ES2583139B1 - METHOD FOR SHORT-TERM CONSERVATION OF LEATHER AND FRESH SKIN - Google Patents
METHOD FOR SHORT-TERM CONSERVATION OF LEATHER AND FRESH SKIN Download PDFInfo
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- 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
Abstract
Método para la conservación a corto plazo de cueros y pieles frescas.#Método para la conservación de cueros y pieles frescas durante un periodo de hasta 10 días mediante el tratamiento de cueros y pieles frescas con una composición acuosa que comprende al menos un agente bactericida seleccionado del grupo que consiste en benzoato sódico, metabisulfito sódico, fluoruro sódico y fluorosilicato sódico y cualquier combinación de los mismos, y al menos un agente quelante seleccionado del grupo que consiste en sales sódicas del ácido etilendiaminotetraacético (EDTA).Method for the short-term preservation of fresh hides and skins # Method for the preservation of fresh hides and skins for a period of up to 10 days by treating fresh hides and skins with an aqueous composition comprising at least one selected bactericidal agent from the group consisting of sodium benzoate, sodium metabisulfite, sodium fluoride and sodium fluorosilicate and any combination thereof, and at least one chelating agent selected from the group consisting of sodium salts of ethylenediaminetetraacetic acid (EDTA).
Description
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DESCRIPCIONDESCRIPTION
METODO PARA LA CONSERVACION A CORTO PLAZO DE CUEROS Y PIELESMETHOD FOR SHORT-TERM CONSERVATION OF LEATHER AND SKIN
FRESCASFRESH
Campo tecnicoTechnical field
La presente invencion se refiere a un metodo para la conservacion de cueros y pieles frescas a corto plazo, es dedr, durante un periodo de hasta 10 d^as, preferentemente de 1 a 6 dias. El metodo es aplicable sin necesidad de complicadas infraestructuras no disponibles en pequenas instalaciones de sacrificio con producciones muy limitadas que no permiten la recogida diaria a centros de conservacion por salado o frio. La presente invencion consigue que los cueros y pieles frescas se conserven sin deterioro hasta su traslado hacia centros de tratamiento por frio o salado, de forma que la logistica resulta mas eficiente.The present invention relates to a method for the preservation of fresh hides and skins in the short term, that is, for a period of up to 10 days, preferably 1 to 6 days. The method is applicable without the need for complicated infrastructure not available in small slaughter facilities with very limited productions that do not allow daily collection to conservation centers by salty or cold. The present invention ensures that fresh hides and skins are preserved without deterioration until they are transferred to cold or salty treatment centers, so that logistics are more efficient.
Antecedentes de la invencionBackground of the invention
La industria tradicional del curtido tiene su materia prima en la piel animal. La parte exterior del cuero de un animal vivo contiene bacterias y otros microorganismos mantenidos bajo control por las defensas inmunologicas del animal. Cuando este muere, el proceso de putrefaction comienza inmediatamente.The traditional tanning industry has its raw material in animal skin. The outer part of a live animal's leather contains bacteria and other microorganisms kept under control by the animal's immune defenses. When he dies, the putrefaction process begins immediately.
El tiempo transcurrido desde el sacrificio del animal hasta la entrada en la cadena de frio o la salazon (que detienen el ataque bacteriano), es critico. La autolisis y el ataque bacteriano de la piel son maximos en el periodo de tiempo que transcurre desde el desuello hasta el momento de la preparation de la conservacion e incluso en las etapas iniciales de esta, ya que en este punto la piel posee toda su humedad y carece de defensas.The time elapsed from the sacrifice of the animal to the entry into the cold chain or salting (which stops the bacterial attack), is critical. The autolysis and the bacterial attack of the skin are maximum in the period of time that elapses from the skinning until the time of the preparation of the preservation and even in the initial stages of this, since at this point the skin has all its moisture and lacks defenses.
El cuero de un animal que se acaba de sacrificar esta constituido por dos tercios de agua y en su superficie se encuentran innumerables bacterias procedentes de los pastizales en los que se ha criado el animal. La sangre, excrementos y contenido intestinal que se encuentra adherido sobre los cueros tras el sacrificio, actuan como alimento de esas bacterias y aceleran la descomposicion del cuero.The leather of an animal that has just been sacrificed is constituted by two thirds of water and on its surface there are innumerable bacteria from the grasslands in which the animal has been raised. The blood, droppings and intestinal contents that are attached to the hides after slaughter, act as food for these bacteria and accelerate the breakdown of the leather.
Por este motivo, se han desarrollado varios metodos para controlar los danos causados porFor this reason, several methods have been developed to control the damage caused by
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la degradation bacteriana en este corto, pero muy importante, periodo de tiempo que va desde el sacrificio del animal hasta la llegada al centro de tratamiento donde se aplican los metodos de conservation habituales.Bacterial degradation in this short, but very important, period of time that goes from the sacrifice of the animal to the arrival at the treatment center where the usual conservation methods are applied.
As^ US 4379709 A describe un metodo para desinfectar y preservar pieles y cueros por contacto con una mezcla de una sal inorganica de zinc y una amida acida primero, y posteriormente con sal comun y un acido con efecto desinfectante y conservante. La eficacia de este tratamiento se puede mejorar con la adicion de conservantes de tipo organico, particularmente acidos carboxflicos.As ^ US 4379709 A describes a method for disinfecting and preserving skins and hides by contact with a mixture of an inorganic salt of zinc and an acidic acid first, and subsequently with common salt and an acid with a disinfectant and preservative effect. The effectiveness of this treatment can be improved with the addition of organic preservatives, particularly carboxylic acids.
