US3485573A - Fat liquoring agent consisting of an epoxy compound and an acid containing ester - Google Patents

Fat liquoring agent consisting of an epoxy compound and an acid containing ester Download PDF

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Publication number
US3485573A
US3485573A US548058A US3485573DA US3485573A US 3485573 A US3485573 A US 3485573A US 548058 A US548058 A US 548058A US 3485573D A US3485573D A US 3485573DA US 3485573 A US3485573 A US 3485573A
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US
United States
Prior art keywords
leather
acid
oil
fat
epoxide
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Expired - Lifetime
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US548058A
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English (en)
Inventor
Rudi Heyden
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Dr Th Boehme KG Chemie Fabrik GmbH and Co
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Dr Th Boehme KG Chemie Fabrik GmbH and Co
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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

  • This invention relates to a fatting agent for leather and to a process for applying same.
  • Fatting agents are introduced onto the fibers of leather during a wet process so that drying may be effected without cohesion of the fibers of leather during drying. Preventing such a cohesion prevents the fibers from sticking together and gives more life to the leather, since the leather fibers may move freely back and forth against each other. When the leather is dry, friction is also prevented by the fatting agent, permanently preventing adhesion of the fibers.
  • natural fatty substances have been used as fatting agents in the preparation of leather to achieve the necessary softness and suppleness.
  • natural fats and oils include for example, lard oil, sheep oil, neatsfoot oil, corn oil, cottonseed oil, olive oil, castor oil, cod oil, sperm oil and others.
  • the substances are generally applied as an oil in water emulsion and are present in the pores of the leather essentially in unbonded form. Consequently,
  • Another object of this invention is to provide a fatting agent that adheres to the leather fiber to provide a pr duct having superior softness and suppleness.
  • a further object of this invention is to provide a process for fatting leather using a novel fatting agent.
  • Another object of this invention is to provide a fatting agent for leather consisting essentially of a mixture of: (a) an epoxidation product of a fatty substance, said product containing more than one epoxide group in the molecule, and (b) a compound containing at least two free acid groups and at least one high molecular weight radical having from about *8 to 36 carbon atoms.
  • the subject matter of the present invention is a fatting agent consisting essentially of a combination of: (a) epoxidation products of fatty substances, said products containing more than one epoxide group in the molecule, and (b) compounds containing at least two free acid groups as well as one or more high-molecular Weight radicals having from 8 to 36, and preferably 12 to 18, carbon atoms. Components (a) and (b) must be miscible with each other.
  • the epoxidized fatty substances of group (a) are primarily obtained by epoxidation of natural unsaturated fats and oils, such as sperm .oil, soybean oil, olive oil, codliver oil, tallow, lard oil,
  • glycerin is common to the structure of all fatty oils, the difference among them exists in the chemical nature of the fatty acids which combine with glycerin. Generally, the above natural fats and oils contain unsaturated fatty acids having from 8 to 20 carbon atoms.
  • the corresponding epoxidation products of synthetic diand poly-esters of polyhydric alcohols containing 2 to 6 carbon atoms such as glycols, glycerin, polyglycols, sugar alcohols, pentaerythrite and the like, with unsaturated fatty acids containing 8 to 20 carbon atoms may be used.
  • the epoxidation products of diand poly-esters of polycarboxyl acids having from 2 to 8 carbon atoms such as oxalic acids, maleic acid, citric acid and phthalic acid, with unsaturated fatty alcohols having from 8 to 20 carbon atoms may also be used.
  • the unsaturated fatty acids obtained from natural fats such as oleic acid, linoleic acid, linolenic acid and ricinenic acid (9,1l-linoleic acid), or mixtures of these fatty acids obtained from natural fats, as well as the unsaturated fatty alcohols prepared therefrom in known fashion may be used.
  • the epoxidation of the above fatty substances is accomplished in known fashion, for instance, with peracids, such as performic acid, peracetic acid, and the like.
  • peracids such as performic acid, peracetic acid, and the like.
  • the double bonds present in the starting material are substantially transformed into epoxide groups.
  • those products are suitable which con tain, on the average, more than one and preferably more than 1.5 epoxide groups per molecule.
  • the fatty substance may have up to 8.5 percent by weight of epoxide oxygen content.
  • the compounds defined as (a) are well known in the art and hence no claim is made specifically thereto.
  • the high molecular Weight compounds of group (b) which contain at least two free acid groups in the molecule are derived from aliphatic, aliphatic-cycloaliphatic, or aliphatic-aromatic compounds which have at least one alkyl radical of 8 to 36, and preferably 12 to 18 carbon atoms.
  • the radicals may be branched chain or unsaturated radicals and may be substituted with customary substituents, such as hydroxyl groups.
  • the acid groups are primarily carboxyl groups. These carboxyl compounds may, however, be partially replaced by those organic phosphoric acid derivatives which contain phosphoric acid ester or phosphonic acid groups in the molecule. The portion of the phosphoric acid derivatives in the total amount of compounds containing the acid groups should not exceed 10% by weight.
  • Examples of compounds of group (b) containing acid groups are the partial esters of triand higher polycarboxylic acids containing two or more free acid groups, especially of citric acid, formed with higher molecular weight alcohols, such as mono-oleyl citric acid ester, mono-2-octyldodecyl citric acid ester, mono-isotridecyl citric acid ester, and the like.
  • the triand higher polycarboxylic acids useful for purposes of this invention may have from 6 to 12 carbon atoms.
