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EP0410862B1 - Method of treating hides and hides thus treated - Google Patents

Method of treating hides and hides thus treated Download PDF

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Publication number
EP0410862B1
EP0410862B1 EP90402108A EP90402108A EP0410862B1 EP 0410862 B1 EP0410862 B1 EP 0410862B1 EP 90402108 A EP90402108 A EP 90402108A EP 90402108 A EP90402108 A EP 90402108A EP 0410862 B1 EP0410862 B1 EP 0410862B1
Authority
EP
European Patent Office
Prior art keywords
lanthanum
treatment
cerium
hide
salts
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
EP90402108A
Other languages
German (de)
French (fr)
Other versions
EP0410862A1 (en
Inventor
Jacques Lemaire
Gérard Gavend
Bernard Vulliermet
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.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie SA
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
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Publication of EP0410862A1 publication Critical patent/EP0410862A1/en
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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
    • 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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/02—Curing raw hides
    • 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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing

Definitions

  • the present invention relates to a method of treating skins and the skins thus treated.
  • It relates more particularly to a treatment making it possible to ensure better conservation from a biological point of view thereof, in particular during the process of preparation thereof before or after their tanning.
  • products or compositions comprising compounds with antifungal or anti-bacterial action such as, for example, tri or pentachlorophenols, paramethacresol, orthophenyphenol and their sodium salts, benzothiazole derivatives (for example, TCMTB), isothiazolones, metal salts such as zinc or copper salts.
  • compounds with antifungal or anti-bacterial action such as, for example, tri or pentachlorophenols, paramethacresol, orthophenyphenol and their sodium salts, benzothiazole derivatives (for example, TCMTB), isothiazolones, metal salts such as zinc or copper salts.
  • these products can also be annoying in the development of skins after tanning, for example.
  • the object of the invention is in particular to remedy these drawbacks by proposing a method of treating the skins to protect them from fungal or bacterial attacks, capable of being applied at all stages or stages of the method for producing a skin.
  • the invention provides a method of treating the skins to protect them from fungal and / or bacterial attacks consisting in treating the latter with a treatment bath comprising at least one salt of lanthanum or of cerium.
  • lanthanum or cerium salts any water-soluble salt such as mineral salts such as nitrates, chlorides, sulfates, for example, organic salts or organosulfonic or gluconate salts.
  • the lanthanum or cerium salts are organic salts derived from a vinyl carboxylic acid such as, for example, acrylic acid, methacrylic acid.
  • the preferred salts of the invention are the lanthanum acrylates and methacrylates.
  • the skins are treated with an amount of lanthanum or cerium expressed as oxide advantageously between 0.02% and 1.25%, preferably between 0.04% and 1.25%.
  • lanthanum expressed as oxide
  • tripe skin skin that is depilated and free of fat and epidermis.
  • the salt is a vinyl carboxylic acid salt
  • free vinyl carboxylic acid is added to the treatment solution.
  • the amount of vinyl anion or of vinyl acid expressed as free vinyl acid is advantageously between 0.5% and 5% of skin in guts, preferably between 1% and 3%.
  • This treatment bath can be used alone or in combination with a skin treatment bath, such as for example the pickling, tanning, or pre-tanning baths such as the BSH or BSS baths, described for example in French patent no. 2 610 643 from the Technical Center for Leather Shoes and Leather Goods.
  • a skin treatment bath such as for example the pickling, tanning, or pre-tanning baths such as the BSH or BSS baths, described for example in French patent no. 2 610 643 from the Technical Center for Leather Shoes and Leather Goods.
  • This antifungal and antibacterial treatment bath is particularly suitable for treating tanned skins in order to preserve them against molds damaging their appearance.
  • the treatment bath according to the invention preserves the skin against attack by fungi such as, for example, aspergillus niger, penicillium funiculosum, rhizopus nigricans, trichoderma viride or bacteria bacilus subtilis, escherichia coli.
  • fungi such as, for example, aspergillus niger, penicillium funiculosum, rhizopus nigricans, trichoderma viride or bacteria bacilus subtilis, escherichia coli.
  • Another advantage of the process of the invention lies in the fact that the treatment agent does not become fixed irreversibly on the skin fiber and therefore can be easily removed by washing.
  • lanthanum or cerium are not harmful and therefore can be discharged into waste water.
  • the method of the invention can be implemented by any known means and for example by impregnation with a treatment bath by passing through a fuller.
  • the invention also relates to skins treated according to the method of the invention and comprising lanthanum and / or cerium.
  • the treated skins advantageously comprise from 0.02% to 1.2% of lanthanum or cerium expressed relative to the weight of dry matter, that is to say after drying in a ventilated oven for 6 hours at 105 ° C and drying at this temperature at constant weight.
  • the treated skins can also comprise vinyl units either in monomeric form or in polymerized form.
  • the skin was divided into strips which were then treated with stabilization baths to obtain B.S.H.
  • This stabilization treatment consists in adding to the pickling solution after neutralization 2% (tripe weight) of aluminum polychlorosulfate (i.e. 0.16% expressed as Al2O3) in the form of an aqueous solution having a basicity of 55%, a desulfation rate of 82% and an Al2O3 content of 8.3% obtained according to the process described in European patent application No. 218487.
  • aluminum polychlorosulfate i.e. 0.16% expressed as Al2O3
  • control strip No. 1 is invaded by mold both in the full-thickness leather and in the split flower.
  • Tests of skin contamination by molds were carried out in a PETRI box, on small samples of leather seeded with microbial cells, at the rate of 1 ⁇ 105 cells per cm2 of leather.
  • the sample thus seeded is placed in an agar medium poured into a PETRI box and itself seeded with the suspension of corresponding microbial molds.
  • the whole is incubated at 30 ° C. in a thermostatically controlled oven.
  • a leather tanned with chromium salts and commonly called “wet-blue” leather, is impregnated with a solution containing an antibacterial compound either in accordance with the invention, or by way of comparison with a known compound and commonly used, namely a derivative of benzothiazole marketed under the name "BUSAN".
  • the lanthanum content, expressed as lanthanum oxide, or the busan content is 0.4%
  • the results are collated in the attached table: ANTIBACTERIAL COMPOSITION % INVASION OF THE SAMPLE AFTER 3 DAYS 6 DAYS 12 DAYS 16 DAYS 27 DAYS - 50% 100% 100% 100% 100% LANTHANE XYLENE SULFONATE 10% 60% 80% 80% 80% LANTHANE GLUCONATE 5% 60% 80% 80% 80% LANTHANE SULFATE 5% 80% 80% 100% 100% LANTHANE ACRYLATE 0% 5% 40% 40% 60% LANTHANE ACRYLATE + ACRYLIC ACID 0% 5% 5% 15% BUSAN 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0%

