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
• • 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
  • C14C3/00—Tanning; Compositions for tanning
  • C14C3/02—Chemical tanning
  • C14C3/08—Chemical tanning by organic agents

Definitions

• the oiling gives leather some of its most important properties for use.
• the following are particularly strongly influenced: elasticity, hardness, toughness, extensibility, absorbency or repellency to water and air permeability.
• the oxidation of the oils used should be as complete as possible, with the duration of the oxidation taking as short a period as possible.
• metal catalysts such as cobalt naphthenate, zinc sulfate, aluminum sulfate or sodium oxalate. Despite the use of catalysts, the oxidation often took several days.
• the leather greasing agents obtained by the oxysulfitation process often showed disadvantageous properties, such as excessive viscosity, especially at low temperatures, unpleasant fish-like odor and insufficient chromium stability.
• Inorganic peroxides and also hydrogen peroxide (DD-A-21 46 28) were usually used to reduce the odor nuisance.
• the object of the present invention was to provide a process for the preparation of greasing compositions based on oxysulfited oils of animal and / or vegetable origin, which requires shorter oxidation times in comparison to known oxysulfitating processes and the use of metal catalysts and odor-reducing substances, such as Peroxides are not mandatory.
• a further object of the invention was to provide compositions based on oxysulfited oils of animal and / or vegetable origin which have improved properties in use compared to the known fatty compositions, such as low viscosity, in particular at lower temperatures, and low odor, better penetration and improved stability against oxidizing compounds.
• the invention also relates to greasing compositions obtainable by a process which comprises the above-mentioned measures.
• compositions serve compositions based on fatty substances of animal origin and / or vegetable origin (component a).
• fatty substances of animal origin are fish oil, oil and its transformation products, claw-claw oil, sperm oil, egg oils and tallow fat. Fish oil and cattle claw oil are preferred.
• fatty substances of vegetable origin can also be used as starting materials.
• fatty substances of vegetable origin are castor oil, rapeseed oil, olive oil, soybean oil, sunflower oil, palm oil, peanut oil, cotton oil and linseed oil. Rapeseed oil and sunflower oil are preferred.
• the fatty substances of animal and vegetable origin mentioned can be used as individual substances or mixtures in the process according to the invention.
• fatty substances of animal or vegetable origin are used as starting materials for the production of the fatty compositions according to the invention, their proportion is 70-99% by weight, based on the total weight of the mixture. If fatty substances of animal and vegetable origin are used, the starting materials have a composition in a ratio between 30 to 99.9% by weight fatty substances of animal origin and 70 to 0.1% by weight fatty substances of vegetable origin, based on the total weight of fatty substances used .
• a preferred composition consists of approximately equal parts of fish oil, claw oil and rapeseed oil.
• component b which differs from the compounds of component a) distinguish and in which R 1 , R 2 , R 3 are, independently of one another, straight-chain or branched, optionally substituted C 1 -C 24 -alkyl radicals, preferably straight-chain, optionally substituted C 16 -C 20 -alkyl radicals, R 4 is hydrogen or a straight-chain or branched, optionally substituted C 1 -C 6 alkyl, m is an integer greater than zero, preferably 1 to 5, particularly preferably 1 and n is an integer greater than zero, preferably 1 to 20.
• Suitable substituents are, for example, OH, OR, NH 2 , NHR 1 , NHR 1 2 , halogen.
• Compounds of the formula II are preferred used as component b), which differ from the compounds of component a) and in which R 1 , R 2 , R 3 , R 4 , m and n have the meaning given above.
• R 5 - COO - R 4 are compounds of the formula III
• R 5 is a straight-chain or branched, optionally OH-substituted C 9 -C 24 alkyl, C 9 -C 24 alkenyl or C 9 -C 24 -alkdienyl radical and R 4 has the meaning given above.
• These compounds of the formula III are optionally present in an amount of up to 30% by weight, based on the total weight of the mixture.
• components b) and c) find lauric acid, palmitic acid, stearic acid, margaric acid, 10-methylstearic acid, oleic acid, linoleic acid, conjugated linoleic acid, linolenic acid and their esters.
• the compounds of the formulas I, II and optionally III can be used as individual substances or in the form of mixtures of two or more individual substances.
• Additives for controlling the final setting can be added to the compositions according to the invention, e.g. Alkanolamines, such as diethanolamine for an optimal pH, hydrocarbons, such as paraffin oil, for the desired viscosity, low-molecular mineral oil or synthetic oils, based on chlorinated or otherwise modified paraffin derivatives, and plasticizers, such as glycerin.
• Alkanolamines such as diethanolamine for an optimal pH
• hydrocarbons such as paraffin oil
• plasticizers such as glycerin.
• additives are preferably added after the greasing compositions have been completed.