  • the higher molecular weight alcohols may have from 8 to 20 carbon atoms.
  • dior higher polycarboxylic acids substituted with high molecular weight hydrocarbon radicals such as N-dodecylasparaginic acid, N-oleyl-citric acid mono-amide, octyladipic acid, oleylmalonic acid, and the like.
  • the dior higher polycarboxylic acids may have from 8 to 36 carbon atoms.
  • suitable organic phosphoric acid derivatives are the mono-alkyl esters of orthophosphoric acid formed with high molecular weight alcohols having from 8 to 20 carbon atoms, such as isotridecyl alcohol, oleyl alcohol, etc.
  • Suitable mixtures of compounds containing both carboxyl groups and phosphoric acid groups consist, for example, of citric acid monooleyl ester, and dodecyl alcohol-phosphoric acid monoester.
  • the fixation of the mixtures consisting of components (a) and (b) in the leather is based upon the fact that the epoxidized fatty substances enter into a reaction with the compounds containing the acid groups to form more or less high polymeric polyester-type products.
  • the reaction proceeds slowly at room temperature, but it may be substantially accelerated by the application of elevated temperatures as well as with the aid of catalysts, such as amines.
  • the fatting agent mixtures are generally employed as aqueous 10 to 20% emulsions, possibly with the addition of emulsifying agents, or as organic solutions.
  • the agents thoroughly penetrate into the leather, where the reaction which forms the polyester compound takes place.
  • the mixtures are, as a rule, not storable over long periods of time because the reaction proceeds even at room temperature, and they must therefore generally be prepared just prior to their employment by admixing the components.
  • the mixture ratio between the epoxide fatty substance and the compound containing the acid groups is normally selected so that as complete a reaction as possible may take place between the reacting groups.
  • good results are also obtained, especially an increase of the dynamic water-resistance of the leather, when one deviates from equivalent ratios, as where an excess of free acid groups may be present.
  • the ratio of the number of epoxide groups to the number of acid groups should preferably be from about 1:1 to 1:2.
  • the fat content of the leather determined by solvent extraction, was 15.4%, and after heating for hours at 80 to 90 C. it was 5.9%.
  • EXAMPLE II 'A chrome-tanned leather was neutralized in customary fashion with 1% ammonium bicarbonate and was then fat-liquored at 60 C. with 11% pure fat in 200% solution, based upon the shaved weight of the leather. After conclusion of the fatting treatment, the leather was acidified with 0.5% formic acid. The fat-liquoring so ution consisted of an emulsion c mposed of the following mixture:
  • EXAMPLE III A leather prepared as in Example II was fat-liquored with 5% pure fat in 200% solution.
  • the fat-liquoring oil had the following composition:
  • Citric acid mono-oleyl ester 41.0 Epoxidized fishtrain oil, epoxide oxygen content 5.9% 32.0 Fatty alcohol (C -C phosphoric acid monoester 3.0 Castor oil, sulfated, 30% 1.5 Concentrated ammonia solution 5.5
  • the air-dried leather had an extractable fat content of 8.9% After heating at 90 C. for 12 hours the extractable fat content was reduced to 2.9%.
  • EXAMPLE V A fatting agent mixture of 49.0 parts by weight of monocitric acid ester of 2-octyl-dodecanol-l and 41.0 parts by weight of epoxide soybean oil (epoxide oxygen content 6.1%) was admixed with 3 parts by weight of the phosphoric acid mono-ester of the fatty alcohol (C C monoglycol ether, and 7 parts by weight of concentrated ammonia.
  • a chrome-tanned calf leather was first neutralized, then fat-liquored with 6% pure fat in 200% solution at 60 C. and finally acidified with 0.5% formic acid.
  • EXAMPLE VI A mixture of 11 parts by weight of citric acid monooleyl ester and 8.8 parts by weight of epoxide soybean oil (epoxide oxygen content 6.1%) was admixed with 0.65 part by weight of concentrated ammonia solution.
  • a leather tanned in customary fashion with a chrome tanning agent was fat-liquored with 6% of the above mixture in 200% of solution at 60 C. The mixture was satisfactorily emulsifiable in water. Immediately after drying, 9.8% of fatting components could be extracted from the leather with methylene chloride. After a storage period of 8 weeks the content of extractable fat was reduced to 2.8% without changing the appearance and feel of the leather.
  • a leather prepared as in Example II was fat-liquored for one hour at 60 C. in 8% pure fat in 200% solution, based upon the shaved weight of the leather.
  • the fatliquoring solution was prepared by diluting the following emulsion:
  • Citric acid mono-oleyl ester 31.8 Epoxide linseed oil, epoxide oxygen content 8.5% 37.5 Water 29.2 Ammonia, 25% 1.5
  • the air-dried leather immediately after the fat-liquoring treatment had an extractable fat content of 9.6%, which was reduced to 4.0% after heating the leather at 50 C. for 24 hours. After a storage period of 8 weeks without add iytional heating, the content of extractable fat was 3.3 o.
  • a process for fatting leather which comprises immersing leather into a fatting agent consisting essentially of a mixture of:
  • an ester containing at least two free carboxylic acid groups, of an unsubstituted, aliphatic polycarboxylic acid containing from 6 to 36 carbon atoms and an unsubstituted aliphatic alcohol containing from 8 to 20 carbon atoms, ratio of the number of epoxide groups in component (a) to the number of acid groups in component (b) is in the range of 1:1 to 1:2; and thereafter removing said leather from said fatting agent.
  • component (b) is a mono-ester of a fatty alcohol with citric acid.
  • Process for fatting leather which comprises immersing leather into a fatting agent consisting essentially of a mixture of:
  • component (b) an ester, containing at least two free carboxylic acid groups, of an unsubstituted aliphatic polycarboxylic acid containing from 6 to 12 carbon atoms, and an unsubstituted aliphatic alcohol containing from 8 to 20 carbon atoms, ratio of the number of epoxide groups in component (a) to the number of acid groups in component (b) is in the range of 1:1 to 1:2; removing said leather from said fatting agent; and curing said leather whereby components (a) and (-b) form a polymeric product.

