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

Definitions

• the present invention relates to an improved method for greasing, filling and waterproofing leather and furs and an improved fatliquor for leather and furs.
• aqueous fat emulsions which are generally based on petrochemically produced or natural oils and fats. These are made water-emulsifiable by partial sulfonation or with the help of emulsifiers or solubilizers.
• DE-A 39 09 614 (1) relates to a process for greasing and waterproofing leather and furskin using sulfonated compounds of succinic acid with unsaturated fatty acids or their esters, amides or alkanolamides, for example a reaction product of oleic acid or an oleic acid derivative with maleic anhydride in the presence of a radical initiator, which was then sulfonated with sulfuric acid.
• alkenyl-substituted saturated dibasic acids such as iso-octadecenylsuccinic acid are suitable for softening leather.
• Organic solvents are also used as solubilizers to achieve sufficient solubility or emulsifiability. Since these are generally not bound by the leather, there are ecological burdens, in particular the waste water from residual liquors and the air from evaporation during the drying process.
• the object of the invention was therefore to provide an improved agent for greasing, filling and waterproofing leather and furs, which no longer has the disadvantages of the prior art.
• a process for greasing, filling and waterproofing leather and furs which is characterized in that for this purpose ene adducts of maleic anhydride with unsaturated fatty acids having 12 to 24 carbon atoms, the C 1 -C 20 -alkyl- or C 2 - to C 20 alkenyl esters, their triglycerides, their amides, their mono- or di (C 2 - to C 4 -alkanol) amides, their mono- or dipolyether amides or their polyether esters or partially or completely by reaction with amines or Alcohols derivatized to add amides or esters.
• the ene adducts mentioned are known in principle from (1) and DE-C 27 54 831 (3).
• they are mentioned as intermediates in the production of the sulfated leather greasing agents claimed there, without being recommended as auxiliaries for leather treatment.
• they are claimed as solubilizers for nonionic surfactants in alkaline aqueous solution.
• the ene adducts are prepared in a known manner by thermal addition of maleic anhydride to unsaturated fatty acids or their derivatives, with about 0.4 to 2 mol, preferably 0.7 to 1 mol, of maleic anhydride being added per mole of unsaturated fatty acid, regardless of its double bond number.
• the addition can be carried out, for example, in boiling toluene or in bulk at 100 to 200 ° C., preferably in the presence of catalytic amounts of iodine.
• the unsaturated fatty acids have 12 to 24, preferably 14 to 18 carbon atoms and one or more olefinic double bonds.
• maleic anhydride is preferably added to each double bond, although this would certainly be possible, since the double bond of the fatty acid is not saturated during the addition, but that of the maleic anhydride.
• the first example of unsaturated fatty acids is oleic acid (cis-9,10-octadecenoic acid), furthermore the trans-isomeric elaidic acid, laurolein- (9,10-eicosen-), eruca- (13,14-docosen-) and called the selacholein (15,16-hexadecene) acid.
• Linoleic (9,10-12,13-octadecadiene) and linolenic (9,10-12,13-15,16-octadecatriene) acid are particularly suitable for suitable fatty acids with two or more olefinic double bonds.
• esters of the unsaturated fatty acids e.g. Methyl, ethyl, propyl, butyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, stearyl, hexadecenyl, oleyl, linolyl or linolenyl esters.
• the triglycerides of unsaturated fatty acids can also contain the predominant proportions, i.e. more than 50 mol%, preferably more than 75 mol%, based on the total fatty acids present in the mixture and containing the aforementioned unsaturated fatty acids as esters.
• unsaturated fatty acids i.e. primarily natural fats and in particular oils
• the predominant proportions i.e. more than 50 mol%, preferably more than 75 mol%, based on the total fatty acids present in the mixture and containing the aforementioned unsaturated fatty acids as esters.
• linseed oil olive oil, castor oil, peanut oil, sesame oil, corn oil, sunflower oil, soybean oil, poppy seed oil, cottonseed oil, hemp oil and palm oil
• the latter also contains considerable proportions of esters with wax alcohols, including unsaturated alcohols.
• Particularly suitable fatty acid amides are the compounds unsubstituted on amide nitrogen.
• N-mono- or N, N-diethanolamides or -isopropanolamides can be used as mono- or di- (C 2 -C 4 -alkanol) amides.
• Suitable mono- or dipolyetheramides are, for example, compounds substituted on amide nitrogen by polyoxyethylene groups with a respective degree of ethoxylation of 1 to 30, in particular 2 to 20.
• Suitable polyether esters are unsaturated fatty acids reacted with 1 to 30 mol, in particular 2 to 20 mol, of ethylene oxide.
• the amide or ester derivatives are prepared in a known manner by adding the amine or alcohol to the ene adduct containing anhydride groups at temperatures between usually 20 and 200 ° C., preferably between 50 and 150 ° C.
• a catalyst for example p-toluenesulfonic acid, can be used for the addition.
• Not more than one mole of amine or alcohol is preferably used per mole of anhydride group.
• the addition can take place, for example, in toluene or in bulk, preferably in the same reaction medium as in the preparation of the ene adduct.
• alcohols such as methyl, ethyl, propyl, butyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, stearyl, oleyl alcohol or alkoxylated fatty or oxo alcohols or carbohydrates such as glucose be used.
• Straight-chain or branched C 1 to C 20 alkanols, in particular C 4 to C 18 alkanols, and C 8 to C 18 alkanols reacted with 2 to 20 mol ethylene oxide and / or propylene oxide per mol alkanol are preferred.
• amines which can be used are mono- or di-N-alkylamines such as n-butylamine, 2-ethylhexylamine, morpholine, piperidine or tallow fatty amine or amino acids such as sarcosine, taurine or iminodiacetic acid or amino alcohols such as iminodiethanol or hydroxyethylamine.
