EP2110446B1 - Gerbung von Fellen und Häuten - Google Patents

Gerbung von Fellen und Häuten Download PDF

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Publication number
EP2110446B1
EP2110446B1 EP20080154833 EP08154833A EP2110446B1 EP 2110446 B1 EP2110446 B1 EP 2110446B1 EP 20080154833 EP20080154833 EP 20080154833 EP 08154833 A EP08154833 A EP 08154833A EP 2110446 B1 EP2110446 B1 EP 2110446B1
Authority
EP
European Patent Office
Prior art keywords
tanning
fruit
extract
tannage
hours
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.)
Not-in-force
Application number
EP20080154833
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English (en)
French (fr)
Other versions
EP2110446A1 (de
Inventor
Stuart Booth
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.)
C&J Clark International Ltd
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C&J Clark International Ltd
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Filing date
Publication date
Application filed by C&J Clark International Ltd filed Critical C&J Clark International Ltd
Priority to EP20080154833 priority Critical patent/EP2110446B1/de
Priority to ES08154833T priority patent/ES2453945T3/es
Publication of EP2110446A1 publication Critical patent/EP2110446A1/de
Application granted granted Critical
Publication of EP2110446B1 publication Critical patent/EP2110446B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/10—Vegetable tanning

Definitions

  • the present invention relates to methods of tanning hides or skins.
  • Tanning of hides or skins to produce leather is an ancient process that takes advantage of the property of hides or skins that they absorb tanning chemicals that prevent putrefaction, increase resistance to moisture and promote suppleness.
  • the tanning process involves the reaction of the tanning chemicals with collagen fibres present in the hide or skin.
  • the most common tanning chemicals are chromium based compounds (e.g. chromium sulfate), synthetic tanning chemicals, alum, aldehydes (e.g. formaldehyde) and vegetable tanning compositions.
  • Vegetable tanning compositions are composed of polyphenolic compounds, with the tanning properties related to the size of the molecule and the number of phenolic -OH groups. Vegetable tanning compositions are sometimes referred to as "tannins". Although the term “tannin” refers to the ancient use of some tannins in the tanning process, the term is now widely applied to any plant-derived large polyphenolic compound containing sufficient hydroxyls and other suitable groups (e.g. carboxyl groups) to form strong complexes with macromolecules whether or not such compounds have previously been used to tan hides or skins.
  • suitable groups e.g. carboxyl groups
  • Vegetable tannins used in tanning are derived from tree bark, in particular, the bark of oak, chestnut, quebracho and mimosa.
  • FR-A-926892 discloses the tanning of hides or skins with aqueous extracts of pulverised oil cake from residues of olive fruits.
  • DE-C-905054 discloses the use of myrobalane fruits in the tanning of leather.
  • JP 2002180099A discloses the tanning of hides or skins with tannin extracts from Tara fruit sheath.
  • the present invention accordingly provides, in a first aspect, a method of tanning hides or skins, the method comprising a fruit tanning step of contacting, for a predetermined time and at a predetermined temperature, a hide or skin with a tanning liquor comprising a fruit tanning extract, characterised in that the fruit tanning extract is derived from cider apples, and wherein the tanning liquor also comprises one or more vegetable or synthetic tanning agents, and in that the fruit tanning step is a fruit re-tannage step, the predetermined time is from 6 to 48 hours and the predetermined temperature is from 25°C to 85°C.
  • the advantage of using a fruit tanning extract is that it is possible to use fruits which are readily available and do not involve the felling, for example, of trees but are an annually renewable resource.
  • the fruit is an edible fruit. This is advantageous because edible fruits are produced in large quantities and a large amount of edible fruit waste is available.
  • the fruit will be a fleshy fruit.
  • the fruits are of the sub-family Maloideae (also known as Pomoideae).
  • Maloideae fruits are produced in large quantities throughout the world and typically contain relatively large quantities of polyphenolic compounds.
  • the fruit is a pome, in particular, an apple.
