WO1993020243A1 - Cuir ameliore - Google Patents

Cuir ameliore Download PDF

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Publication number
WO1993020243A1
WO1993020243A1 PCT/EP1993/000711 EP9300711W WO9320243A1 WO 1993020243 A1 WO1993020243 A1 WO 1993020243A1 EP 9300711 W EP9300711 W EP 9300711W WO 9320243 A1 WO9320243 A1 WO 9320243A1
Authority
WO
WIPO (PCT)
Prior art keywords
leather
skins
anhydride
hides
fatty acids
Prior art date
Application number
PCT/EP1993/000711
Other languages
English (en)
Inventor
Giovanni Manzo
Original Assignee
Exxon Chemical Patents Inc.
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 Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Priority to DE69314168T priority Critical patent/DE69314168T2/de
Priority to JP5517045A priority patent/JPH07505184A/ja
Priority to EP93906600A priority patent/EP0632840B1/fr
Publication of WO1993020243A1 publication Critical patent/WO1993020243A1/fr

Links

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

  • Impermeable leather lacking water-repellent properties, will become considerably wet on the surface when in contact with water before inhibiting penetration of the water. Hitherto, water-repellent properties have been obtained by a hydrophobic coating however, the movement of the leather during use, will displace this coating, with consequent loss of the water-repellent properties. For this reason, water-repellent leathers do not respond well to the I.U.P. 10 dynamic impermeability test. Moreover, it is well known that leathers can lose their impermeability or water repellent properties or lubrication when washed with surfactants or solvents.
  • leather is generally treated with a strong acid such as sulphuric acid and then with a metal tanning agent generally based on chromium or aluminium compounds. This tends to result in the leather retaining a positive charge particularly in the bulk of the leather even if the surface is subsequently neutralised.
  • a strong acid such as sulphuric acid
  • a metal tanning agent generally based on chromium or aluminium compounds.
  • United States Patent 3784400 uses amines (such as morpholine) as emulsifiers for the alkyl or alkenyl succinic anhydride.
  • amines such as morpholine
  • the alkyl or alkenyl group contains an average of 12 to 18 carbon atoms whilst in United States Patent 3784400, the alkenyl group contains from 12 to 24 carbon atoms.
  • the materials are applied under acidic conditions to leather without any prior neutralisation.
  • tanned leather is treated with an aqueous emulsion of a mixture of an alkyl or alkenyl carboxylic acid or anhydride or derivative thereof whose alkyl or alkenyl group contains at least 16 carbon atoms from 15% to 60% by weight fatty acids under alkaline conditions of a PH from 9 to 10 and, after treatment such as vegetable or synthetic resins secondary retanning and any colouring, the system is acidified to enable bonding of the acid or anhydride to the leather or the tanning agents contained therein.
  • This process of the invention is not simply an impregnation but a full penetration into the hide followed by a chemical reaction between the dermic material and/or the tanning agent and the carboxylic acid or anhydride.
  • the leather obtained by the process described above is further retanned with metal salts to achieve water-repellent and water proofing properties.
  • the invention provides tanned leather impregnated with a " mixture of a polyalkenyl succinic acid or anhydride or derivative thereof particularly a polyisobutenyl succinic anhydride in which the polyalkenyl group contains at least 25 preferably at least 30 carbon atoms and fatty acids, said mixture containing from 15 to 60% by weight of fatty acids. Also provided is such impregnated leather which has been retanned with the metal salts.
  • the invention provides the use of an emulsion of a mixture of alkyl or alkenyl carboxylic acid or anhydride or derivative thereof in which the alkyl or alkenyl group contains at least 16 carbon atoms and from 15% to 60% by weight based on the weight of the mixture of fatty acids in the treatment of leather under alkaline conditions.
  • the alkyl or alkenyl carboxylic acids or anhydrides used in the present invention are preferably alkyl or alkenyl derivatives of dicarbox lic acids or anhydrides the preferred materials being alkyl or alkenyl succinic acids or anhydrides whose alkyl or alkenyl group contains at least 16 carbon atoms.
  • polypropenyl or polybutenyl succinic acids containing at least 30 especially at least 60 carbon atoms in the polypropenyl or polybutenyl group are particularly useful.
  • the materials may be acids or anhydrides or their derivatives such as the sulphonated derivative thereof.
  • dicarboxylic products it is believed t at once the product has fully penetrated the hide, the subsequent acidification enables one carboxyl group to bond with the metal tanning agents in the leather leaving free carboxyl ⁇ groups. These may partake in subsequent reactions such as final retanning with metal salts which has been found to give such a significant improvement in waterproofing and water repellanc .
  • Saturated and unsaturated monocarboxylic acids may also be used but it is preferred that they be used in combination with an aldehyde such as formaldehyde, acetaldehyde, or glutaraldehyde to enable subsequent Mannich reaction between the naturally occurring amino groups in the leather and the methyl groups of the acid or a double bond in an unsaturated acid, so again providing free carboxyl groups for further reactions after penetration and acidification.
  • an aldehyde such as formaldehyde, acetaldehyde, or glutaraldehyde
  • Suitable fatty acids useful in the mixtures of this invention are mono-carboxylic acids such as stearic, oleic, palmitic acids and tall oil fatty acids or mixtures thereof. Mixtures of mono and di-carboxylic acids may also be used and we have found a mixture of Cg to C19 mono and di-carboxylic acids to be particularly useful.
  • the acid mixtures of this invention are applied to the leather as aqueous emulsions and any suitable non-ionic, cationic or anionic emulsifier may be used.