• the starting materials located in a suitable reactor are subjected to an oxidation at a temperature above 40 ° C., preferably in the range from 40 to 90 ° C., particularly preferably 50 to 80 ° C.
• the oxidation is preferably carried out by introducing a moderate air flow into the composition at a rate of 200 to 400 l / h.
• the end point of the oxidation is indicated by the sufficient sulfitability of the oxidized fat.
• a sample is taken from the reaction mixture during the oxidation and sulfited as described below.
• Sufficient sulfitability is understood to mean that when this oxisulfited sample, preferably 10% by weight in water, is introduced, a fine emulsion is formed which is stable over a period of at least one day at room temperature and has a chromium stability of at least 5 hours . It has been shown that the end point of the oxidation and thus these properties are generally reached 10 to 30 hours earlier than in the known processes.
• the oxidized fatty substances can be reacted with a 10 to 40% by weight, preferably 20 to 30% by weight, aqueous solution of a strong base, such as alkali metal hydroxide.
• a strong base such as alkali metal hydroxide.
• the solution of a sulfitizing agent is added to the oxidized starting materials.
• a sulfitizing agent find aqueous solutions of sodium pyrosulfite, sodium bisulfite or sulfur trioxide.
• concentration of the aqueous solutions is in the range from 5 to 50% by weight, preferably 20 to 40% by weight.
• the reaction mixture is heated.
• the reaction mixture is usually heated to the boiling point.
• the reaction mixture is heated until a sample taken meets the desired requirements with regard to appearance, emulsifiability in water and resistance to electrolytes, in particular chromium.
• the sample should be clear when it is removed, i.e. be transparent and without discoloration.
• the sample With regard to the emulsifiability in water, the sample should form a stable, finely divided emulsion. These requirements are assessed by just looking at them.
• the chromium stability of the sample should be given over a period of more than 5 hours, preferably at least 10 hours.
• the chromium stability of the oxysulfited fatty substances is tested as follows. 5 ml of the oxysulfited sample are dispersed in 90 ml of distilled water in a calibrated 100 ml measuring cylinder. 5 ml of an aqueous chromium sulfate solution are added to this dispersion with vigorous shaking.
• the chromium sulfate solution consists of a solution of 56 g of basic chromium sulfate of the formula Cr (OH) SO 4 ⁇ nH 2 O with 25% by weight Cr 2 O 3 . The time until phase separation occurs is the measure of the chromium stability.
• the greasing compositions according to the invention are suitable as well emulsifiable electrolyte-resistant greasing agents for the greasing of demanding fur wild garments, clothing, velor, furniture, gloves and fine upper leather and are preferably used for pre-greasing and greasing after washing.
• the greased leathers have a good grip and fullness with tight scars.
• the greasing compositions according to the invention are preferably suitable as leather greasing agents. It has been shown that the products penetrate the leather well and give it a soft, light but full feel.
• 323 g of fish oil, 337 g of claw oil, 300 g of rapeseed oil and 40 g of ®Prifac acid 8968 (manufacturer: Unichema, Chemie GmbH, DE) at 70 ° C with atmospheric oxygen (speed: 340 l / h) are in a 2 l reactor. oxidized. After 40 hours the mixture has a viscosity of 3 minutes 30 seconds, measured with a "Ford cup" No. 2 at 27 ° C. After the oxidation has ended, 25.6 g of a 30% strength by weight aqueous NaOH solution are added at a temperature of 40 ° C. with stirring. The solution is stirred for 30 minutes at the temperature which arises due to the occurrence of heat.
• Example 1 323 g of fish oil, 337 g of claw oil and 300 g of rapeseed oil and 40 g of ®Prifac acid 8961 are reacted analogously to Example 1. After 60 hours, the mixture has a viscosity of 6 minutes 10 seconds, measured using a "Ford cup" No. 2 at 27 ° C. The sulfitation takes place analogously to Example 1. The viscosity of the end product is 18 minutes 25 seconds, measured with a "Ford cup" No. 2 at 27 ° C. Chromium is stable over a period of more than 5 hours.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Treatment And Processing Of Natural Fur Or Leather (AREA)
• Glass Compositions (AREA)
• Polishing Bodies And Polishing Tools (AREA)
• Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
• Lubricants (AREA)
• Fats And Perfumes (AREA)

Applications Claiming Priority (2)

Publications (2)

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• 1993
  • 1993-03-31 HR HR930646A patent/HRP930646A2/hr not_active Application Discontinuation
  • 1993-04-01 ES ES93105420T patent/ES2110017T3/es not_active Expired - Lifetime
  • 1993-04-01 DE DE59307407T patent/DE59307407D1/de not_active Expired - Fee Related
  • 1993-04-01 EP EP93105420A patent/EP0564980B1/de not_active Expired - Lifetime
  • 1993-04-07 BR BR9301466A patent/BR9301466A/pt not_active Application Discontinuation
  • 1993-04-08 TR TR93/0283A patent/TR26705A/xx unknown
  • 1993-04-09 KR KR1019930005926A patent/KR930021798A/ko not_active Application Discontinuation
  • 1993-04-09 SI SI9300189A patent/SI9300189A/sl unknown
  • 1993-04-09 JP JP5083531A patent/JPH06128600A/ja not_active Withdrawn
  • 1993-04-09 TW TW082102652A patent/TW227018B/zh active

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