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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)
US548058A 1965-05-20 1966-05-06 Fat liquoring agent consisting of an epoxy compound and an acid containing ester Expired - Lifetime US3485573A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEB0082021 1965-05-20

Publications (1)

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US3485573A true US3485573A (en) 1969-12-23

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Country Status (10)

Country Link
US (1) US3485573A (fr)
AT (1) AT262491B (fr)
BE (1) BE681325A (fr)
CH (1) CH467863A (fr)
DE (1) DE1494819A1 (fr)
ES (1) ES326906A1 (fr)
FI (1) FI43329C (fr)
FR (1) FR1480573A (fr)
GB (1) GB1138146A (fr)
NL (1) NL6605446A (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957426A (en) * 1973-03-08 1976-05-18 Henkel & Cie G.M.B.H. Fatty acid ester mixtures liquid at low temperatures and process
DE2622363A1 (de) * 1975-05-20 1976-12-02 Matsushita Electric Ind Co Ltd Mikrowellenofen mit tuerabschirmung
US5653789A (en) * 1994-05-23 1997-08-05 Permagrain Products, Inc. Water base conditioner for acrylic wood flooring
US5853427A (en) * 1995-07-12 1998-12-29 The United States Of America As Represented By The Secretary Of Agriculture Use of polymerizable oil for leather fatliquor
US5880242A (en) * 1996-03-04 1999-03-09 Baxter International Inc. Nonpolymeric epoxy compounds for cross linking biological tissue and bioprosthetic grafts prepared thereby
US6106555A (en) * 1998-12-15 2000-08-22 Av Healing Llc Method for tissue fixation
US20040152864A1 (en) * 2000-05-24 2004-08-05 Milko Ess Composition based on renewable raw materials
US20060090393A1 (en) * 2004-10-29 2006-05-04 Rowland Robert G Epoxidized ester additives for reducing lead corrosion in lubricants and fuels
US10323373B2 (en) * 2016-02-15 2019-06-18 Walter J. Boasso Method and apparatus for erosion control and environmental protection
US20230021884A1 (en) * 2019-11-28 2023-01-26 Orineo BV Cured epoxy resin coating

