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
  • C14C1/00—Chemical treatment prior to tanning
  • C14C1/02—Curing raw hides

Definitions

• the present invention relates to leather processing and in particular, to a method of
• microorganisms such as bacteria and fungi may come from many sources, including the animal
• Proteins constitute about 33% of the composition of fresh hides
• Finished leather is primarily collagen, which is
• finished leather is primarily collagen, damage to skins and hides from collagenase produced by microorganisms during stages of processing and
• preservatives may work well in inhibiting or killing microorganisms, they are generally not
• enzymes can remain active and can cause damage even after the microorganisms that produced
• Collagenase belongs to the class of proteins known as metalloproteinases, which are proteases that require the presence of a metal ion in order to function. It has been previously
• aminocarboxylic acid derivatives such as
• EDTA ethylenediaminetetraacetic acid
• EGTA tetraacetic acid
• aminocarboxylic acid derivatives as collagenase inhibitors has not been known or appreciated in
• proteolytic enzymes such as metalloproteinases that come into contact with the skins and hides or that are present in fluids or surfaces with which the skins and hides come into contact
• metalloproteinases that are produced by microorganisms or that are endogenous enzymes that
• a feature of the present invention is to provide a composition and method for protecting animal skins and hides from proteolytic enzymes such as metalloproteinases that are produced by microorganisms that come into contact with the skins and hides or that are present
• the present invention further provides a composition and method to protect skins and
• the present invention further provides a composition and method to protect skins and
• the present invention provides a method of
• the method includes applying a solution containing at
• At least one metalloproteinase inhibitor to the animal skin or hide or to a fluid or solid surface that
• the present invention further provides a method of preventing or inhibiting putrefaction, degradation or deterioration of an animal skin or hide, the method comprising
• animal skin or hide or to a fluid or solid surface that contacts the animal skin or hide.
• the present invention further provides a method of producing leather including the
• a solution containing at least one metalloproteinase inhibitor is
• the present invention further provides a composition containing at least an aqueous
• the dipping or soaking solution contains at least one metalloproteinase inhibitor.
• the present invention further provides a composition containing an animal skin or
• hide having a solution containing at least one metalloproteinase inhibitor applied to at least one
• the present invention is directed to a method of treating an animal skin or hide to
• skin As used herein, the terms “skin,” “animal skin,” “hide,” or “animal hide” are all used interchangeably to refer to the flayed or stripped skin or outer layer of an animal, particularly of
• leather examples include, but are not limited to, cattle, pigs, deer, kangaroos, goats,
• the method of the present invention can be carried out at any time after an animal
• leather processing for example, an animal skin or hide is detached from a fallen or slaughtered
• the animal skin or hide may be stored or transported
• a skin or hide can be treated with a metalloproteinase inhibitor according to method of the present invention at least once between the time that a skin or hide is stripped
• the method of the present invention is not limited to leather processing and can be
• present invention can be used if a skin or hide is to be dried without tanning.
• inhibitor is applied to an animal skin or hide or to a fluid that contacts the skin or hide or to a
• proteolytic enzyme refers to any enzyme from a bacteria, fungi, or animal source that cleaves
• metaloproteinase hydrolyzes peptide bonds and breaks up a protein.
• metaloproteinase metaloprotease
• metalopeptidase hydrolyzes peptide bonds and breaks up a protein.
• collagenase is a hydrophilicity-sensitive enzyme that requires a metal ion in order to function.
• collagenase is a hydrophilic polymer that has a metal ion in order to function.
• metalloproteinase that hydrolyzes peptide bonds of collagen and that requires a zinc ion (e.g.,
• the metalloproteinase inhibitor used in the method of the present invention is a material, such as a compound, or a mixture of compounds, or a composition that is capable of
• an inhibitor of a metalloproteinase can be a chelator, such as a chelator of a divalent metal ion,
• a metal chelator can bind to the zinc ion at the catalytic site of a collagenase, thereby blocking, or preventing, or reducing the action of the collagenase.