Este metodo se centra basicamente en la conservacion por un periodo corto de tiempo (“short-term”), con el objetivo principal de reducir la cantidad de cloruro sodico utilizada en la preservation y previo tratamiento de los cueros en un bano acuoso al que se adicionan una serie de productos quimicos. Sin embargo, este metodo exige la existencia de una infraestructura de tratamiento no disponible habitualmente en centros de production carnicas, y que presupone un costo elevado.This method basically focuses on the conservation for a short period of time (“short-term”), with the main objective of reducing the amount of sodium chloride used in the preservation and prior treatment of the hides in an aqueous bath to which They add a series of chemicals. However, this method requires the existence of a treatment infrastructure not usually available in meat production centers, and that presupposes a high cost.
US 4713078 A (tambien publicada como ES 8706838 A1) divulga un metodo para conservar cueros, pellejos y pieles crudos de animales usando una solution acuosa que contiene un 0,1 % de cianamida y agentes surfactantes. Asi, en este documento se propone un metodo para almacenamiento “short-term” con un uso reducido de cloruro sodico.US 4713078 A (also published as ES 8706838 A1) discloses a method for preserving raw hides, skins and skins of animals using an aqueous solution containing 0.1% cyanamide and surfactants. Thus, this document proposes a method for "short-term" storage with reduced use of sodium chloride.
US 4935031 A propone un metodo de preservacion de corta duration de cueros y pieles utilizando una solucion de un compuesto clorado alcalino, por ejemplo clorito sodico, conteniendo adicionalmente un compuesto fenolico, sulfonados, fosfatos emulsionantes con efecto higroscopico que ayuden a la penetration de la solucion en el cuero. Sin embargo, este metodo implica la preparation de mezclas complejas y una aplicacion manual costosa desde el punto de vista economico.US 4935031 A proposes a method of preservation of short duration of hides and skins using a solution of an alkaline chlorinated compound, for example sodium chlorite, additionally containing a phenolic compound, sulphonates, emulsifying phosphates with hygroscopic effect that help the penetration of the solution in leather However, this method involves the preparation of complex mixtures and an economically expensive manual application.
US 5096553 A divulga un metodo con lavado, descarnado, eliminado del estiercol adherido, para posteriormente sumergirlas en una solucion antiseptica, escurrido del exceso de humedad e irradiado. Sin embargo, el metodo que se describe en este documento presenta una alta complejidad que necesita de instalaciones de irradiation complejas, no disponibles en la mayoria de centros de recoleccion.US 5096553 A discloses a method with washing, decaring, removed from the adhered manure, to subsequently immerse them in an antiseptic solution, drained from excess moisture and irradiated. However, the method described in this document presents a high complexity that requires complex irradiation facilities, not available in most collection centers.
EP 0932704 B1 describe una composition que contiene un antibiotico polieter y unEP 0932704 B1 describes a composition containing a polyether antibiotic and a
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tensoactivo para la conservacion a corto plazo de cueros y pieles. En este documento se describen antecedentes de composiciones para preservar cueros y pieles en las que se anaden aditivos antibacterianos a la sal comun. Estos aditivos incluyen, por ejemplo, el naftaleno, el p-cloro-m-creosol, el fluorosilicato sodico, compuestos de ortanotina, fenoles dorados, derivados de piridina, compuestos de amonio cuaternario, sales de zinc, el acido monocloroacetico.surfactant for the short-term preservation of hides and skins. This document describes background of compositions for preserving leathers and skins in which antibacterial additives are added to common salt. These additives include, for example, naphthalene, p-chloro-m-creosol, sodium fluorosilicate, orthanotine compounds, golden phenols, pyridine derivatives, quaternary ammonium compounds, zinc salts, monochloroacetic acid.
US 6375861 B1 presenta una combinacion de compuestos activos para la conservacion de cueros y pieles que incluye al menos un compuesto fenolico y al menos un compuesto heterodclico de nitrogeno. Adicionalmente, esta patente describe el potencial bacteriostatico-bactericida de diferentes compuestos fenolicos y azoicos para utilizarlos en formulaciones empleadas en procesos de curtido.US 6375861 B1 presents a combination of active compounds for the preservation of hides and skins that includes at least one phenolic compound and at least one heterocyclic nitrogen compound. Additionally, this patent describes the bacteriostatic-bactericidal potential of different phenolic and azo compounds to be used in formulations used in tanning processes.
WO 2014/191862 A1 propone un proceso en seco para preservar cueros y pieles mediante el uso de una composicion seca conservante que incluye un acido solido y una mezcla de cloruro sodico y cloruro de potasio en proporcion variable, de tal manera que se consiga un pH de la piel de 3,5. Este metodo es aplicable sobre pieles ovinas y/o caprinas y no sobre cueros vacunos. Asimismo, la exigencia de una determinacion previa de la humedad antes de la aplicacion del metodo de conservacion, hace que sea un metodo "de laboratorio” mas que de uso practico industrial, donde el estado de la materia prima puede variar sustancialmente segun distintos factores (ej. areas, origenes, temporadas, etc).WO 2014/191862 A1 proposes a dry process to preserve hides and skins by using a dry preservative composition that includes a solid acid and a mixture of sodium chloride and potassium chloride in varying proportions, so that a pH is achieved of the skin of 3.5. This method is applicable on sheep and / or goatskins and not on cattle hides. Likewise, the requirement of a previous determination of the humidity before the application of the conservation method, makes it a "laboratory" method rather than a practical industrial use, where the state of the raw material can vary substantially according to different factors ( eg areas, origins, seasons, etc).