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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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Adornments (AREA)
  • Stringed Musical Instruments (AREA)
  • Disintegrating Or Milling (AREA)
  • Pinball Game Machines (AREA)
  • Laminated Bodies (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Materials For Medical Uses (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Glass Compositions (AREA)
  • Gloves (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

Method for the antifungal and/or antibacterial treatment of hides. This method consists in treating these hides with a bath containing a lanthanum or cerium salt, for example a lanthanum acrylate.

Description

La présente invention concerne un procédé de traitement de peaux et les peaux ainsi traitées.The present invention relates to a method of treating skins and the skins thus treated.

Elle concerne plus particulièrement un traitement permettant d'assurer une meilleure conservation d'un point de vue biologique de celles-ci, notamment au cours du procédé d'élaboration de celles-ci avant ou après leur tannage.It relates more particularly to a treatment making it possible to ensure better conservation from a biological point of view thereof, in particular during the process of preparation thereof before or after their tanning.

Actuellement, les peaux sont généralement commercialisées sous différentes formes :

  • à l'état brut (salé, saumuré, salé - sec et frais, etc ...)
  • à l'état picklé (traitement par une solution d'acide fort en présence de sel)
  • à l'état prétanné reversible (B.S.H. ou B.S.S., wet white, dry white, par exemple)
  • à l'état tanné (par exemple par un traitement au chrome)
  • à l'état semi-ouvré (appelé "stain")
  • ou à l'état fini.
Currently, skins are generally marketed in different forms:
  • unprocessed (salted, brined, salted - dry and fresh, etc ...)
  • pickled (treatment with a strong acid solution in the presence of salt)
  • in the reversible pretanned state (BSH or BSS, wet white, dry white, for example)
  • in the tanned state (for example by treatment with chromium)
  • in the semi-worked state (called "stain")
  • or in the finished state.

Ces peaux sont souvent transportées ou stockées dans des lieux non adaptés pour leur conservation, notamment les conditions d'humidité, de salubrité sont propices au développement d'une contamination bactérienne et/ou fongique des peaux. Les différentes solutions de traitement utilisées dans chaque étape de l'élaboration d'une peau peuvent présenter une action antibactérienne ou antifongique. Toutefois, celle-ci n'est pas suffisante pour assurer une protection suffisante.These skins are often transported or stored in places unsuitable for their conservation, in particular the conditions of humidity and sanitation are favorable to the development of bacterial and / or fungal contamination of the skins. The different treatment solutions used in each stage of skin development can have an antibacterial or antifungal action. However, this is not sufficient to provide sufficient protection.