• the metalloproteinase inhibitor may be, but is not limited to, an aminocarboxylic acid or a polyaminocarboxylic acid or a salt thereof. As used herein, the term "polyaminocarboxylic acid"
• chelator is preferably at least two groups that can bind to a metal ion, such as, for example, at least two carboxylic acid groups. Another way of stating this is that the chelator is preferably at
• Non-limiting examples of metalloproteinase inhibitors include
• EDTA ethylenediaminetetraacetic acid
• ethylenediaminetetraacetic acid disodium salt Na 2 EDTA or disodium EDTA
• ethylenediaminetetraacetic acid trisodium salt Na 3 EDTA or trisodium EDTA
• ethylenediaminetetraacetic acid tetrasodium salt Na 4 EDTA or tetrasodium EDTA
• ethylenediaminetetraacetic acid dipotassium salt K 2 EDTA
• ethylenediaminetetraacetic acid dipotassium salt K 2 EDTA
• tripotassium salt K 3 EDTA
• NH 4 EDTA ethylenediaminetetraacetic acid ammonium salt
• ethylenediaminetetraacetic acid diammonium salt (NH 4 ) 2 EDTA).
• NH 4 ) 2 EDTA ethylenediaminetetraacetic acid diammonium salt
• ED3A ethylenediaminetriacetic acid
• salt thereof ethylenediaminetriacetic acid
• metalloproteinase inhibitors include ethylene glycol-bis( ⁇ -aminoethylether)-N,N,N'N'-tetraacetic
• EGTA tetrasodium salt
• Na 4 EGTA tetrasodium salt
• aminocarboxylic acids aminocarboxylic acids, polyaminocarboxylic acids and salts thereof, and methods of their preparation are disclosed, for example, in the following U.S. patents incorporated herein by
• metalloproteinase inhibitors include S,S'-ethylenediamine disuccinic acid (EDDS), 1 ,2-diaminocyclohexene- N,N,N',N'-tetraacetic acid (CDTA) and N-(2-hydroxyethyl)ethylenediamine-N,N'-triacetic acid
• HEEDTA metalloproteinase inhibitors
• MGDA methylglycinediacetic acid
• GLUDA N,N-bis(carboxymethyl)glutamate
• phenanthroline 8-hydroxyquinoline
• phosphonic acid derivatives such as amino-tris methylene phosphonic acid, e.g., sold by Buckman Laboratories under the tradename "Phos 2”, diethylene triamine pentamethylene phosphonic acid, e.g., sold by Buckman Laboratories under
• Still other examples of metalloproteinase inhibitors include citric acid and salts of citric
• more than one metalloproteinase inhibitor can be used.
• deterioration of an animal skin or hide due to an action of a metalloproteinase refers to any reduction in the putrefaction, degradation, or deterioration of an animal skin or hide and is not
• all or substantially all metalloproteinase activity is stopped. For instance, preferably, at least 90%, at least 95%, at least 99% of all metalloproteinase activity and/or related effects is stopped.
• the metalloproteinase inhibitor may be applied to an animal skin or hide by any convenient method, such as, for example, by applying the metalloproteinase inhibitor directly to
• water to form a solution and spraying the solution onto the animal skin or hide.
• metalloproteinase inhibitor is applied directly to the animal skin or hide, instead of in a solution, it is not admixed with an extender or carrier material.
• the metalloproteinase inhibitor can be
• any technique that can apply a substance to a substrate can be used in the present
• the metalloproteinase inhibitor can be combined in a solution with other components
• an extender or carrier e.g., solid
• a solid absorbent e.g., a solid absorbent
• the metalloproteinase inhibitor can be applied alone as a solid, e.g., powder, or liquid without any solid extender or carrier, like
• a solid extender or carrier is preferably not used, since
• the metalloproteinase inhibitor can be combined with any liquid bath or
• an aqueous solution containing the metalloproteinase inhibitor may be sprayed onto an animal skin or hide immediately after flaying (for example, within hours of flaying) to provide immediate protection against putrefaction.