Asi, la presente invencion se refiere a un metodo de conservacion a corto plazo o "short term”, en particular durante un periodo de hasta 10 dias, preferiblemente entre 1 y 6 dias, por tratamiento, en particular mediante inmersion, pulverizacion o irrigacion, de cueros o pieles de animales recien sacrificados con soluciones acuosas de diferentes productos, o de sus combinaciones, que permite un rapido tratamiento bacteriostatico o bactericida. La aplicacion del metodo de la presente invencion inmediatamente despues del sacrificio del animal facilita una logistica eficiente en la recogida, manipulacion y traslado de las pieles y cueros frescos hasta los centros de tratamiento por frio o salado en condiciones optimas de conservacion a temperatura ambiente.Thus, the present invention relates to a short term or "short term" preservation method, in particular for a period of up to 10 days, preferably between 1 and 6 days, per treatment, in particular by immersion, spraying or irrigation, of leathers or skins of animals recently slaughtered with aqueous solutions of different products, or of their combinations, which allows a rapid bacteriostatic or bactericidal treatment.The application of the method of the present invention immediately after the slaughter of the animal facilitates efficient logistics in the collection , handling and transfer of fresh skins and leathers to cold or salty treatment centers under optimal conditions of preservation at room temperature.
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DefinicionesDefinitions
A efectos de esta patente, se entiende por cuero fresco o crudo y piel fresca o cruda el pellejo de un animal que no ha sido sometido a ningun proceso de conservation.For the purposes of this patent, fresh or raw leather and fresh or raw skin are understood as the skin of an animal that has not undergone any conservation process.
A efectos de esta patente, cuero curtido y piel curtida se refieren al pellejo de un animal trasformado por un proceso fisico-quimico de curtido.For the purposes of this patent, tanned leather and tanned skin refer to the skin of an animal transformed by a physical-chemical tanning process.
A efectos de la presente invention, cuero se refiere preferentemente y de manera no excluyente a pellejos de un animal de gran tamano, por ejemplo pellejos bovinos y/o equinos.For the purposes of the present invention, leather preferably and non-exclusively refers to skin of a large animal, for example bovine and / or equine skin.
A efectos de la presente invencion, piel se refiere preferentemente y de manera no excluyente a pellejos de un animal de pequeno tamano, por ejemplo pellejos ovinos y/o caprinos.For the purposes of the present invention, skin preferably and non-exclusively refers to skins of a small animal, for example sheep and / or goatskins.
Description de la invencionDescription of the invention
La presente invencion se refiere a un metodo para la conservacion de cueros y pieles frescas procedentes de animales sacrificados, preferentemente el metodo de la invencion se aplica en el plazo maximo de una hora tras el desuello, mediante el tratamiento de las pieles y cueros frescas con una composition acuosa que comprende al menos un agente bactericida seleccionado del grupo que consiste en benzoato sodico, metabisulfito sodico, fluoruro sodico, fluorosilicato sodico y cualquier combination de los mismos; y al menos un agente quelante seleccionado del grupo que consiste en sales sodicas del acido etilendiaminotetraacetico (EDTA), preferentemente, sales di- o tri-sodicas de EDTA. Sin embargo, aunque se prefiere la utilization de sales sodicas de EDTA, en el metodo de la presente invencion tambien podria utilizarse NTA (Acido Nitrilo Triacetico), DTPA (Acido dietilen triamino pentacetico), STPP (Tripolifosfato de Sodio) como agentes quelantes.The present invention relates to a method for the preservation of fresh hides and skins from slaughtered animals, preferably the method of the invention is applied within a maximum period of one hour after skinning, by treating the skins and fresh hides with an aqueous composition comprising at least one bactericidal agent selected from the group consisting of sodium benzoate, sodium metabisulfite, sodium fluoride, sodium fluorosilicate and any combination thereof; and at least one chelating agent selected from the group consisting of sodium salts of ethylenediaminetetraacetic acid (EDTA), preferably di- or tri-sodium salts of EDTA. However, although the use of sodium salts of EDTA is preferred, in the method of the present invention NTA (Triacetic Nitrile Acid), DTPA (Pentacetic triamine diethylene acid), STPP (Sodium Tripolyphosphate) could also be used as chelating agents.
En la presente invencion, las sales del EDTA tienen un importante efecto potenciador de bactericidas especialmente frente a bacterias gram-negativas que son las mas abundantes en la superficie del cuero, especialmente las Pseudomonas. Dichas sales poseen un poder secuestrante de iones Mg y Ca que provoca una solubilization parcial de las paredesIn the present invention, EDTA salts have an important bactericide enhancing effect especially against gram-negative bacteria that are the most abundant on the surface of the leather, especially Pseudomonas. Said salts possess a sequestering power of Mg and Ca ions that causes a partial solubilization of the walls.
celulares de las bacterias, aumentando su permeabilidad a los biocidas presentes. Elbacteria cells, increasing their permeability to the biocides present. He
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mecanismo de accion del EDTA esta basado en su accion extracelular, y en la absorcion y precipitacion intracelular de quelatos metalicos teniendo un espectro de accion mas amplio que otros agentes quelantes.EDTA's mechanism of action is based on its extracellular action, and on the intracellular absorption and precipitation of metal chelates having a broader spectrum of action than other chelating agents.
En realizaciones preferidas de la presente invention, el metodo de conservation que se describe en este documento comprende el tratamiento de las pieles y cueros frescas mediante inmersion, pulverization o irrigation de la composition acuosa. En particular, en aquellas realizaciones en las que el tratamiento se realiza por pulverizacion o irrigacion, la composicion acuosa se aplica por la parte del cuero donde se encuentra el pelo.In preferred embodiments of the present invention, the conservation method described herein comprises the treatment of fresh skins and leathers by immersion, pulverization or irrigation of the aqueous composition. In particular, in those embodiments in which the treatment is carried out by spraying or irrigation, the aqueous composition is applied by the part of the leather where the hair is located.