Pour cela, il a déjà été proposé d'utiliser des produits ou compositions comprenant des composés à action antifongique ou anti-bactérienne tel que, par exemple, les tri ou pentachlorophénols, paraméthacrésol, orthophényphénol et leurs sels de sodium, les dérivés du benzothiazole (par exemple, le TCMTB), les isothiazolones, les sels métalliques tels que les sels de zinc ou de cuivre.For this, it has already been proposed to use products or compositions comprising compounds with antifungal or anti-bacterial action such as, for example, tri or pentachlorophenols, paramethacresol, orthophenyphenol and their sodium salts, benzothiazole derivatives ( for example, TCMTB), isothiazolones, metal salts such as zinc or copper salts.

Ces produits spécifiques présentent des inconvénients car ils sont généralement difficilement éliminables. Ainsi, si les peaux sont traitées avec de tels produits avant ou pendant les opérations de rivière, ceux-ci seront présents dans les déchets récupérés au cours de l'élaboration de la peau par exemple, l'écharnage. Ces déchets pollués ne peuvent être récupérés, notamment dans la fabrication du collagène.These specific products have drawbacks because they are generally difficult to eliminate. Thus, if the skins are treated with such products before or during river operations, these will be present in the waste recovered during the development of the skin, for example, fleshing. This polluted waste cannot be recovered, especially in the manufacture of collagen.

Par ailleurs, ces produits spécifiques se retrouvent dans les eaux résiduaires de traitement des peaux provoquant une pollution non acceptable pour l'environnement. Ces produits peuvent également avoir un effet toxique pour les procédés de traitement des eaux résiduaires (traitement biologique) mis en oeuvre dans les stations d'épuration des eaux.In addition, these specific products are found in waste water from skin treatment causing pollution that is not acceptable to the environment. These products can also have a toxic effect for wastewater treatment processes (biological treatment) implemented in water treatment plants.

De plus, ces produits peuvent également être génants dans l'élaboration des peaux après tannage, par exemple.In addition, these products can also be annoying in the development of skins after tanning, for example.

L'invention a notamment pour objet de remédier à ces inconvénients en proposant un procédé de traitement des peaux pour les préserver des attaques fongiques ou bactériennes, susceptible d'être appliqué à tous les stades ou étapes du procédé d'élaboration d'une peau.The object of the invention is in particular to remedy these drawbacks by proposing a method of treating the skins to protect them from fungal or bacterial attacks, capable of being applied at all stages or stages of the method for producing a skin.

A cet effet, l'invention propose un procédé de traitement des peaux pour les préserver des attaques fongiques et/ou bactériennes consistant à traiter celles-ci avec un bain de traitement comprenant au moins un sel de lanthane ou de cérium.To this end, the invention provides a method of treating the skins to protect them from fungal and / or bacterial attacks consisting in treating the latter with a treatment bath comprising at least one salt of lanthanum or of cerium.

Par sels de lanthane ou de cérium, on entend tout sel soluble dans l'eau tel que les sels minéraux comme les nitrates, chlorures, sulfates, par exemple, les sels organiques ou les sels organosulfoniques ou gluconates.By lanthanum or cerium salts is meant any water-soluble salt such as mineral salts such as nitrates, chlorides, sulfates, for example, organic salts or organosulfonic or gluconate salts.

Il est connu d'utiliser des solutions de sels de lanthane ou de cerium comme antimicrobiens dans des compositions médicales, cosmétiques, de nettoyage (EP-A-0037224) ou pour la conservation du bois (US-A-4743473).It is known to use lanthanum or cerium salt solutions as antimicrobials in medical, cosmetic, cleaning compositions (EP-A-0037224) or for the preservation of wood (US-A-4743473).

Selon une caractéristique préférée de l'invention, les sels de lanthane ou cérium sont des sels organiques dérivant d'un acide carboxylique vinylique tel que, par exemple, l'acide acrylique, l'acide méthacrylique.According to a preferred characteristic of the invention, the lanthanum or cerium salts are organic salts derived from a vinyl carboxylic acid such as, for example, acrylic acid, methacrylic acid.

Les sels préférés de l'invention sont les acrylates et méthacrylates de lanthane.The preferred salts of the invention are the lanthanum acrylates and methacrylates.

Les peaux sont traitées avec une quantité de lanthane ou cérium exprimé en oxyde comprise avantageusement entre 0,02 % et 1,25 %, de préférence entre 0,04 % et 1,25 %.The skins are treated with an amount of lanthanum or cerium expressed as oxide advantageously between 0.02% and 1.25%, preferably between 0.04% and 1.25%.

Ces pourcentages représentent la masse de composé par exemple de lanthane (exprimée en oxyde) ajoutée pour traiter 100 kg de peau en tripe. Par peau en tripe on entend une peau épilée et débarrassée des graisses et épiderme.These percentages represent the mass of compound, for example lanthanum (expressed as oxide) added to treat 100 kg of skin in guts. By tripe skin is meant skin that is depilated and free of fat and epidermis.

