturated acyl radical with 16 to 24 carbon atoms and 1, 2, 3, 4 and / or 5 double bonds and R 2 represents a linear or branched alkyl radical with 1 to 8 carbon atoms.
• Typical examples are sulfonation products of esters of methanol, ethanol, butanol, octanol and in particular 2-ethylhexanol with palmoleic acid, oleic acid, elaidic acid, petroselinic 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 as components such as rapeseed oil, sunflower and / or olive oil fatty 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 according to Fall film principle work, are preferred.
• Sulfuric acid, oleum, chlorosulfonic acid and gaseous sulfur trioxide can be used as sulfating agents.
• the latter is usually diluted with an inert gas, preferably air or nitrogen, and used 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 in the case of chlorosulfonic acid or sulfur trioxide can be 1: 0.95 to 1: 1.3 and preferably 1: 1.0 to 1: 1.15. If sulfuric acid or oleum is used as the sulfonating agent, it is advantageous to use this in deficit, ie 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. With regard to the viscosity of the feedstocks 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 sulfonation products obtained during the sulfonation are stirred into aqueous bases, neutralized and adjusted to a pH of 6.5 to 8.5.
• the bases for the neutralization are 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-C 2-4 -alkanolamines, for example mono-, Di- and triethanolamine as well as primary, secondary or tertiary C 1-4 -alkylamines and glucamines into consideration.
• the neutralization bases are preferably used in the form of 5 to 55% by weight aqueous solutions, 5 to 25% by weight aqueous sodium hydroxide solutions being preferred.
• the sulfonation products can be added in a manner known per se by adding Hydrogen peroxide or sodium hypochlorite solution are bleached.
• Hydrogen peroxide or sodium hypochlorite solution based on the Solids content in the solution of the sulfonation products, 0.2 to 2 wt .-% hydrogen peroxide, calculated used as a 100% substance, or corresponding amounts of sodium hypochlorite.
• the pH of the Solutions can be prepared using suitable buffering agents, e.g. with sodium phosphate or citric acid be kept constant. To stabilize against bacterial attack, preservation 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, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether, ⁇ -methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, Glycerol ether, Hydroxymischethersulfate, 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 oligogluco
• 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 polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, alk (en) yl oligoglycosides, fatty acid-N-alkyl glucamides, polyol fatty acid sorbate sorbate sorbate esters, zukkester ester sorbate.
• 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 amido betaines, aminopropionates, aminoglycinates, 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.
• the fatliquoring agents can be other common ones Auxiliaries and additives included.
• the proportion of sulfonation products is Agents according to the invention 15 to 90 and preferably 20 to 80 wt .-% based on the agent.
• the agents are dosed so that 20 to 1 kg of leather or fur (calculated as fold weight) 1000, preferably 30 to 80 g of the agent are eliminated.
• Sulfation products of unsaturated fatty acid lower alkyl esters confer as a component of fatliquoring agents
• leather and fur have an improved lardiness and suppleness, a pleasant grip and increased water repellency.
• a particular advantage is that the sulfonation products are also highly concentrated and have low viscosity and are accordingly easy to use in liquid formulations have it incorporated. They also show in comparison with other known anionic fatliquoring agents a significantly lower tendency to form fat rashes.
• Colorings are brilliant with good levelness.
• Another object of the invention relates therefore the use of the sulfonation products mentioned as anionic surfactants for greasing Leather and furs.
• the aqueous phase containing the ammonium sulfate formed was then separated off and discarded.
• the organic value phase was adjusted to a pH of 7.5.
• the resulting oleic acid 2-ethylhexyl ester sulfonate / sulfate had the following composition: anionic surfactants: 42.3% by weight, unsulfated components: 42.0% by weight, sodium sulfate: 3.8% by weight, water: 11.9 % By weight.
• the anionic surfactant content (WAS) and the unsulfonated content (US) were determined according to the DGF standard methods, Stuttgart 1950-1984, H-III-10 and G-II-6b.
• the resulting oleic acid 2-ethylhexyl ester sulfonate had the following composition: anionic surfactants: 26.3% by weight, unsulfated components: 3.5% by weight, sodium sulfate: 1.1% by weight, water: 69.1% by weight. -%.
• Example 1 Manufacture of sheep clothing leather. Wet blue material was first washed and then retanned. The details of the amounts used and the duration of the process steps are summarized in Table 1. A soft leather with a full, round handle and an even, flowery color was obtained.
• Example 2 Manufacture of furniture leather. Wet blue material was washed, retanned, neutralized, stained and greased. The details of the amounts used and the duration of the process steps are summarized in Table 2. Cloth-soft, chubby, slightly slimy furniture leather was obtained.
• Example 3 Preparation of beef suede. Crust leather was paperback and dyed. The details of the amounts used and the duration of the process steps are summarized in Table 3. A silky suede fiber with brilliant coloring and a beautiful writing effect was obtained.
• Example 4 Manufacture of cowhide leather. Wet blue material was washed, neutralized, washed again and retanned. The details of the amounts used and the duration of the process steps are summarized in Table 4. A very soft leather with good fullness and uniform, brilliant coloring was obtained.

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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)

Applications Claiming Priority (3)

Publications (2)

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• 1994
  • 1994-05-31 DE DE4418942A patent/DE4418942A1/de not_active Withdrawn
• 1995
  • 1995-05-22 WO PCT/EP1995/001941 patent/WO1995033077A1/de active IP Right Grant
  • 1995-05-22 PT PT95920858T patent/PT763139E/pt unknown
  • 1995-05-22 DE DE59509641T patent/DE59509641D1/de not_active Expired - Fee Related
  • 1995-05-22 EP EP95920858A patent/EP0763139B1/de not_active Expired - Lifetime
  • 1995-05-22 ES ES95920858T patent/ES2164768T3/es not_active Expired - Lifetime
  • 1995-05-22 JP JP8500254A patent/JPH10501010A/ja active Pending

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