Las pieles y cueros tratados mediante pulverizacion o irrigacion se pueden conservar a una temperatura entre 15 y 40°C durante un periodo de 5 dias, preferentemente hasta 3 dias, antes de realizar el tratamiento posterior que permita su conservacion por periodos mas largos. De forma particularmente ventajosa, las pieles y cueros tratados mediante inmersion en la composicion acuosa se pueden conservar a temperatura ambiente, en particular entre 15 y 40°C, durante un periodo de hasta 10 dias, sin que se produzcan degradaciones por autolisis o degradaciones bacterianas. De esta forma, tanto si el tratamiento se realiza por inmersion, como si se realiza por pulverizacion o irrigacion, es posible transportar las pieles y cueros tratados sin necesidad de refrigeration hacia centros de curtido o hacia centros de recoleccion donde se les de un tratamiento posterior que permita su conservacion por periodos de tiempo mas largos.The skins and leathers treated by spraying or irrigation can be stored at a temperature between 15 and 40 ° C for a period of 5 days, preferably up to 3 days, before carrying out the subsequent treatment that allows their preservation for longer periods. Particularly advantageously, skins and hides treated by immersion in the aqueous composition can be stored at room temperature, in particular between 15 and 40 ° C, for a period of up to 10 days, without causing autolysis or bacterial degradation. . In this way, whether the treatment is carried out by immersion, as if it is carried out by spraying or irrigation, it is possible to transport the treated skins and leathers without the need for refrigeration to tanning centers or to collection centers where they are given a subsequent treatment that allows its preservation for longer periods of time.
En una realization preferida de la presente invencion, el tratamiento de los cueros y pieles frescas con la composicion acuosa tiene lugar a una temperatura ambiente de entre 25 y 40 °C. De esta forma se aumenta la accion preservante de la composicion acuosa.In a preferred embodiment of the present invention, the treatment of fresh hides and skins with the aqueous composition takes place at an ambient temperature between 25 and 40 ° C. In this way the preservative action of the aqueous composition is increased.
En otra realizacion preferida, el metodo para la conservacion que se describe en esta solicitud comprende la inmersion de los cueros y pieles frescas en la composicion acuosa durante un periodo mmimo de 24 horas. Pasado este tiempo los cueros y las pieles tratadas se pueden sacar de la solution y conservarse entre 15 y 35 °C, mas preferentemente entre 20 y 25°C. De forma alternativa, los cueros y pieles tambien pueden conservarse en la solucion acuosa que se describe en esta solicitud de patentes.In another preferred embodiment, the method of preservation described in this application comprises immersion of the fresh hides and skins in the aqueous composition for a minimum period of 24 hours. After this time, the treated hides and skins can be removed from the solution and stored between 15 and 35 ° C, more preferably between 20 and 25 ° C. Alternatively, the hides and skins can also be stored in the aqueous solution described in this patent application.
En otra realizacion preferida, el metodo para la conservacion que se describe en estaIn another preferred embodiment, the method of preservation described in this
solicitud comprende pulverizacion o irrigacion de los cueros y pieles frescas, por la parterequest includes spraying or irrigating fresh leathers and skins, on the part
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donde esta el pelo, en la composition acuosa a razon de 0,5 a 1,5 litros de composition por m2 de superficie del cuero o piel a tratar, preferentemente entre 0,75 litro/m2 y 1,0 litro/m2. Posteriormente, los cueros se pueden plegar para su almacenamiento y transporte, preferentemente segun el eje cabeza-cola, manteniendo el pelo en el interior del pliegue.where the hair is, in the aqueous composition at a rate of 0.5 to 1.5 liters of composition per m2 of surface of the leather or skin to be treated, preferably between 0.75 liter / m2 and 1.0 liter / m2. Subsequently, the leathers can be folded for storage and transport, preferably according to the head-tail axis, keeping the hair inside the fold.
De manera preferida, cuando el metodo comprende el tratamiento de los cueros y pieles frescas por inmersion, la concentration del agente bactericida en la composicion acuosa es de entre 1.000 y 50.000 ppm. En particular, en aquellas realizaciones de la invention en las que el agente bactericida es benzoato sodico, fluoruro sodico, metabisulfito sodico o una combinacion cualquiera de los anteriores, la concentracion del agente bactericida en la composicion acuosa es preferentemente de entre 2.000 y 50.000 ppm y, mas preferentemente, de entre 15.000 y 25.000 ppm. Por otro lado, en aquellas realizaciones particulares de la invencion en las que el agente bactericida es silicofluoruro sodico, la concentracion del agente bactericida en la composicion acuosa es preferentemente de entrePreferably, when the method comprises the treatment of fresh hides and skins by immersion, the concentration of the bactericidal agent in the aqueous composition is between 1,000 and 50,000 ppm. In particular, in those embodiments of the invention in which the bactericidal agent is sodium benzoate, sodium fluoride, sodium metabisulfite or any combination of the foregoing, the concentration of the bactericidal agent in the aqueous composition is preferably between 2,000 and 50,000 ppm and , more preferably, between 15,000 and 25,000 ppm. On the other hand, in those particular embodiments of the invention in which the bactericidal agent is sodium silicofluoride, the concentration of the bactericidal agent in the aqueous composition is preferably between
1.000 y 6.000 ppm y mas preferentemente de entre 2.500 y 4.000 ppm.1,000 and 6,000 ppm and more preferably between 2,500 and 4,000 ppm.