Les pourcentages donnés dans le texte ci-dessous expriment toujours la quantité de produit ajoutée pour traiter 100 kg de peau en tripe, sauf indication contraire.The percentages given in the text below always express the amount of product added to treat 100 kg of skin in guts, unless otherwise indicated.

Avantageusement quand le sel est un sel d'acide carboxylique vinylique, de l'acide carboxylique vinylique libre est ajoutée à la solution de traitement.Advantageously when the salt is a vinyl carboxylic acid salt, free vinyl carboxylic acid is added to the treatment solution.

Selon une autre caractéristique de l'invention, la quantité d'anion vinylique ou d'acide vinylique exprimée en acide vinylique libre est avantageusement comprise entre 0,5 % et 5 % de peau en tripe, de préférence entre 1 % et 3 %.According to another characteristic of the invention, the amount of vinyl anion or of vinyl acid expressed as free vinyl acid is advantageously between 0.5% and 5% of skin in guts, preferably between 1% and 3%.

Ce bain de traitement peut être utilisé seul ou en combinaison avec un bain de traitement de la peau, tel que par exemple les bains de picklage, tannage, ou de prétannage comme les bains BSH ou BSS, décrits par exemple dans le brevet français n° 2 610 643 du Centre Technique Cuir Chaussure et Maroquinerie.This treatment bath can be used alone or in combination with a skin treatment bath, such as for example the pickling, tanning, or pre-tanning baths such as the BSH or BSS baths, described for example in French patent no. 2 610 643 from the Technical Center for Leather Shoes and Leather Goods.

Ce bain de traitement antifongique et antibactérien convient notamment pour traiter les peaux tannées afin de les préserver contre les moisissures endommageant l'aspect de celles-ci.This antifungal and antibacterial treatment bath is particularly suitable for treating tanned skins in order to preserve them against molds damaging their appearance.

Ainsi le bain de traitement conforme à l'invention préserve les peaux contre l'attaque des champignons tels que par exemple l'aspergillus niger, le penicillium funiculosum, le rhizopus nigricans, le trichoderma viride ou les bactéries bacilus subtilis, escherichia coli.Thus the treatment bath according to the invention preserves the skin against attack by fungi such as, for example, aspergillus niger, penicillium funiculosum, rhizopus nigricans, trichoderma viride or bacteria bacilus subtilis, escherichia coli.

Un autre avantage du procédé de l'invention réside dans le fait que l'agent de traitement ne se fixe pas de façon irréversible sur la fibre de la peau et donc peut être éliminé aisément par lavage.Another advantage of the process of the invention lies in the fact that the treatment agent does not become fixed irreversibly on the skin fiber and therefore can be easily removed by washing.

Ainsi, les traitements ultérieurs de celle-ci ne seront pas altérés.Thus, subsequent processing thereof will not be altered.

De plus, le lanthane ou le cérium ne sont pas nocifs et donc peuvent être rejetés dans les eaux résiduaires.In addition, lanthanum or cerium are not harmful and therefore can be discharged into waste water.

Par ailleurs, les monomères vinyliques (acryliques ou méthacryliques) résiduels sont facilement polymérisables, cette polymérisation inhibant l'effet gênant de ces monomères.Furthermore, residual vinyl (acrylic or methacrylic) monomers are easily polymerizable, this polymerization inhibiting the annoying effect of these monomers.

Le procédé de l'invention peut être mis en oeuvre par tout moyen connu et par exemple par l'imprégnation par un bain de traitement par passage dans un foulon.The method of the invention can be implemented by any known means and for example by impregnation with a treatment bath by passing through a fuller.

L'invention a également pour objet des peaux traitées selon le procédé de l'invention et comprenant du lanthane et/ou du cérium.The invention also relates to skins treated according to the method of the invention and comprising lanthanum and / or cerium.

Selon une autre caractéristique, les peaux traitées comprennent advantageusement de 0,02 % à 1,2 % de lanthane ou cérium exprimé par rapport au poids de matière sèche, c'est-à-dire après un séchage en étuve ventilée pendant 6 heures à 105°C et une dessication à cette température à poids constant.According to another characteristic, the treated skins advantageously comprise from 0.02% to 1.2% of lanthanum or cerium expressed relative to the weight of dry matter, that is to say after drying in a ventilated oven for 6 hours at 105 ° C and drying at this temperature at constant weight.

Les peaux traitées peuvent comprendre également des motifs vyniliques soit sous forme monomère, soit sous forme polymérisée.The treated skins can also comprise vinyl units either in monomeric form or in polymerized form.