• the aqueous solution containing the metalloproteinase inhibitor may be sprayed onto an animal skin or hide immediately after flaying (for example, within hours of flaying) to provide immediate protection against putrefaction.
• solution may also contain bactericides, fungicides, and/or insecticides and/or may contain agents
• the animal skin or hide may be dipped or soaked in a chilling solution containing the metalloproteinase inhibitor.
• Adding a metalloproteinase inhibitor to a chilling solution may allow for chilling to be done at a
• the chilling solution may be at a temperature of greater than freezing and lower than room temperature (e.g., less than 3O 0 C).
• room temperature e.g., less than 3O 0 C.
• the metalloproteinase inhibitor can be combined with an aqueous brining
• animal hides are dipped or soaked, or can be combined with a curing or pickling solution.
• the metalloproteinase solution may be added to any aqueous
• the metalloproteinase inhibitor can be added to any dipping or soaking solution that is
• the amount of the metalloproteinase inhibitor applied to the animal skin or hide is not critical and can be any amount effective to prevent or inhibit the putrefaction, degradation, and/or
• the amount of metal loproteinase inhibitor can vary, for example, according to the method of application of the
• the amount of the metalloproteinase inhibitor according to environmental conditions, according to the amount and condition of the metalloproteinase thought to be present, and/or according to the degree of prevention or inhibition desired.
• the amount of the metalloproteinase inhibitor according to environmental conditions, according to the amount and condition of the metalloproteinase thought to be present, and/or according to the degree of prevention or inhibition desired.
• the amount of the metalloproteinase inhibitor for example, the amount of the metalloproteinase inhibitor
• added to an animal skin or hide can be from about 0.00001% to about 10% or more by weight
• the amount of the metalloproteinase is based on the animal skin or hide. As another example, the amount of the metalloproteinase
• inhibitor added to an animal skin or hide can be from about 0.0001% to about 5% by weight
• the amount of the metalloproteinase inhibitor added to an animal skin or hide can be from about 0.001% to about 2% by weight based
• animal skins or hides are added to a fluid such as a dipping or soaking solution or bath, the
• animal skins or hides are preferably drummed to spread the metalloproteinase throughout the
• the metalloproteinase inhibitor may also be added to a fluid that comes into contact
• an animal skin or hide such as, for example, any dipping or soaking solution or bath in
• a metalloproteinase inhibitor may be added to the aqueous dipping, soaking, brining, curing, or pickling solution between the times that it is used, to deactivate any metalloproteinase that may remain in the solution.
• the metalloproteinase inhibitor added to a fluid is not critical and can be a concentration that is
• the amount of the metalloproteinase inhibitor added to the fluid can be from about 0.00001% to about 10% or more, preferably from about 0.0001% to about 5%
• the fluid and most preferably from about 0.001% to about 2% by weight of the fluid.
• the fluid most preferably from about 0.001% to about 2% by weight of the fluid.
• amount of the metalloproteinase inhibitor added to the fluid can be from about 0.00001% to
• the metalloproteinase inhibitor may also be applied to any solid surface that comes
• metalloproteinases that may be produced, for example, by bacterial or fungal contaminants on the
• solid surface refers to any surface in a slaughterhouse or leather processing area or
• tanning facility such as walls, raceways, floors, platforms, frames, hoists, pallets, tables, hooks,
• slaughterhouse leather processing facility, or hide storage facility that the animal skin or hide may come into contact with during slaughter, storage or processing.