En otras realizaciones particulares de la invencion, cuando el metodo comprende el tratamiento de los cueros y pieles frescas por inmersion y, preferentemente, la concentracion de agente bactericida es tal como se define en el parrafo anterior, la concentracion del agente quelante en la composicion acuosa es de entre 1.000 y 10.000 ppm, mas preferentemente de entre 4.000 y 6.000 ppm.In other particular embodiments of the invention, when the method comprises the treatment of fresh hides and skins by immersion and, preferably, the concentration of bactericidal agent is as defined in the preceding paragraph, the concentration of the chelating agent in the aqueous composition it is between 1,000 and 10,000 ppm, more preferably between 4,000 and 6,000 ppm.
De forma alternativa, cuando el metodo para la conservation de pieles y cueros frescos que aqu se describe comprende el tratamiento mediante pulverization o irrigation, la concentracion del agente bactericida en la composicion acuosa es de entre 5.000 y 50.000 ppm. En particular, en aquellas realizaciones de la invencion en las que el agente bactericida es benzoato sodico, fluoruro sodico, metabisulfito sodico o una combination cualquiera de los anteriores, la concentracion del agente bactericida en la composicion acuosa es preferentemente de entre 20.000 y 50.000 ppm y, mas preferentemente, de entreAlternatively, when the method for the conservation of fresh skins and leathers described herein comprises the treatment by spraying or irrigation, the concentration of the bactericidal agent in the aqueous composition is between 5,000 and 50,000 ppm. In particular, in those embodiments of the invention in which the bactericidal agent is sodium benzoate, sodium fluoride, sodium metabisulfite or any combination of the foregoing, the concentration of the bactericidal agent in the aqueous composition is preferably between 20,000 and 50,000 ppm and , more preferably, between
25.000 y 35.000 ppm.25,000 and 35,000 ppm.
En otras realizaciones particulares de la invencion, cuando el metodo comprende el tratamiento de los cueros y pieles frescas por pulverizacion o irrigacion y, preferentemente, la concentracion de agente bactericida es tal como se define en el parrafo anterior, laIn other particular embodiments of the invention, when the method comprises the treatment of fresh hides and skins by spraying or irrigation and, preferably, the concentration of bactericidal agent is as defined in the preceding paragraph, the
concentracion del agente quelante en la composicion acuosa es de entre 2.000 y 20.000concentration of the chelating agent in the aqueous composition is between 2,000 and 20,000
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ppm, mas preferentemente de entre 6.000 y 10.000 ppm.ppm, more preferably between 6,000 and 10,000 ppm.
Adicionalmente, esta solicitud de patente tambien se refiere a una composition acuosa para la conservation de cueros y pieles frescas, que comprende al menos un agente bactericida seleccionado del grupo que consiste en benzoato sodico, metabisulfito sodico, fluoruro sodico y fluorosilicato sodico y cualquier combination de los mismos, y al menos un agente quelante seleccionado del grupo que consiste en sales sodicas del acido etilendiaminotetraacetico (EDTA).Additionally, this patent application also refers to an aqueous composition for the conservation of fresh hides and skins, comprising at least one bactericidal agent selected from the group consisting of sodium benzoate, sodium metabisulfite, sodium fluoride and sodium fluorosilicate and any combination of the same, and at least one chelating agent selected from the group consisting of sodium salts of ethylenediaminetetraacetic acid (EDTA).
En una realization preferida de la presente invention, la composicion acuosa comprende una concentration de agente bactericida entre 1.000 y 50.000 ppm. Mas preferentemente entre 15.000 y 50.000 ppm, cuando el agente bactericida se selecciona del grupo que consiste en benzoato sodico, metabisulfito sodico, fluoruro sodico y una combinacion de los anteriores; y una concentracion entre 1.000 y 6.000 ppm, cuando el agente bactericida es silicofluoruro sodico.In a preferred embodiment of the present invention, the aqueous composition comprises a concentration of bactericidal agent between 1,000 and 50,000 ppm. More preferably between 15,000 and 50,000 ppm, when the bactericidal agent is selected from the group consisting of sodium benzoate, sodium metabisulfite, sodium fluoride and a combination of the foregoing; and a concentration between 1,000 and 6,000 ppm, when the bactericidal agent is sodium silicofluoride.
En particular, cuando la composicion acuosa comprende entre 15.000 y 25.000 ppm de un agente bactericida seleccionado entre benzoato sodico, metabisulfito sodico, fluoruro sodico y una combinacion de los anteriores, esta composicion resulta particularmente ventajosa para utilizar en el metodo para la conservacion de pieles y cueros frescos mediante inmersion de las pieles y cueros frescos en la composicion acuosa.In particular, when the aqueous composition comprises between 15,000 and 25,000 ppm of a bactericidal agent selected from sodium benzoate, sodium metabisulfite, sodium fluoride and a combination of the above, this composition is particularly advantageous for use in the method for the preservation of skins and fresh leathers by immersion of the skins and fresh leathers in the aqueous composition.
Por otro lado, cuando la composicion acuosa comprende entre 25.000 y 50.000 ppm de un agente bactericida seleccionado entre benzoato sodico, metabisulfito sodico, fluoruro sodico y una combinacion de los anteriores, esta composicion resulta particularmente ventajosa para utilizar en el metodo para la conservacion de pieles y cueros frescos mediante pulverization o irrigation de la composicion acuosa sobre las pieles y cueros frescos.On the other hand, when the aqueous composition comprises between 25,000 and 50,000 ppm of a bactericidal agent selected from sodium benzoate, sodium metabisulfite, sodium fluoride and a combination of the above, this composition is particularly advantageous for use in the method for the preservation of skins. and fresh leathers by pulverization or irrigation of the aqueous composition on fresh leathers and leathers.