D'autres détails, avantages et but de la présente invention apparaîtront plus clairement au vu des exemples donnés ci-dessous uniquement à titre indicatif.

  • Une première série d'essais a été réalisée sur une peau de bovin complètement déchaulée.
Other details, advantages and object of the present invention will appear more clearly in the light of the examples given below only for information.
  • A first series of tests was carried out on completely uncharged bovine skin.

Cette peau a été découpée en tranches d'un poids de 2000 grammes. Chaque tranche a été traitée par une solution acide de picklage dont la composition sera donnée ci-dessous :

  • échantillon 1 essai témoin
       bain de picklage : 100 % d'eau ; 10 % de NaCl ; 1,5 % d'acide sulfurique ; pH = 2,8.
    Le traitement a duré 3 heures.
    Ces pourcentages expriment la masse de composé ajouté pour 100 kg de peau en tripe.
    Il en est de même pour les exemples suivants.
  • échantillon 2
       bain de picklage : 100 % d'eau ; 10 % NaCl ; 1,5 % d'acide sulfurique ; 1,96 % de nitrate de lanthane (0,725 % en La₂O₃) ; pH = 4,0.
    Le traitement a duré 3 heures.
  • échantillon 3
       Une solution d'acrylate de lanthane et d'acide acrylique contenant 172,8 g/l en La₂O₃ et 476,3 g/l en acide acrylique est additionnée dans un bain de picklage contenant 100 % d'eau et 10 % de sel pour obtenir une concentration en acide acrylique égale à 2 % en La₂O₃ égale à 0,725 %.
    La peau est traitée pendant 3 heures à un pH = 5,8.
This skin was cut into slices weighing 2000 grams. Each slice was treated with an acid pickling solution, the composition of which will be given below:
  • sample 1 control test
    pickling bath : 100% water; 10% NaCl; 1.5% sulfuric acid; pH = 2.8.
    The treatment lasted 3 hours.
    These percentages express the mass of compound added per 100 kg of tripe skin.
    The same is true for the following examples.
  • sample 2
    pickling bath : 100% water; 10% NaCl; 1.5% sulfuric acid; 1.96% lanthanum nitrate (0.725% in La₂O₃); pH = 4.0.
    The treatment lasted 3 hours.
  • sample 3
    A solution of lanthanum acrylate and acrylic acid containing 172.8 g / l of La₂O₃ and 476.3 g / l of acrylic acid is added to a pickling bath containing 100% water and 10% salt for obtain a concentration of acrylic acid equal to 2% in La₂O₃ equal to 0.725%.
    The skin is treated for 3 hours at a pH = 5.8.

Ces échantillons sont stockés dans une enceinte à 18-20°C avec une humidité relative de 85 %.These samples are stored in an enclosure at 18-20 ° C with a relative humidity of 85%.

Dans ces conditions de stockage, des taches de moisissure apparaissent sur l'échantillon 1 témoin après 18 jours de stockage tandis que les échantillons 2 et 3 ne présentent aucune évolution.

  • Une deuxième série d'essais a été réalisée sur une peau de bovin picklée avec un bain de picklage comprenant 100 % d'eau, 5 % de NaCl, 1,5 % d'acide sulfurique.
Under these storage conditions, mold spots appear on the control sample 1 after 18 days of storage while samples 2 and 3 show no change.
  • A second series of tests was carried out on a pickled bovine skin with a pickling bath comprising 100% water, 5% NaCl, 1.5% sulfuric acid.

La peau a été divisée en bandes qui ont été ensuite traitées par des bains de stabilisation pour obtenir des peaux B.S.H.The skin was divided into strips which were then treated with stabilization baths to obtain B.S.H.

Ce traitement de stabilisation consiste à ajouter à la solution de picklage après neutralisation 2 % (poids en tripe) de polychlorosulfate d'aluminium (soit 0,16 % exprimée en Al₂O₃) sous forme d'une solution aqueuse présentant une basicité de 55 %, un taux de désulfatation de 82 % et une teneur en Al₂O₃ de 8,3 % obtenu selon le procédé décrit dans la demande de brevet européen n° 218487.This stabilization treatment consists in adding to the pickling solution after neutralization 2% (tripe weight) of aluminum polychlorosulfate (i.e. 0.16% expressed as Al₂O₃) in the form of an aqueous solution having a basicity of 55%, a desulfation rate of 82% and an Al₂O₃ content of 8.3% obtained according to the process described in European patent application No. 218487.

Au cours de ce traitement, un agent de traitement antifongique et/ou antiseptique a été ajouté au bain de stabilisation, avec neutralisation du bain pour obtenir un pH égal à environ 4.