  • Apples are known to contain polyphenolic compounds, including quercetin, catechin, gallic acid, phloretin and chlorogenic acid. Surprisingly, it has been discovered that these compounds have properties that make them suitable for use in tanning of hides or skins. Apples are particularly advantageous because the apple, apple juice and cider industries (cider being an alcoholic beverage produced from apples) produce large quantities of apples and waste products, much of which will contain these polyphenolic compounds.
  • polyphenolic compounds in apples depends very much on the variety of the apple, as well as climate and other growing conditions. Typically, apples grown under low nitrogen regimes or adverse weather conditions tend to contain more polyphenolic compounds. These compounds are also increased in amount if nutrients are restricted during the growing season of the apple. There is also a possibility of using unripe apples which typically contain higher quantities of the polyphenolic compounds.
  • the type of apple is a cider apple.
  • the use of cider apples is advantageous because many cider apples contain high quantities of polyphenolic compounds and also because, typically, the flesh of the apple has a fibrous texture making it easier to extract the juice.
  • bittersweet and bittersharp cider apples are preferred varieties for use in the method of the present invention.
  • Bittersweet apples impart the characteristic flavour of English West Country ciders and are typically low in acid and high in polyphenolic compounds (the "tannin" component of the cider).
  • Bittersharp apples are relatively high both in acid and polyphenolic compounds. Examples of varieties of bittersweet or bittersharp apples include Michelin or Dabinett.
  • the method of the present invention further comprises one or more further tannage steps.
  • These tannage steps may be vegetable or synthetic tannage steps and may take place either before or after the fruit tanning step.
  • the method may also further comprise one or more of the following steps after the fruit tanning step: neutralisation, fatliquoring, fixation and finishing.
  • the method may comprise one or more of the following steps before the fruit tanning step: soaking, liming and/or dehairing, fleshing, splitting, pickling, samming and shaving.
  • the fruit tanning step is a fruit retannage step.
  • the fruit tanning step takes place after a first tannage step which, as discussed above, may involve a vegetable (e.g. chestnut, oak, mimosa or other tree bark or wood extract) or synthetic tanning agent.
  • a vegetable e.g. chestnut, oak, mimosa or other tree bark or wood extract
  • synthetic tanning agent e.g. synthetic tanning agent
  • the tanning liquor also comprises one or more vegetable or synthetic tanning agents in addition to the fruit tanning extract.
  • the fruit tanning extract would be between 20 and 60% of the tanning liquor usually by weight, occasionally by volume.
  • the fruit tanning extract would be between 25 and 50%, more preferably between 25 and 40% of the tanning liquor. If dried fruit tanning extract were to be used then the dried (e.g. spray dried) fruit tanning extract would be between 5 and 25% preferably 5 and 20% and most preferably 5 and 15% of the tanning liquor by weight.
  • the predetermined time involved in the fruit tanning step is from 6 hours to 48 hours, preferably from 6 to 36 and more preferably from 12 to 24 hours.
  • the predetermined temperature is preferably from 25 to 85°C, more preferably from 25 to 50°C, most preferably from 25 to 40°C.
  • the fruit tanning extract is preferably obtainable by aqueous extraction of pulped fruit at elevated temperature.
  • Alternative extraction methods which may be used include solvent extraction or aqueous extraction by boiling under pressure.
  • aqueous extraction at elevated temperature not under pressure is primarily one of cost but it also reduces the likelihood of degradation of the polyphenolic compound in the fruit extract.
  • the elevated temperature is preferably between 40 and 100°C, more preferably between 50 and 80°C and most preferably between 50 and 75°C.
  • the pulped fruit from which the fruit tanning extract is obtained in the most preferred embodiment is apple pomace either before or after pressing of the juice for cider.
  • the apple pomace may be either wet pomace or dried pomace (e.g. spray dried pomace) or a mixture of the two.
  • Trials were carried out using simple aqueous extraction of wet or dry apple waste by heating in water at 70°C, aqueous extraction under pressure and solvent extraction.