En otras realizacion particulares de la invencion, la concentracion del agente quelante en la composicion acuosa es de entre 1.000 y 20.000 ppm. En particular, cuando la composicion acuosa comprende entre 1.000 y 10.000 ppm, mas preferentemente de entre 4.000 y 6.000 ppm del agente quelante, esta composicion resulta particularmente ventajosa para utilizar en el metodo para la conservacion de pieles y cueros frescos mediante inmersion en la composicion acuosa.In other particular embodiments of the invention, the concentration of the chelating agent in the aqueous composition is between 1,000 and 20,000 ppm. In particular, when the aqueous composition comprises between 1,000 and 10,000 ppm, more preferably between 4,000 and 6,000 ppm of the chelating agent, this composition is particularly advantageous for use in the method for the preservation of fresh skins and leathers by immersion in the aqueous composition. .
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Por otro lado, cuando la composition acuosa comprende entre 2.000 y 20.000 ppm, mas preferentemente de entre 6.000 y 10.000 ppm del agente quelante, esta composicion resulta particularmente ventajosa para utilizar en el metodo para la conservation de pieles y cueros frescos mediante pulverization o irrigation de la composicion acuosa sobre las pieles y cueros frescos.On the other hand, when the aqueous composition comprises between 2,000 and 20,000 ppm, more preferably between 6,000 and 10,000 ppm of the chelating agent, this composition is particularly advantageous for use in the method for the conservation of fresh skins and leathers by pulverization or irrigation of the aqueous composition on the skins and fresh leathers.
A no ser que se indique expresamente lo contrario, las concentraciones que se incluyen en la presente solicitud de patente estan expresadas en peso respecto al peso total de la composicion acuosa (ppm).Unless expressly stated otherwise, the concentrations included in the present patent application are expressed by weight with respect to the total weight of the aqueous composition (ppm).
EjemplosExamples
Se describen a continuation una serie de ejemplos de la presente invention, si bien el alcance de la misma no se encuentra limitado a los detalles de los ejemplos en modo alguno.A series of examples of the present invention are described below, although the scope thereof is not limited to the details of the examples in any way.
EJEMPLO 1: Se toman cueros de vacuno, machos y hembras, de un rango de pesos en fresco de 20 a 30 kg, procedentes de animales del Centro de Espana que fueron sacrificados durante el mes de Julio, con temperaturas ambientes de entre 30 y 35°C. Los animales fueron sacrificados en un plazo de entre 30 y 60 minutos antes de su inmersion en bano de la composicion preservante, con una temperatura de los cueros entre 33-35°C y un tercio de ellos aproximadamente con restos de estiercol adheridos a la piel. Los cueros se introdujeron en la composicion acuosa tal y como procedian de la lmea de matanza sin ninguna limpieza posterior al sacrificio y anterior a la inmersion en bano. La relation en peso entre cuero fresco/composicion preservante era de 2:1, la composicion acuosa estaba a una temperatura de bano de 18°C, y contema 20.000 ppm de benzoato sodico como agente bactericida y 5.000 ppm de la sal tri-sodica del acido etilendiaminotetraacetico (EDTA) como agente quelante. Los cueros se mantuvieron en la solution acuosa durante un periodo de 24 horas y a una temperatura del bano entre 25 y 30°C durante un periodo de 4 dias. Posteriormente, los cueros se extrajeron de la solucion acuosa y se conservaron entre 20 y - 30°C por un periodo de hasta 6 dias despues de su extraction del bano.EXAMPLE 1: Beef, male and female leathers of a fresh weight range of 20 to 30 kg are taken from animals from the Center of Spain that were slaughtered during the month of July, with ambient temperatures between 30 and 35 ° C. The animals were sacrificed within 30 to 60 minutes before immersion in the bath of the preservative composition, with a temperature of the leathers between 33-35 ° C and about a third of them with remains of manure attached to the skin . The leathers were introduced into the aqueous composition as they came from the slaughter line without any cleaning after slaughter and prior to bath immersion. The weight ratio between fresh leather / preservative composition was 2: 1, the aqueous composition was at a bath temperature of 18 ° C, and contained 20,000 ppm of sodium benzoate as a bactericidal agent and 5,000 ppm of the tri-sodium salt of the ethylenediaminetetraacetic acid (EDTA) as chelating agent. The leathers were kept in the aqueous solution for a period of 24 hours and at a bath temperature between 25 and 30 ° C for a period of 4 days. Subsequently, the leathers were extracted from the aqueous solution and kept between 20 and -30 ° C for a period of up to 6 days after their bath extraction.
EJEMPLO 2: Se siguio el procedimiento descrito en detalle en el ejemplo 1, utilizando una composicion acuosa que contema 20.000 ppm de fluoruro sodico como agente bactericida yEXAMPLE 2: The procedure described in detail in Example 1 was followed, using an aqueous composition containing 20,000 ppm of sodium fluoride as a bactericidal agent and
5.000 ppm de la sal tri-sodica del acido etilendiaminotetraacetico (EDTA) como agente5,000 ppm of the tri-sodium salt of ethylenediaminetetraacetic acid (EDTA) as an agent
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quelante.chelator
EJEMPLO 3: Se siguio el procedimiento descrito en detalle en el ejemplo 1, utilizando una composition acuosa que contema 3.500 ppm de silicofluoruro sodico como agente bactericida y 5.000 ppm de la sal tri-sodica del acido etilendiaminotetraacetico (EDTA) como agente quelante.EXAMPLE 3: The procedure described in detail in Example 1 was followed, using an aqueous composition containing 3,500 ppm of sodium silicofluoride as a bactericidal agent and 5,000 ppm of the tri-sodium salt of ethylenediaminetetraacetic acid (EDTA) as a chelating agent.