• Saturated or unsaturated secondary or in particular primary aliphatic amines having a total of 1 to 30, in particular 4 to 18, carbon atoms are preferred.
• ene adducts of maleic anhydride are added to unsaturated fatty acids having 14 to 18 carbon atoms, their C 14 to C 18 alkenyl esters or their triglycerides, but in particular to oleic acid, oleic acid oleate or a triglyceride which is more than 50 mol% unsaturated fatty acids with 14 to 18 carbon atoms, based on the total fatty acids present in the mixture, as an ester, or partially or completely by reaction with aliphatic amines with a total of 1 to 30 carbon atoms or with C 1 - to C 20 alkanols or en-adducts derivatized with alkoxylated alcohols to form amides or esters.
• the anhydride groups still present in the attached maleic anhydride hydrolyze to carboxylate groups, together with the original carboxyl groups, which are also still in salt form the unsaturated fatty acids ensure the solubility of the products to be used according to the invention.
• the products described also have a hydrophobic effect, i.e. Leather and furs treated with them become water-repellent and only absorb small amounts of water.
• aqueous emulsions of the ene adducts to be used according to the invention contain no additional emulsifiers. It is known that leather and furs which have been treated with products containing emulsifiers have to undergo complex processes after treatment with these agents, e.g. an aftertreatment with polyvalent metal salts, to make the emulsifiers in the leather or in the fur skins ineffective, which cause a negative effect on the hydrophobizing effect of these products.
• the present invention also relates to fatliquoring, filling and waterproofing agents for leather and furs, which contain the described ene adducts of maleic anhydride with unsaturated fatty acids or their derivatives.
• the leather treatment compositions according to the invention are suitable for the treatment of all customary tanned hides.
• the tanned hides are usually deacidified before treatment. They may have been stained before treatment. However, coloring can also only be carried out after the treatment according to the invention.
• the tanned skins are expediently mixed with the aqueous emulsions of the ene adducts in an aqueous liquor, which can be obtained by diluting the emulsions with water, at pH values from 4 to 10, preferably from 5 to 8, and temperatures from 20 to 60 ° C. , preferably 30 to 50 ° C, treated for a period of 0.1 to 5 hours, in particular 0.5 to 2 hours. This treatment takes place, for example, by drumming in a barrel.
• the amount of emulsion required, based on the shaved weight of the leather or the wet weight of the fur skins, is 0.1 to 30% by weight, preferably 1 to 20% by weight.
• the fleet length i.e. the percentage weight ratio of the treatment liquor to the goods, based on the shaved weight of the leather or the wet weight of the fur skins, is usually 10 to 1000%, preferably 30 to 150% for leather and 50 to 500% for fur skins.
• the pH of the treatment liquor is adjusted by adding acids, preferably organic acids, e.g. Formic acid, adjusted to a pH of 3 to 5, preferably 3.5 to 4.
• acids preferably organic acids, e.g. Formic acid, adjusted to a pH of 3 to 5, preferably 3.5 to 4.
• treatment with the aqueous emulsion of the ene adducts can take place before or after the retanning step.
• Example 2 Analogously to Example 1, 348 g of ester oil (hydrogenation iodine number 112.6) were reacted with 166 g of maleic anhydride. 13 g of unreacted maleic anhydride and 535 g of product were obtained.
• the leather obtained was very soft, supple, well filled and evenly colored.
• the leather thus obtained was very soft and easy to grip.
• Chrome-tanned cowhide with a fold thickness of 1.8 mm which has been deacidified to a pH of 5.0 and dyed with 0.7% by weight of a conventional anionic aniline dye was drummed with 15% active substance of the emulsion from Example 3, based on the shaved weight, for 30 minutes at 40 ° C. in a tanning drum and then treated with 3% of a conventional synthetic tanning agent for one hour. Then the leather was brought to a pH of 3.6 with formic acid and finished as usual.
• the leather thus obtained felt pleasantly soft and easy to grip.
• Example 4 The emulsion from Example 4 was used analogously to the procedure given in Example 9.
• the leather thus obtained showed soft and round grip properties.
• Example 5 The emulsion from Example 5 was used analogously to the procedure given in Example 9.
• the leather thus obtained was soft and pleasant to the touch.
• Example 6 The emulsion from Example 6 was used analogously to the procedure given in Example 9.
• the leather obtained was soft with a slightly slimy feel. No water penetration occurred in the penetrometer within 12 hours at 10% compression.
• Example 7 The emulsion from Example 7 was used analogously to the procedure given in Example 9.
• the leather thus obtained was pleasantly soft and easy to grip.
• Example 8 The emulsion from Example 8 was used analogously to the procedure given in Example 9.
• the leather obtained has a pleasantly soft feel and an even color.

Landscapes

• 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)

Applications Claiming Priority (3)

Publications (2)

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Family Applications (1)

Country Status (7)

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• 1992
  • 1992-03-21 DE DE4209243A patent/DE4209243A1/de not_active Withdrawn
• 1993
  • 1993-03-10 JP JP5516216A patent/JPH06507937A/ja active Pending
  • 1993-03-10 WO PCT/EP1993/000543 patent/WO1993019210A1/de active IP Right Grant
  • 1993-03-10 AT AT93905332T patent/ATE159987T1/de active
  • 1993-03-10 EP EP93905332A patent/EP0585431B1/de not_active Expired - Lifetime
  • 1993-03-10 AU AU36321/93A patent/AU661125B2/en not_active Ceased
  • 1993-03-10 ES ES93905332T patent/ES2108265T3/es not_active Expired - Lifetime
  • 1993-03-10 DE DE59307630T patent/DE59307630D1/de not_active Expired - Lifetime

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