• solid surface is not meant to include particulate materials. It is intended that the method
• a surface in a leather processing facility may harbor microorganisms that produce metalloproteinases, and such metalloproteinases may be splashed onto an animal skin or hide or may be splashed onto a surface that directly contacts an animal
• the metalloproteinase inhibitor can be applied directly to a surface that directly or indirectly contacts the animal skin or hide or can be
• a fluid medium such as, for example, water
• the amount of the metalloproteinase inhibitor added to the liquid can be from about 0.00001% to about 10%, preferably from about 0.0001% to about 5%
• the present invention further relates to a composition containing a dipping or soaking
• dipping or soaking solution contains at least one metalloproteinase inhibitor.
• the metalloproteinase inhibitor is as defined above and can be a chelator, such as a chelator of a
• the metalloproteinase inhibitor may be an aminocarboxylic acid or a polyaminocarboxylic acid or a salt thereof.
• the metalloproteinase inhibitor may be an aminocarboxylic acid or a polyaminocarboxylic acid or a salt thereof.
• the metalloproteinase inhibitor may be ethylenediaminetetraacetic acid (EDTA) or a salt thereof,
• ethylenediaminetetraacetic acid disodium salt Na 2 EDTA or disodium
• EDTA ethylenediaminetetraacetic acid trisodium salt
• Na 3 EDTA or trisodium EDTA ethylenediaminetetraacetic acid trisodium salt
• ethylenediaminetetraacetic acid tetrasodium salt Na 4 EDTA or tetrasodium EDTA
• ethylenediaminetetraacetic acid dipotassium salt K 2 EDTA
• tripotassium salt K 3 EDTA
• NH 4 EDTA ethylenediaminetetraacetic acid ammonium salt
• ethylenediaminetetraacetic acid diammonium salt (NH 4 ) 2 EDTA).
• NH 4 ) 2 EDTA ethylenediaminetetraacetic acid diammonium salt
• the metalloproteinase inhibitors may be ethylene glycol-bis( ⁇ -aminoethylether)-N,N,N'N'-
• EGTA tetraacetic acid
• salt thereof such as, for example, the tetrasodium salt, Na 4 EGTA.
• metalloproteinase inhibitors include S,S'-ethylenediamine
• HMEDTA hydroxyethyl)ethylenediamine-N,N'-triacetic acid
• MGDA methylglycinediacetic acid
• GLUDA bis(carboxymethyl)glutamate
• ortho-phenanthroline ortho-phenanthroline
• 8-hydroxyquinoline 8-hydroxyquinoline
• phosphonic acid derivatives such as amino-tris methylene phosphonic acid, e.g., sold by
• metalloproteinase inhibitors include citric acid and salts of citric acid, gluconic acid, and salts of
• the amount of the metalloproteinase inhibitor contained in the dipping or soaking solution is not critical and may be any amount effective to prevent or inhibit the putrefaction, degradation, and/or deterioration of the animal hides or skins
• the amount of the metalloproteinase inhibitor in the dipping is not limited to the amount of the metalloproteinase inhibitor in the dipping.
• or soaking solution can be from about 0.00001% to about 10%, preferably from about 0.0001%
• the amount of the metalloproteinase inhibitor in the dipping or soaking solution can be from about 0.00001% to
• the dipping or soaking solution contains 2% by weight based on the dipping or soaking solution.
• aqueous solution that is used to treat animal skins or hides, including, but not limited to cleaning, chilling, curing, pickling, liming and/or deliming
• solutions and/or solutions for softening or hydrating an animal skin or hide.
• the present invention further relates to an animal skin or hide having at least one
• the metalloproteinase inhibitor applied to at least one surface thereof.
• inhibitor is as defined above and can be a chelator, such as a chelator of a divalent metal ion.