EJEMPLO 4: Se siguio el procedimiento descrito en detalle en el ejemplo 1, utilizando una composicion acuosa que contema 20.000 ppm de metabisulfito sodico como agente bactericida y 5.000 ppm de la sal tri-sodica del acido etilendiaminotetraacetico (EDTA) como agente quelante.EXAMPLE 4: The procedure described in detail in Example 1 was followed, using an aqueous composition containing 20,000 ppm of sodium metabisulfite as a bactericidal agent and 5,000 ppm of the tri-sodium salt of ethylenediaminetetraacetic acid (EDTA) as a chelating agent.
EJEMPLO 5: Se toman cueros vacunos, machos y hembras, de un rango de pesos en fresco de 20 a 30 kg, procedentes de animales del Centro de Espana que fueron sacrificados durante el mes de Julio, con temperaturas ambientes de 30-35°C. Los animales fueron sacrificados en un plazo de entre 30 y 60 minutos antes de la inmersion de los cueros en el bano con la composicion preservante, con una temperatura de los cueros entre 33- 35°C, y un tercio de ellos aproximadamente con restos de estiercol adheridos a la piel. Los cueros se introdujeron en la composicion acuosa tal y como procedian de la lmea de matanza sin ninguna limpieza posterior al sacrificio y anterior a la inmersion en bano, La relation en peso entre cuero fresco/composicion preservante era de 2:1, la composicion acuosa estaba a una temperatura de bano de 18°C, y contema 20.000 ppm de benzoato sodico como agente bactericida y 5.000 ppm de la sal tri-sodica del acido etilendiaminotetraacetico (EDTA) como agente quelante. Los cueros se mantuvieron en la solution acuosa durante un periodo de 7 dias y a una temperatura del bano entre 20 y 25°C Posteriormente, los cueros se extrajeron de la solucion acuosa y se conservaron entre 20 y 30°C por un periodo de hasta 3 dias despues de su extraction del bano.EXAMPLE 5: Cattle, male and female leathers, from a fresh weight range of 20 to 30 kg, are taken from animals from the Center of Spain that were slaughtered during the month of July, with ambient temperatures of 30-35 ° C . The animals were slaughtered within 30 to 60 minutes before the immersion of the leathers in the bathroom with the preservative composition, with a temperature of the leathers between 33-35 ° C, and about a third of them with remains of manure attached to the skin. The leathers were introduced into the aqueous composition as they came from the slaughter line without any cleaning after slaughter and prior to bath immersion. The weight ratio between fresh leather / preservative composition was 2: 1, the aqueous composition it was at a bath temperature of 18 ° C, and contained 20,000 ppm of sodium benzoate as a bactericidal agent and 5,000 ppm of the tri-sodium salt of ethylenediaminetetraacetic acid (EDTA) as a chelating agent. The leathers were kept in the aqueous solution for a period of 7 days and at a bath temperature between 20 and 25 ° C Subsequently, the leathers were extracted from the aqueous solution and kept between 20 and 30 ° C for a period of up to 3 days after his bath extraction.
EJEMPLO 6: Se siguio el procedimiento descrito en detalle en el ejemplo 5, utilizando una composicion acuosa que contema 20.000 ppm de fluoruro sodico como agente bactericida yEXAMPLE 6: The procedure described in detail in Example 5 was followed, using an aqueous composition containing 20,000 ppm of sodium fluoride as a bactericidal agent and
5.000 ppm de la sal tri-sodica del acido etilendiaminotetraacetico (EDTA) como agente quelante.5,000 ppm of the tri-sodium salt of ethylenediaminetetraacetic acid (EDTA) as a chelating agent.
EJEMPLO 7: Se siguio el procedimiento descrito en detalle en el ejemplo 5, utilizando unaEXAMPLE 7: The procedure described in detail in example 5 was followed, using a
composicion acuosa que contema 3.500 ppm de silicofluoruro sodico como agenteaqueous composition containing 3,500 ppm of sodium silicofluoride as an agent
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bactericida y 5.000 ppm de la sal tri-sodica del acido etilendiaminotetraacetico (EDTA) como agente quelante.bactericidal and 5,000 ppm of the tri-sodium salt of ethylenediaminetetraacetic acid (EDTA) as a chelating agent.
EJEMPLO 8: Se siguio el procedimiento descrito en detalle en el ejemplo 5, utilizando una composition acuosa que contema 20.000 ppm de metabisulfito sodico como agente bactericida y 5.000 ppm de la sal tri-sodica del acido etilendiaminotetraacetico (EDTA) como agente quelante.EXAMPLE 8: The procedure described in detail in Example 5 was followed, using an aqueous composition containing 20,000 ppm of sodium metabisulfite as a bactericidal agent and 5,000 ppm of the tri-sodium salt of ethylenediaminetetraacetic acid (EDTA) as a chelating agent.
Los cueros procesados segun se describe en los ejemplos 1-9 se procesaron, curtiendolos al cromo y evaluando su estado de conservation, sin apreciar ningun dano por ese objeto. Posteriormente se siguio el proceso normal de fabrication, con un re-curtido mixto cromo- sintetico y evaluando el estado de los cueros tras el tenido y secado, sin que se observara ninguna incidencia en cuanto al estado de conservacion de los mismos, ni diferencias apreciables entre los procesos seguidos en los ejemplos 1-4. Tampoco se observaron diferencias en comparacion con cueros procesados por el mismo metodo de curtido, que no han sido sometidos previamente a los tratamientos de conservacion detallados en esta solicitud de patente.The processed leathers as described in examples 1-9 were processed, tanning them to the chrome and evaluating their conservation status, without appreciating any damage for that object. Subsequently, the normal manufacturing process was followed, with a mixed chromosynthetic re-tanning and evaluating the condition of the leather after it had been dried and dried, without observing any incidence regarding the state of preservation of the leather, nor appreciable differences between the processes followed in examples 1-4. Nor were differences observed in comparison with leathers processed by the same tanning method, which have not previously undergone the preservation treatments detailed in this patent application.