  • the tannin content was measured using the Official SLTC method and the Lowenthal Permanganate Titration method (as used in the cider industry). There is a difference in the tannin content between the wet and dry apple wastes. The results showed that for the dry apple waste (using the Lowenthal Permanganate Titration) the tannin content is about 0.06% by weight compared to about 0.04% by weight for the wet apple waste.
  • the spray dried apple waste is weighed and introduced into a tanning processing drum. 700% of water (relative to the weight of apple waste) is added at 74°C and the drum is run to obtain a homogenous mix. After 5 min the temperature is checked and a further 120% of water at 80°C is added. At this stage the extract is a viscous slurry at temperature of 60°C. The process is run for a further 2.5 hours with continuous monitoring of temperature and appearance.
  • biocide (Myacid AS) is added to reduce the potential for putrefaction.
  • the process is run for a further 10 min and left overnight to cool.
  • the drum is run for 10 min to re-mix the extract which is then filtered using either an Archimedean screw technique or filter press.
  • a further 0.04% of biocide and 0.04% of fungicide are added to the final extracted liquid.
  • 80 kg of dried pomace results in about 220 kg of liquid tannin extract being obtained with a moisture content of 96% by weight and 4% unfiltered solids.
  • the liquid tannin extract obtained from the apple extraction is used in combination with vegetable tannins and syntans to tan bovine hides to produce leather.
  • the hides are prepared for tanning using the conventional beamhouse process of soaking, liming, fleshing, splitting, and pickling. They are then sammed and shaved to 1.1 - 1.2 mm substance and placed into a drum containing 150% water and 0.5% oxalic acid to minimise the iron staining. They are washed with water at 20°C and are ready for tanning.
  • the collagen fibre is stabilized and converted to leather by the cross-linking action of the tanning agents rendering the hide no longer susceptible to putrefaction.
  • Tanning also increases the tensile strength and heat resistance.
  • the hides are pretanned using 70% water, 2% Paralene PGS and 2% Sellasol SL. These syntans assist penetration of the vegetable tanning chemicals. This is followed by the main vegetable tannins using 10% Quebracho ATO, 5% Mimosa and 5% Chestnut. This process lasts for 60 min at 20°C.
  • the apple retanning is carried out in a separate process using 100% water, 45% liquid apple tanning extract, 5% Chestnut, 5% Fitapor GT, 1.5% of Manacryl SRG and 1% of Dermadol ID.
  • a blend of apple tannin and conventional vegetable retanning agents and a resin retannage are used. This process takes place at 30°C for 6 hours and is then run intermittently overnight (5min/hour).
  • the retanning process improves the feel and handle of the leather, fills the looser parts of the leather, improves the resistance to alkali, perspiration and general wear characteristics.
  • a light oxalic acid wash is given again to minimise the risk of iron staining, using 100% water at 30°C and 0.5% oxalic acid for 30 min. This is followed by neutralisation with 50% water at 40°C, 2% sodium formate and 4% Dermaflex FR/C to obtain pH 4.5-4.8. This assists penetration of the subsequent fatliquoring.
  • the fatliquoring is a combination of 8% Dermadol BK, 3.5% Dermadol MC, 1.5% Dermadol ID and 5% Tresin ML Liq for 60 min.
  • Leathers are fatliquored to lubricate the fibres and achieve product-specific characteristics of softness and drape.
  • the leathers are given a last oxalic acid wash and a little syntan to dry the surface.
  • the final treatment is fixation of the chemicals with 1% Remsol ALM and 1% formic acid.
  • finishing operations are carried out.
  • a range of mechanical finishing operations such as buffing/dedusting, dry milling (mechanical softening) and polishing are carried out.
  • a surface coat is also applied to provide protection, hand feel, colour and gloss and to meet the customer requirements.
  • Table 1 Tanning process Step n° Operation chemical % Time min T (°C) pH Comments Water 150 20 Oxalic acid 0.5 20 Drain and wash Water 70 20 Paralene PGS 2 Sellasol SL 2 30 tannage Quebracho ATO 10 Mimosa 5 Chestnut Bark 5 60 20 Drain Retan Water 100 Apple Extract 45 Chestnut Bark 5 Fitapor GT 5 Manacryl SRG 1.5 Dermadol ID 1 6 hours + 5 min/hour 30 Run automatically overnight Drain Water 100 30 Oxalic acid 0.50 Drain and wash Neutralise Water 50 40 Sodium formate 2 Dermaflex FR/C 4 15 pH 4.5 - 4.8 Fatliquor Dermadol BK 8 Dermadol MC 4 Dermadol ID 2 Tresin MG Liq 5 60 Oxalic acid 0.3 Retan Remsol ALM 1 15 Fixation Formic acid 1 20