  • bande n°1
       Sans agent de traitement antifongique et/ou antiseptique.
  • bande n°2
       Une solution contenant de l'acrylate de lanthane et de l'acide acrylique (172,8 g/ exprimé en La₂O₃ et 476,3 g en acide acrylique), de manière à avoir 0,4 % exprimé en La₂O₃ par rapport au poids de tripe (poids de peau).
  • bande n°3
       23,8 g d'acrylate de lanthane sont ajoutés au bain de stabilisation pour avoir une teneur de 0,04 % exprimé en La₂O₃ par rapport au poids de tripe.
  • bande n°4
       Un agent antiseptique classique commercialisé sous le nom commercial "Busan 30" est ajouté au bain de stabilisation pour avoir une concentration de 0,07 % par rapport au poids de tripe.
During this treatment, an antifungal and / or antiseptic treatment agent was added to the stabilization bath, with neutralization of the bath to obtain a pH equal to approximately 4.
  • tape n ° 1
    Without antifungal and / or antiseptic treatment agent.
  • tape n ° 2
    A solution containing lanthanum acrylate and acrylic acid (172.8 g / expressed in La₂O₃ and 476.3 g in acrylic acid), so as to have 0.4% expressed in La₂O₃ relative to the weight of tripe (skin weight).
  • strip 3
    23.8 g of lanthanum acrylate are added to the stabilization bath to have a content of 0.04% expressed as La₂O₃ relative to the weight of tripe.
  • strip n ° 4
    A conventional antiseptic agent sold under the trade name "Busan 30" is added to the stabilization bath to have a concentration of 0.07% relative to the weight of tripe.

Ces différentes bandes sont stockées en chambre humide à une température de 18-20°C avec 85 % d'humidité.These different bands are stored in a humid chamber at a temperature of 18-20 ° C with 85% humidity.

Ainsi au bout de 11 semaines de stockage, seule la bande témoin n° 1 est envahie par les moisissures tant au niveau du cuir pleine épaisseur que de la fleur refendue.Thus after 11 weeks of storage, only the control strip No. 1 is invaded by mold both in the full-thickness leather and in the split flower.

Par ailleurs, une partie de ces bandes a été soumise à un traitement de tannage au chrome ou un tannage végétal.In addition, part of these bands was subjected to a chrome tanning treatment or a vegetable tanning.

Ces essais de tannages ont montré que le traitement des peaux avec un bain selon l'invention n'influe pas sur les conditions de tannage et les propriétés des peaux tannées obtenues.These tanning tests have shown that the treatment of hides with a bath according to the invention does not influence the tanning conditions and the properties of the tanned hides obtained.

Un dosage du lanthane sur les peaux BSH a montré que la teneur en lanthane par rapport à la matière sèche est de 0,07 % pour la bande 3 et de 0,46 % pour la bande 2.An assay of lanthanum on BSH skins has shown that the lanthanum content relative to the dry matter is 0.07% for band 3 and 0.46% for band 2.

Des essais de contamination de peaux par des moisissures ont été réalisés en boîte de PETRI, sur de petits échantillons de cuir ensemencés avec des cellules microbiennes, à raison de 1 x 10⁵ cellules par cm² de cuir.Tests of skin contamination by molds were carried out in a PETRI box, on small samples of leather seeded with microbial cells, at the rate of 1 × 10⁵ cells per cm² of leather.

L'échantillon ainsi ensemencé est disposé dans un milieu gélosé coulé en boîte de PETRI et lui-même ensemencé avec la suspension de moisissures microbiennes correspondantes.The sample thus seeded is placed in an agar medium poured into a PETRI box and itself seeded with the suspension of corresponding microbial molds.

L'ensemble est mis à incuber à 30°C en étuve thermostatée.The whole is incubated at 30 ° C. in a thermostatically controlled oven.

Le développement des moisissures sur le cuir et le milieu gélosé est observe.The development of molds on the leather and the agar medium is observed.

Dans une première série de tests, un cuir tanné avec des sels chromés, et appelé communément cuir "wet-blue" est imprégné avec une solution contenant un composé antibactérien soit conforme à l'invention, soit à titre de comparaison avec un composé connu et couramment employé, à savoir un dérivé du benzothiazole commercialisé sous le nom "BUSAN".In a first series of tests, a leather tanned with chromium salts, and commonly called "wet-blue" leather, is impregnated with a solution containing an antibacterial compound either in accordance with the invention, or by way of comparison with a known compound and commonly used, namely a derivative of benzothiazole marketed under the name "BUSAN".