EJEMPLO 9: Se toman cueros de vacuno, machos y hembras, de un rango de pesos en fresco de 20 a 30 kg, procedentes de animales del Centro de Espana que fueron sacrificados durante el mes de Julio, con temperaturas ambientes de entre 30 y 35°C. Los animales fueron sacrificados en un plazo de entre 30 y 60 minutos antes de su tratamiento con un pulverizador a una presion de 4 bares, por la parte del pelo de la composicion preservante y una cantidad de 3 litros por cuero, con un area estimada de los mismos de 3,5 m2 con una temperatura de los cueros entre 33-35°C y un tercio de ellos aproximadamente con restos de estiercol adheridos a la piel. Los cueros se trataron de la forma descrita tal y como procedian de la lmea de matanza sin ninguna limpieza posterior al sacrificio y anterior a la pulverization. El composicion acuosa reservante se preparo con agua de red a una temperatura de 18°C, y contenia 30.000 ppm de benzoato sodico como agente bactericida yEXAMPLE 9: Cow hides, male and female, of a range of fresh weights of 20 to 30 kg are taken, from animals from the Center of Spain that were slaughtered during the month of July, with ambient temperatures between 30 and 35 ° C. The animals were slaughtered within a period of 30 to 60 minutes before their treatment with a spray at a pressure of 4 bars, for the part of the hair of the preservative composition and an amount of 3 liters per leather, with an estimated area of the same of 3.5 m2 with a temperature of the leathers between 33-35 ° C and about a third of them with remains of manure attached to the skin. The leathers were treated as described as they came from the slaughter line without any cleaning after slaughter and prior to pulverization. The reserve aqueous composition was prepared with network water at a temperature of 18 ° C, and contained 30,000 ppm of sodium benzoate as a bactericidal agent and
7.000 ppm de la sal tri-sodica del acido etilendiaminotetraacetico (EDTA) como agente quelante. Los cueros se plegaron tras el tratamiento siguiendo el eje cabeza-cola, y posteriormente de forma trasversal, formando un paquete con 4 dobles y con el pelo al interior, se almacenaron apilados en un box estanco, pulverizandose la parte de la carne con 1 litro/cuero al apilarse, se conservaron entre 20 y -30°C por un periodo de hasta 5 dias despues de su tratamiento.7,000 ppm of the tri-sodium salt of ethylenediaminetetraacetic acid (EDTA) as a chelating agent. The leathers were folded after the treatment following the head-tail axis, and subsequently in a transverse way, forming a package with 4 doubles and with the hair inside, they were stored stacked in a sealed box, pulverizing the part of the meat with 1 liter / leather when stacked, they were stored between 20 and -30 ° C for a period of up to 5 days after their treatment.
EJEMPLO 10: Se siguio el procedimiento descrito en detalle en el ejemplo 9, utilizando una composition acuosa que contema 30.000 ppm de metabisulfito sodico como agente bactericida y 7.000 ppm de la sal tri-sodica del acido etilendiaminotetraacetico (EDTA) como 5 agente quelante.EXAMPLE 10: The procedure described in detail in Example 9 was followed, using an aqueous composition containing 30,000 ppm of sodium metabisulfite as a bactericidal agent and 7,000 ppm of the tri-sodium salt of ethylenediaminetetraacetic acid (EDTA) as a chelating agent.
EJEMPLO 11: Se siguio el procedimiento descrito en detalle en el ejemplo 9, utilizando una composicion acuosa que contema 30.000 ppm de fluoruro sodico como agente bactericida yEXAMPLE 11: The procedure described in detail in Example 9 was followed, using an aqueous composition containing 30,000 ppm of sodium fluoride as a bactericidal agent and
7.000 ppm de la sal tri-sodica del acido etilendiaminotetraacetico (EDTA) como agente 10 quelante7,000 ppm of the tri-sodium salt of ethylenediaminetetraacetic acid (EDTA) as a chelating agent
Los cueros procesados segun se describen en los ejemplos 9 a 11 se procesaron, curtiendolos al cromo y evaluando su estado de conservation, sin apreciar ningun dano por ese objeto. Posteriormente se siguio el proceso normal de fabrication, con un re-curtido 15 mixto cromo-sintetico y evaluando el estado de los cueros tras el tenido y secado, sin que se observara ninguna incidencia en cuanto al estado de conservacion de los mismos, ni diferencias apreciables entre los procesos seguidos en los ejemplos 1-8. Tampoco se observaron diferencias en comparacion con cueros procesados por el mismo metodo de curtido, que no han sido sometidos previamente a los tratamientos de conservacion 20 detallados en esta solicitud de patente.The processed leathers as described in examples 9 to 11 were processed, tanning them to the chrome and evaluating their conservation status, without appreciating any damage for that object. Subsequently, the normal manufacturing process was followed, with a mixed chrome-synthetic re-tanning and evaluating the condition of the leather after it had been dried and dried, without observing any incidence regarding the state of preservation of the leather, or differences appreciable among the processes followed in examples 1-8. Nor were differences observed in comparison with leathers processed by the same tanning method, which have not previously undergone the preservation treatments detailed in this patent application.
Claims (15)
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| US20060112494A1 (en) * | 2004-12-01 | 2006-06-01 | David Oppong | Method of protecting an animal skin product from metalloproteinase activity |
| US20150361514A1 (en) * | 2014-06-17 | 2015-12-17 | The United States Of America, As Represented By The Secretary Of Agriculture | Methods For Preserving Untanned Animal Hides |
| ES2538029B1 (en) * | 2015-05-21 | 2016-04-05 | Comercial E Industrial García Sánchez, S.A. | Method for improving salting of hides and skins by adding bactericidal agents to sodium chloride |
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