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2123073A1 (en) * 1970-11-13 1972-09-08 Henry Jacques Transfer printed leather - by hot pressing tanned leather against a support printed with sublimable dyes

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2822235A (en) * 1953-11-09 1958-02-04 Bohme Fettchemie Gmbh Method of leather-fatting
US2872428A (en) * 1955-01-31 1959-02-03 Shell Dev Polyepoxide emulsions and method of treating textiles therewith
US3050480A (en) * 1958-01-20 1962-08-21 Archer Daniels Midland Co Protective film forming compositions and resultant films
US3101238A (en) * 1960-06-11 1963-08-20 Bohme Fettchemie Gmbh Fat liquoring with reaction product of epoxidized esters and polybasic inorganic acids
US3291557A (en) * 1963-01-07 1966-12-13 Battelle Development Corp Alkyl dicarboxylic acid treatment of leather

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2822235A (en) * 1953-11-09 1958-02-04 Bohme Fettchemie Gmbh Method of leather-fatting
US2872428A (en) * 1955-01-31 1959-02-03 Shell Dev Polyepoxide emulsions and method of treating textiles therewith
US3050480A (en) * 1958-01-20 1962-08-21 Archer Daniels Midland Co Protective film forming compositions and resultant films
US3101238A (en) * 1960-06-11 1963-08-20 Bohme Fettchemie Gmbh Fat liquoring with reaction product of epoxidized esters and polybasic inorganic acids
US3291557A (en) * 1963-01-07 1966-12-13 Battelle Development Corp Alkyl dicarboxylic acid treatment of leather

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957426A (en) * 1973-03-08 1976-05-18 Henkel & Cie G.M.B.H. Fatty acid ester mixtures liquid at low temperatures and process
DE2622363A1 (de) * 1975-05-20 1976-12-02 Matsushita Electric Ind Co Ltd Mikrowellenofen mit tuerabschirmung
US5653789A (en) * 1994-05-23 1997-08-05 Permagrain Products, Inc. Water base conditioner for acrylic wood flooring
US5853427A (en) * 1995-07-12 1998-12-29 The United States Of America As Represented By The Secretary Of Agriculture Use of polymerizable oil for leather fatliquor
US5880242A (en) * 1996-03-04 1999-03-09 Baxter International Inc. Nonpolymeric epoxy compounds for cross linking biological tissue and bioprosthetic grafts prepared thereby
US6106555A (en) * 1998-12-15 2000-08-22 Av Healing Llc Method for tissue fixation
US6231614B1 (en) 1998-12-15 2001-05-15 Av Healing Llc Method for tissue fixation
US20040152864A1 (en) * 2000-05-24 2004-08-05 Milko Ess Composition based on renewable raw materials
US6946541B2 (en) * 2000-05-24 2005-09-20 Dlw Aktiengesellschaft Composition based on renewable raw materials
US20060090393A1 (en) * 2004-10-29 2006-05-04 Rowland Robert G Epoxidized ester additives for reducing lead corrosion in lubricants and fuels
WO2006049687A1 (fr) * 2004-10-29 2006-05-11 Chemtura Corporation Additifs d'esters epoxydes pour reduire la corrosion par le plomb dans les lubrifiants et les carburants
US10323373B2 (en) * 2016-02-15 2019-06-18 Walter J. Boasso Method and apparatus for erosion control and environmental protection
US20230021884A1 (en) * 2019-11-28 2023-01-26 Orineo BV Cured epoxy resin coating

Also Published As

Publication number Publication date
CH467863A (de) 1969-01-31
ES326906A1 (es) 1967-07-01
BE681325A (fr) 1966-11-21
FI43329C (fi) 1971-03-10
NL6605446A (fr) 1966-11-21
FR1480573A (fr) 1967-05-12
AT262491B (de) 1968-06-10
DE1494819A1 (de) 1969-12-04
FI43329B (fr) 1970-11-30
GB1138146A (en) 1968-12-27

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