La teneur en lanthane, exprimé en oxyde de lanthane, ou la teneur en busan est de 0,4 %
   Les résultats sont rassemblés dans le tableau ci-joint : COMPOSITION ANTIBACTERIENNE % ENVAHISSEMENT DE L'ECHANTILLON APRES 3 JOURS 6 JOURS 12 JOURS 16 JOURS 27 JOURS ― 50 % 100 % 100 % 100 % 100 % XYLENE SULFONATE DE LANTHANE 10 % 60 % 80 % 80 % 80 % GLUCONATE DE LANTHANE 5 % 60 % 80 % 80 % 80 % SULFATE DE LANTHANE 5 % 80 % 80 % 100 % 100 % ACRYLATE DE LANTHANE 0 % 5 % 40 % 40 % 60 % ACRYLATE DE LANTHANE + ACIDE ACRYLIQUE 0 % 5 % 5 % 5 % 15 % BUSAN 0 % 0 % 0 % 0 % 0 % The lanthanum content, expressed as lanthanum oxide, or the busan content is 0.4%
The results are collated in the attached table: ANTIBACTERIAL COMPOSITION % INVASION OF THE SAMPLE AFTER 3 DAYS 6 DAYS 12 DAYS 16 DAYS 27 DAYS - 50% 100% 100% 100% 100% LANTHANE XYLENE SULFONATE 10% 60% 80% 80% 80% LANTHANE GLUCONATE 5% 60% 80% 80% 80% LANTHANE SULFATE 5% 80% 80% 100% 100% LANTHANE ACRYLATE 0% 5% 40% 40% 60% LANTHANE ACRYLATE + ACRYLIC ACID 0% 5% 5% 5% 15% BUSAN 0% 0% 0% 0% 0%

Une autre série de tests a été réalisée selon le même protocole mais en utilisant des peaux prétannées avec une solution d'aluminium appelée peau BSH.Another series of tests was carried out according to the same protocol but using pre-tanned skins with an aluminum solution called BSH skin.

Ainsi, on a observé que la peau imprégnée par 0,4 % de lanthane (exprimé en La₂ 0₃) avec de l'acrylate de lanthane est envahie à 75 % après 6 jours, et que celle imprégnée avec une solution d'acrylate de lanthane dans l'acide acrylique est envahie à 50 % après 10 jours et 75 % après 24 jours, tandis qu'une peau ne comprenant pas d'agents anti-bactériens est envahie à 100 % après 3 jours.Thus, it was observed that the skin impregnated with 0.4% lanthanum (expressed as La₂ 0₃) with lanthanum acrylate is invaded at 75% after 6 days, and that that impregnated with a lanthanum acrylate solution in acrylic acid is 50% invaded after 10 days and 75% after 24 days, while a skin not comprising anti-bacterial agents is 100% invaded after 3 days.

Ces tests ont également été réalisés avec des peaux ayant subi un tannage végétal. Ils ont montré que le mélange acrylate de lanthane et acide acrylique permet de retarder l'envahissement par les moisissures de quelques jours (6 jours environ), dans les conditions des tests, alors que ces peaux non traitées sont envahies très rapidement (1 jour).These tests were also carried out with skins having undergone vegetable tanning. They have shown that the mixture of lanthanum acrylate and acrylic acid makes it possible to delay mold invasion by a few days (approximately 6 days), under the test conditions, while these untreated skins are invaded very quickly (1 day) .

Claims (12)

  1. An antifungal and antibacteriai treatment method for hides, characterised in that it consists of treating them in a treatment bath comprising at least one lanthanum or cerium salt.
  2. A method according to claim 1, characterised in that the lanthanum or cerium salt is a water soluble or dispersable salt selected from the group comprising nitrates, halides, sulphates and organic salts.
  3. A method according to claim 2, characterised in that the organic lanthanum or cerium salts are vinyl or organosulphonic carboxylic acid salts or gluconates.
  4. A method according to claim 3, characterised in that the vinyl carboxylic acid salts are salts of acrylic acid or methacrylic acid.
  5. A method according to claim 4, characterised in that the treatment bath contains a free vinyl carboxylic acid.
  6. A method according to any one of the preceding claims, characterised in that the weight of lanthanum or cerium, expressed as the oxide added for the hide treatment, is between 0.02% and 1.25% of pelt, preferably between 0.04% and 1.25%.
  7. A method according to any one of the preceding claims, characterised in that the weight of the vinyl carboxylic anion and/or the vinyl carboxylic acid, expressed as free vinyl carboxylic acid added for the hide treatment, is between 0.5% and 5% of pelt, preferably between 1% and 3% of pelt.
  8. A method according to any one of the preceding claims, characterised in that the antifungal and antibacerial treatment bath is used in combination with one of the hide treatment baths.
  9. A method according to any one of the preceding claims, characterised in that it consists of treating tanned or partially tanned hides.
  10. A hide, characterised in that it contains lanthanum or cerium.
  11. A hide according to claim 10, characterised in that it contains vinyl groups in the monomeric or polymerised state.
  12. A hide according to claim 10 or claim 11, characterised in that the lanthanum or cerium content, expressed as the oxide, is between 0.04% and 1.2% with respect to the dry matter.
EP90402108A 1989-07-28 1990-07-23 Method of treating hides and hides thus treated Expired - Lifetime EP0410862B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8910195 1989-07-28
FR8910195A FR2650294B1 (en) 1989-07-28 1989-07-28 PROCESS FOR TREATING SKINS, AND SKINS OBTAINED

