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EP0632840B1 - Verbessertes leder - Google Patents

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Publication number
EP0632840B1
EP0632840B1 EP93906600A EP93906600A EP0632840B1 EP 0632840 B1 EP0632840 B1 EP 0632840B1 EP 93906600 A EP93906600 A EP 93906600A EP 93906600 A EP93906600 A EP 93906600A EP 0632840 B1 EP0632840 B1 EP 0632840B1
Authority
EP
European Patent Office
Prior art keywords
leather
skins
hides
mixture
water
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP93906600A
Other languages
English (en)
French (fr)
Other versions
EP0632840A1 (de
Inventor
Giovanni Manzo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Callaway Chemical Corp
Original Assignee
Callaway Chemical Corp
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Filing date
Publication date
Application filed by Callaway Chemical Corp filed Critical Callaway Chemical Corp
Publication of EP0632840A1 publication Critical patent/EP0632840A1/de
Application granted granted Critical
Publication of EP0632840B1 publication Critical patent/EP0632840B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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

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.
  • 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.
  • EP-A-0 324 5366 if tanned leather is treated with an emulsion of an organic carboxylic acid or anhydride or derivative thereof under alkaline conditions so that reaction of the carboxylic acid or anhydride and the metal ions in the tanned leather is impeded there is greater penetration into the leather by the product. Subsequent acidification ensures an effective bond between the acid and the leather resulting in a significant improvement in the lubrication and fullness of the leather.
  • EP-A-0 324 5366 In European Patent Application 893000380.0 (EP-A-0 324 536) we also described the treatment of leather with blends of the alkyl or alkenyl succinic anhydride and fatty acids.
  • the ratio of the alkyl or alkenyl succinic anhydride to the fatty acids is important and should be higher than that disclosed in EP 89300038.0 (EP-A-0 324 536).
  • EP 89300038.0 EP-A-0 324 536
  • EP-A-0 324 536 permits a reduction in the amount of emulsifier, which leads to improved water repellancy of the leather.
  • the use of higher amounts of fatty acids can also overcome some surface cracking problems particularly with thick leather.
  • 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 dicarboxylic 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.
  • the materials may be acids or anhydrides or their derivatives such as the sulphonated derivative thereof.
  • 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
  • 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.
  • glutaraldehyde is another preferred 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 emulsion with a component obtained by mixing water, fatty acids and ammonium typically at 40°C for from 5-20 minutes.
  • 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 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.
  • 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)

Claims (8)

  1. Verfahren, umfassend das Behandeln von gegerbten Fellen oder Häuten mit einer wäßrigen Emulsion aus einem Gemisch aus (a) einer Alkyl- oder Alkenylcarbonsäure oder einem Anhydrid oder Derivat davon, das mindestens 25 Kohlenstoffatome in der Alkyl- oder Alkenylgruppe enthält, und (b) aus mehr als 23,08 % bis zu 60 Gew.-% Fettsäuren, bezogen auf das Gewicht des Gemisches von (a) und (b), wobei die Behandlung bei einem pH-Wert von 9 bis 10 durchgeführt wird und danach die behandelten Felle oder Häute angesäuert werden, worin die Fettsäure aus Stearin-, Olein- und Palmitinsäuren ausgewählt wird oder ein Gemisch von C6-C19 Mono- und Dicarbonsäuren ist.
  2. Verfahren nach Anspruch 1, worin die wäßrige Emulsion Wasser, die Carbonsäure, ein Anhydrid oder Derivat davon, die Fettsäuren und einen Emulgator umfaßt.
  3. Verfahren nach einem der Ansprüche 1 oder 2, worin die behandelten Felle oder Häute mit Metallsalzen nachgegerbt werden, um freie Carbonsäuregruppen oder Gruppen von Derivaten davon, die bei der Behandlung verwendet werden, als auch die Farbstoffe und die organischen Nachgerbungsmittel zu fixieren.
  4. Verfahren nach Anspruch 3, worin die behandelten Felle oder Häute schließlich mit Chrom oder Aluminiumsalzen nachgegerbt werden.
  5. Verfahren nach Anspruch 3 oder 4, worin nach der Nachgerbung die nachgegerbten Felle oder Häute mit einem Mittel behandelt werden, um die Wasserstoffbrücken zwischen der Carbonsäure oder einem Anhydrid oder irgendeinem Derivat davon und dem Leder zu zerstören.
  6. Verfahren nach Anspruch 5, worin das Mittel Methylenchlorid ist.
  7. Behandeltes Leder oder Häute, die mit einem Gemisch nach einem der Ansprüche 1 bis 6 imprägniert wurden.
  8. Verwendung einer Emulsion oder eines Gemisches nach einem der Ansprüche 1 bis 6 bei der Behandlung von gegerbten Fellen oder Häuten bei einem pH-Wert von 9 bis 10.
EP93906600A 1992-03-27 1993-03-24 Verbessertes leder Expired - Lifetime EP0632840B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB929206791A GB9206791D0 (en) 1992-03-27 1992-03-27 Improved leather
GB9206791 1992-03-27
PCT/EP1993/000711 WO1993020243A1 (en) 1992-03-27 1993-03-24 Improved leather

Publications (2)

Publication Number Publication Date
EP0632840A1 EP0632840A1 (de) 1995-01-11
EP0632840B1 true EP0632840B1 (de) 1997-09-24

Family

ID=10713018

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93906600A Expired - Lifetime EP0632840B1 (de) 1992-03-27 1993-03-24 Verbessertes leder

Country Status (7)

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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230212214A1 (en) 2020-05-25 2023-07-06 Nissan Chemical Corporation Cleavable dna-encoded library

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1297942A (de) * 1969-03-04 1972-11-29
US3668124A (en) * 1970-05-13 1972-06-06 Pennwalt Corp Composition and method for treating dry-cleanable soil-resistant leathers
US3749669A (en) * 1971-06-21 1973-07-31 Us Agriculture Lubricants for hides and leather
GB8800299D0 (en) * 1988-01-07 1988-02-10 Manzo G Process for production of improved lubricated leather

Also Published As

Publication number Publication date
EP0632840A1 (de) 1995-01-11
ATE158617T1 (de) 1997-10-15
WO1993020243A1 (en) 1993-10-14
CA2132834A1 (en) 1993-10-14
JPH07505184A (ja) 1995-06-08
GB9206791D0 (en) 1992-05-13
DE69314168D1 (de) 1997-10-30
DE69314168T2 (de) 1998-05-07

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