  • any suitable non-ionic, cationic or anionic emulsifier may be used.
  • emulsifier examples of other emulsifiers are the cationic sulphonates, and the anionic amine sulphonates.
  • fatty acids used in the present invention act also as co-emulsifiers and not only reduce the need for traditional emulsifiers but if used in the proportions of this invention allow a better product penetration which contributes significantly to improve the surface finish of the leather.
  • the polyalkenyl succinic acid or anhydride emulsion is prepared by mixing water, emulsifier (preferably an alkoxy emulsifier) and ammonium hydroxide at typically 60°-80°C for from 5-20 minutes and blending this
  • emulsifier preferably an alkoxy emulsifier
  • ammonium hydroxide typically 60°-80°C for from 5-20 minutes
  • a preferred emulsion contains for 1000 parts by weight of the alkyl or alkenyl carboxylic acid or anhydride or derivative thereof from 150 to 600 parts by weight of fatty acids, from 300 to 1000 parts by weight of water, from 50 to 200 parts by weight of emulsifier and sufficient base, preferably ammonia, to ensure the PH is in the range 9 to 10.
  • the treatment by the aqueous emulsion may be carried out using the typical drumming techniques used for leather treatment.
  • the tanned leather is in a drum in water at about 50°-60°C at a pH from 5-6.
  • the pH in the drum is raised to about 9 to 10 preferably by the addition of aqueous, ammonia although other bases such as amines, inorganic hydroxides, carbonates and bicarbonates may be used or a mixture of them may be used.
  • bases such as amines, inorganic hydroxides, carbonates and bicarbonates may be used or a mixture of them may be used.
  • 5-15 wt% of the formulation of this invention based on the weight of the tanned, shaved skins is used.
  • the secondary retanning is a conventional process to provide reactive fillers to increase the thickness and fullness of the leather.
  • Suitable materials are vegetable tanning (e.g. wattle, chestnust, quebracho) or synthetic retanners or resins.
  • the process of the present invention produces well lubricated leather, furthermore when the polyalkenyl materials containing more than 30 carbon atoms the lubricated leather has notably improved fullness.
  • the well lubricated leather is water absorbing owing to the presence of free carboxylic groups. If a sulphonated carboxylic acid has been used the sulphonic group which is not coupled can also have an influence on the water- absorbing properties of the material.
  • a further final tanning treatment (after dyeing and retanning with synthetic or vegetable tanning or resins) with metal salts such as chromium or aluminium basic salts block these groups and produce leather which, after appropriate washing and drying, is impermeable as well as well lubricated and extremely full.
  • the retanning with chromium or aluminium salts may not, however, impart the ultimate water-repellent characteristics because the treated leather may contain some residual carboxylic acid or carboxylic acid metal salt complex within the body of the leather. These are often bonded to the leather by hydrogen bonding and water repellancy may be further improved by a treatment to destroy the hydrogen bonding which encourages migration to the surface of the leather to impart water repellency. For example treatment with methylene chloride optionally together with water is very effective. Alternatively the leather retanned with metal salts may be treated with a surfactant, followed by contact with a basic ammonia solution for approximately 15 minutes .
  • Treatment of the leather under alkaline conditions enables the use of aqueous emulsions of the acids anhydrides or derivatives of emulsifier:acid ratios of 1:50.
  • Choice of suitable surfactants also makes it possible to operate in baths having the same and even a greater dilution than that usually used in the leather dyeing, re-tanning and oiling process.
  • the invention also enables the production of leathers which are well lubricated, impermeable and water-repellent having improved fullness and touch at low cost, in contrast with existing agents, such as those used to impart impermeability and water-repellent properties to leather, whose cost is often extremely high.
  • the invention enables the production of lubricated, impermeable and water-repellent leathers which do not lose these properties after washing or dry cleaning and ageing.
  • Example 1 uses a polyisobutylene succinic anhydride from Exxon Chemical whose polyisobutylene group contained an average of 96 carbon atoms.
  • Example 1 uses a polyisobutylene succinic anhydride from Exxon Chemical whose polyisobutylene group contained an average of 96 carbon atoms.
  • Chrome leather which had not been neutralized is treated at a pH 9 to 10 in a revolving drum with 200 wt% based on weight of leather of an alkaline solution containing 20- 25g/litre of ammonium hydroxide.
  • the drum is allowed to revolve for 20-30 minutes and then 5 to 15 wt% based on the drum content of the emulsion of the mixture of alkyl succinic acid and fatty acids is added.
  • the drum is allowed to revolve from 40 minutes to 2 hours depending on the thickness of the hides or skins, then the pH is brought to 7-7.5 by the addition of formic acid and the required quantity of dye is added. This is followed by re-tanning with organic compounds and treatment with formic acid until a pH value of 3-3.5 is reached.
  • the bath is discarded and the leather is re-tanned with 8-10% of chromium salt in 80% of water.
  • the drum is allowed to revolve for approximately 40 minutes to 1 hour and 30 minutes depending on the thickness of the hides or skins.
  • Basification is carried out to pH 5 with a dilute solution of sodium bicarbonate.
  • the bath is discarded and the hides or skins are washed continuously for approximately 20 minutes to wash out the water-absorbing substances being present on the surface of the leather.
  • the hides or skins are dried and then re-finished in the usual manner.
  • the wet hides or skins can be treated with a mixture of 10% water and 5% methylene chloride for approximately 20 minutes to further improve impermeability.