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EP0410862A1 EP0410862A1 (en) 1991-01-30
EP0410862B1 true EP0410862B1 (en) 1995-07-05

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JP (1) JPH0717920B2 (en)
KR (1) KR950000075B1 (en)
CN (1) CN1049527A (en)
AT (1) ATE124727T1 (en)
AU (1) AU5983990A (en)
BR (1) BR9003683A (en)
CS (1) CS277501B6 (en)
DD (1) DD296705A5 (en)
DE (1) DE69020659D1 (en)
FI (1) FI903775A0 (en)
FR (1) FR2650294B1 (en)
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IE (1) IE902735A1 (en)
IL (1) IL95193A (en)
MA (1) MA21916A1 (en)
NO (1) NO903322L (en)
NZ (1) NZ234621A (en)
PT (1) PT94841A (en)
RO (1) RO109558B1 (en)
RU (1) RU2052507C1 (en)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8011132B2 (en) 2004-12-23 2011-09-06 Becker Underwood Inc. Enhanced shelf life and on seed stabilization of liquid bacterium inoculants
US8020343B2 (en) 2004-12-23 2011-09-20 Becker Underwood Inc. Enhanced shelf life and on seed stabilization of liquid bacterium inoculants

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2650293B1 (en) * 1989-07-28 1994-06-24 Rhone Poulenc Chimie NON-TANNED SKINS, BIOLOGICALLY STABLE, IN WET FORM
FR2790767B1 (en) * 1999-03-11 2001-06-08 Snf Sa USE OF SUPERABSORBENT POLYMERS FOR THE TREATMENT OF RAW SKIN, CORRESPONDING COMPOSITIONS AND METHOD AND SKIN THUS TREATED
KR20040000686A (en) * 2002-06-25 2004-01-07 주식회사 펜타팜 Functional cloth and products for generating anion and far-infrared ray
KR101304797B1 (en) 2005-09-13 2013-09-05 디티에스 엘엘씨 Systems and methods for audio processing
KR101346490B1 (en) 2006-04-03 2014-01-02 디티에스 엘엘씨 Method and apparatus for audio signal processing

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EP0037224A1 (en) * 1980-03-24 1981-10-07 THE PROCTER & GAMBLE COMPANY Rare earth metal carboxylates, their use as antimicrobial agents, and medicinal, cosmetic and cleansing compositions containing them
JPH0634149B2 (en) * 1986-09-02 1994-05-02 日本電気株式会社 Display device
US4743473A (en) * 1987-02-20 1988-05-10 Rhone-Poulenc Inc. Method of preserving wood with lanthanide derivatives

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8011132B2 (en) 2004-12-23 2011-09-06 Becker Underwood Inc. Enhanced shelf life and on seed stabilization of liquid bacterium inoculants
US8020343B2 (en) 2004-12-23 2011-09-20 Becker Underwood Inc. Enhanced shelf life and on seed stabilization of liquid bacterium inoculants

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FR2650294B1 (en) 1991-10-25
ZA905879B (en) 1991-05-29
NO903322D0 (en) 1990-07-26
MA21916A1 (en) 1991-04-01
FR2650294A1 (en) 1991-02-01
BR9003683A (en) 1991-09-03
HU904672D0 (en) 1991-01-28
JPH03115500A (en) 1991-05-16
KR950000075B1 (en) 1995-01-09
ATE124727T1 (en) 1995-07-15
DD296705A5 (en) 1991-12-12
RU2052507C1 (en) 1996-01-20
PT94841A (en) 1991-03-20
NZ234621A (en) 1992-12-23
JPH0717920B2 (en) 1995-03-01
AU5983990A (en) 1991-01-31
CS372990A3 (en) 1992-08-12
CS277501B6 (en) 1993-03-17
IL95193A (en) 1994-05-30
NO903322L (en) 1991-01-29
KR910003117A (en) 1991-02-26
IL95193A0 (en) 1991-06-10
FI903775A0 (en) 1990-07-27
EP0410862A1 (en) 1991-01-30
RO109558B1 (en) 1995-03-30
HUT56399A (en) 1991-08-28
DE69020659D1 (en) 1995-08-10
IE902735A1 (en) 1991-02-27
CN1049527A (en) 1991-02-27

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