• the metalloproteinase inhibitor may be an aminocarboxylic acid or a
• polyaminocarboxylic acid or a salt thereof As a non-limiting example, the metalloproteinase
• EDTA ethylenediaminetetraacetic acid
• Na 2 EDTA or disodium EDTA ethylenediaminetetraacetic acid disodium salt
• ethylenediaminetetraacetic acid ' trisodium salt Na 3 EDTA or trisodium EDTA
• ethylenediaminetetraacetic acid tetrasodium salt Na 4 EDTA or tetrasodium EDTA
• ethylenediaminetetraacetic acid dipotassium salt K 2 EDTA
• ethylenediaminetetraacetic acid tripotassium salt K 3 EDTA
• ethylenediaminetetraacetic acid ammonium salt NH 4 EDTA
• ethylenediaminetetraacetic acid diammonium salt (NH 4 ) 2 EDTA).
• NH 4 ) 2 EDTA ethylenediaminetetraacetic acid diammonium salt
• the metalloproteinase inhibitors may be ethylene glycol-bis( ⁇ -aminoethylether)-N,N,N'N'-
• tetraacetic acid or a salt thereof, such as, for example, the tetrasodium salt, Na 4 EGTA.
• metalloproteinase inhibitors include S,S'-ethylenediamine
• EDDS disuccinic acid
• CDTA l,2-diaminocyclohexene-N,N,N',N'-tetraacetic acid
• HEEDTA N-(2- hydroxyethyl)ethylenediamine-N,N'-triacetic acid
• metalloproteinase inhibitors include methylglycinedi acetic acid (MGDA), N 5 N-
• GLUDA bis(carboxymethyl)glutamate
• ortho-phenanthroline ortho-phenanthroline
• 8-hydroxyquinoline 8-hydroxyquinoline
• phosphonic acid derivatives such as amino-tris methylene phosphonic acid, e.g., sold by
• metalloproteinase inhibitors include citric acid and salts of citric acid, gluconic acid, and salts of
• applied to the animal skin or hide is not critical and can be any amount effective to prevent or inhibit the putrefaction, degradation, and/or deterioration of the animal skin or hide.
• the amount of the metalloproteinase inhibitor applied to the animal skin or hide can be any amount of the metalloproteinase inhibitor applied to the animal skin or hide.
• the metalloproteinase inhibitor may be rinsed off immediately or before tanning or may be left on the animal skin or hide.
• any treatment time for any of the above-discussed embodiments can be any treatment time for any of the above-discussed embodiments.
• the treatment time is a variable and depends upon the method chosen to apply the
• the treatment time can be one hour to one day or longer, and when used for fresh hide preservation, the
• inhibitor can be added to the mixing drum and drummed for an hour or two or more.
• the treatment times can vary from one minute to one hour, to six hours, to twenty-four hours,
• the nutrient agar was prepared and autoclaved and then was cooled to 55°C.
• the inhibitors were added to petri dishes, and the nutrient agar-azocoll medium was added and carefully mixed to give the desired
• test cultures secreted collagenase into the
• Table 1 Anticollagenase activities of chemicals using Pseudomonas fluorescens as a source of collagenase (Example 1). Compound Cone. Growth/Days Collagenase Activity/Days
• Table 2 Anticollagenase activity of chemicals using Aeromonas salmonicida as a source of collagenase (Example 2).
• the compounds were effective as collagenase inhibitors at concentrations that were well below what would be required to stop bacterial growth.
• EDTA trisodium EDTA, tetrasodium EDTA, and tetrasodium EGTA.
• the nutrient agar was prepared and autoclaved and then was cooled to 55°C.
• Azocol was added to give a final concentration of 0.5%.
• the inhibitors were added to petri
• Fresh hides were obtained from a tannery and were cut into pieces of approximately 2 cm square. One 2x2 cm hide sample was placed on top of the agar containing
• Treated samples were incubated at 30° C and evaluated after 24 hours, 2 days , 3
• Table 3 Anticollagenase activities of chemicals using collagenase from mixed bacteria on fresh hide samples (Example 3). Compound Cone. Growth/Days Collafienase Activity/Days

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Treatment And Processing Of Natural Fur Or Leather (AREA)
• Cosmetics (AREA)
• Enzymes And Modification Thereof (AREA)

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• 2004
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