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  • 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 (10)

  1. Verfahren zum Gerben von Fellen und Häuten, wobei das Verfahren Folgendes beinhaltet:
    einen Obstgerbschritt, um für eine vorbestimmte Zeit und bei einer vorbestimmten Temperatur ein Fell oder eine Haut mit einer einen Obstgerbextrakt enthaltenden Gerbbrühe in Kontakt zu bringen, dadurch gekennzeichnet, dass der Obstgerbextrakt von Mostäpfeln gewonnen wird und wobei die Gerbbrühe auch ein oder mehrere pflanzliche oder synthetische Gerbmittel enthält, und dadurch, dass der Obstgerbschritt ein Obstnachgerbschritt ist, wobei die vorbestimmte Zeit 6 bis 48 Stunden und die vorbestimmte Temperatur 25°C bis 85°C beträgt.
  2. Verfahren nach Anspruch 1, das ferner ein oder mehrere Gerbschritte beinhaltet.
  3. Verfahren nach Anspruch 1 oder Anspruch 2, das ferner einen oder mehrere der folgenden Schritte nach dem Obstgerbschritt beinhaltet: Neutralisierung, Fettung, Fixierung und Veredelung.
  4. Verfahren nach einem der vorherigen Ansprüche, das ferner einen oder mehrere der folgenden Schritte vor dem Obstgerbschritt beinhaltet: Einweichen, Kalken und/oder Enthaaren, Entfleischen, Teilen, Beizen, Abwelken und Falzen.
  5. Verfahren nach einem der vorherigen Ansprüche, das ferner einen oder mehrere Gerbschritte vor dem Obstnachgerbschritt beinhaltet.
  6. Verfahren nach einem der vorherigen Ansprüche, wobei die vorbestimmte Zeit 6 Stunden bis 36 Stunden beträgt.
  7. Verfahren nach einem der vorherigen Ansprüche, wobei die vorbestimmte Zeit 12 Stunden bis 24 Stunden beträgt.
  8. Verfahren nach einem der vorherigen Ansprüche, wobei die vorbestimmte Temperatur 25°C bis 50°C beträgt.
  9. Verfahren nach einem der vorherigen Ansprüche, wobei die vorbestimmte Temperatur 25°C bis 40°C beträgt.
  10. Verfahren nach einem der vorherigen Ansprüche, wobei der Obstgerbextrakt durch wässrige Extraktion von Fruchtfleisch bei erhöhter Temperatur erhalten werden kann.
EP20080154833 2008-04-18 2008-04-18 Gerbung von Fellen und Häuten Not-in-force EP2110446B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20080154833 EP2110446B1 (de) 2008-04-18 2008-04-18 Gerbung von Fellen und Häuten
ES08154833T ES2453945T3 (es) 2008-04-18 2008-04-18 Curtido de cueros y pieles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20080154833 EP2110446B1 (de) 2008-04-18 2008-04-18 Gerbung von Fellen und Häuten

Publications (2)

Publication Number Publication Date
EP2110446A1 EP2110446A1 (de) 2009-10-21
EP2110446B1 true EP2110446B1 (de) 2014-02-19

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP20080154833 Not-in-force EP2110446B1 (de) 2008-04-18 2008-04-18 Gerbung von Fellen und Häuten

Country Status (2)

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EP (1) EP2110446B1 (de)
ES (1) ES2453945T3 (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002541B (zh) * 2010-05-24 2013-04-24 孟凡标 一种栲胶鞣毛革一体工艺
CN103290150B (zh) * 2013-05-16 2014-12-24 伊犁霍尔果斯枣索制革厂 一种奶牛毛皮地毯的生产工艺
CN103710475A (zh) * 2013-11-28 2014-04-09 湖州立方农艺科技发展有限公司 一种皮革鞣制工艺
ITUA20162349A1 (it) * 2016-04-06 2017-10-06 Glycolor S R L Uso del lattosio in combinazione con estratti vegetali naturali per la concia metal free di pelli animali
ES2959478T3 (es) 2018-03-28 2024-02-26 Handelmaatschappij A Smit En Zoon B V Tratamiento del cuero incluyendo el empleo de pectina
BR112022000631A2 (pt) * 2019-07-16 2022-03-03 Curtidos Trevino S A De C V Método para a produção de couro sustentável com a utilização de subprodutos de partes de todas as variedades e espécies da planta do gênero persea, o que inclui tanto a espécie americana como a variedade de hass
IT202100004289A1 (it) * 2021-02-24 2022-08-24 Sandro MELIANI Metodo per conciare pelli animali per la produzione di sottopiedi per calzature
EP4180541B1 (de) 2021-11-15 2024-05-15 Cyclica S.r.l. Verfahren zur herstellung eines gegerbten produkts
CN114669279B (zh) * 2022-04-12 2023-09-15 西南科技大学 铋基植物单宁@胶原纤维水热炭高效固载碘蒸气材料的制备及应用
DE102022121017A1 (de) * 2022-08-19 2024-02-22 Tfl Ledertechnik Gmbh Vegetabile Extrakte zum Gerben

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE905054C (de) * 1942-01-16 1954-02-25 C F Roser G M B H Verfahren zur Herstellung von Gerbstoffauszuegen aus gerbstoffhaltigen Fruechten
FR926892A (fr) * 1945-10-11 1947-10-14 Perfectionnements Ind Soc Et Perfectionnements relatifs au traitement du grignon d'olive
JP2002180099A (ja) * 2000-12-18 2002-06-26 Teikoku Kasei Kogyo Kk 着色皮革の製造方法

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Publication number Publication date
ES2453945T3 (es) 2014-04-09
EP2110446A1 (de) 2009-10-21

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