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)

Abstract

Produits en cuir bien lubrifiés, imperméables et résistants à l'eau obtenus par l'imprégnation de peaux tannées, dans des conditions alcalines, par une émulsion ou par un mélange d'acides ou anhydrides carboxyliques d'alkyle ou d'alcényle contenant au moins 16 atomes de carbone, et notamment d'acide polyisobutényl-succinique ou de son anhydride contenant au moins 30 atomes de carbone, et d'acides gras selon des quantités prédéterminées; puis par un nouveau tannage à l'aide de solutions basiques ou de ladite émulsion pouvant également contenir des acides gras.
PCT/EP1993/000711 1992-03-27 1993-03-24 Cuir ameliore WO1993020243A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE69314168T DE69314168T2 (de) 1992-03-27 1993-03-24 Verbessertes leder
JP5517045A JPH07505184A (ja) 1992-03-27 1993-03-24 改良なめし革
EP93906600A EP0632840B1 (fr) 1992-03-27 1993-03-24 Cuir ameliore

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB929206791A GB9206791D0 (en) 1992-03-27 1992-03-27 Improved leather
GB9206791.7 1992-03-27

Publications (1)

Publication Number Publication Date
WO1993020243A1 true WO1993020243A1 (fr) 1993-10-14

Family

ID=10713018

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/000711 WO1993020243A1 (fr) 1992-03-27 1993-03-24 Cuir ameliore

Country Status (7)

Country Link
EP (1) EP0632840B1 (fr)
JP (1) JPH07505184A (fr)
AT (1) ATE158617T1 (fr)
CA (1) CA2132834A1 (fr)
DE (1) DE69314168T2 (fr)
GB (1) GB9206791D0 (fr)
WO (1) WO1993020243A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021241528A1 (fr) 2020-05-25 2021-12-02 日産化学株式会社 Bibliotheque codée par adn clivable

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2119083A1 (de) * 1970-05-13 1971-11-25 Pennwalt Corp., Philadelphia, Pa. (V.StA.) Schmiermittel-Zubereitung zur Lederbehandlung
GB1297942A (fr) * 1969-03-04 1972-11-29
US3749669A (en) * 1971-06-21 1973-07-31 Us Agriculture Lubricants for hides and leather
EP0324536A1 (fr) * 1988-01-07 1989-07-19 Exxon Chemical Patents Inc. Cuir aux caractèristiques améliorées

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1297942A (fr) * 1969-03-04 1972-11-29
DE2119083A1 (de) * 1970-05-13 1971-11-25 Pennwalt Corp., Philadelphia, Pa. (V.StA.) Schmiermittel-Zubereitung zur Lederbehandlung
US3749669A (en) * 1971-06-21 1973-07-31 Us Agriculture Lubricants for hides and leather
EP0324536A1 (fr) * 1988-01-07 1989-07-19 Exxon Chemical Patents Inc. Cuir aux caractèristiques améliorées

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021241528A1 (fr) 2020-05-25 2021-12-02 日産化学株式会社 Bibliotheque codée par adn clivable
KR20230015347A (ko) 2020-05-25 2023-01-31 닛산 가가쿠 가부시키가이샤 절단 가능한 dna 코드화 라이브러리

Also Published As

Publication number Publication date
JPH07505184A (ja) 1995-06-08
DE69314168D1 (de) 1997-10-30
CA2132834A1 (fr) 1993-10-14
EP0632840B1 (fr) 1997-09-24
GB9206791D0 (en) 1992-05-13
EP0632840A1 (fr) 1995-01-11
ATE158617T1 (de) 1997-10-15
DE69314168T2 (de) 1998-05-07

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