EP3409795B1 - Cuir ou article en cuir de reptile mettant en oeuvre un agent de traitement au chrome hexavalent, et procédé de fabrication de ceux-ci - Google Patents

Cuir ou article en cuir de reptile mettant en oeuvre un agent de traitement au chrome hexavalent, et procédé de fabrication de ceux-ci Download PDF

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Publication number
EP3409795B1
EP3409795B1 EP17744370.2A EP17744370A EP3409795B1 EP 3409795 B1 EP3409795 B1 EP 3409795B1 EP 17744370 A EP17744370 A EP 17744370A EP 3409795 B1 EP3409795 B1 EP 3409795B1
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EP
European Patent Office
Prior art keywords
leather
hexavalent chromium
compound
group
chromium
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EP17744370.2A
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German (de)
English (en)
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EP3409795A4 (fr
EP3409795A1 (fr
Inventor
Yuji Akao
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Citizen Watch Co Ltd
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Citizen Watch Co Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/04—Mineral tanning
    • C14C3/06—Mineral tanning using chromium compounds
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0031—Carpet, upholstery, fur or leather cleansers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/2034—Monohydric alcohols aromatic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2058—Dihydric alcohols aromatic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/28—Multi-step processes
    • 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
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/32—Material containing basic nitrogen containing amide groups leather skins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/24—Organic substances containing heavy metals
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40—Inorganic substances
    • A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state

Definitions

  • the present invention relates to a method for producing a reptile leather or leather article using a hexavalent chromium treatment agent and to a reptile leather or leather article produced using a hexavalent chromium treatment agent.
  • leather articles are used in various products such as watchbands and handbags.
  • the visual appearance of the leather enhances the commercial value of watchbands and handbags, increasing the level of satisfaction of consumers. It is needless to say that such products are designed to allow the leather to be in direct touch with the user's skin and that the feel of the leather against the skin further enhances an added value to the products.
  • Production of such a leather article entails making a large leather sheet in advance.
  • an animal skin to be used in the leather article such as the skin of crocodile or cow, is obtained first.
  • the skin as obtained has low durability and cannot be used by itself.
  • the skin is subjected to tanning.
  • This tanning imparts heat resistance and durability to the skin, so that a leather is produced from the skin.
  • the leather thus obtained is dyed with a desired color, or the surface texture of the leather is modified. In this manner, a sheet of leather is obtained.
  • a process is performed in which the sheet is cut into a shape suitable for the intended use, and the cut sheet is attached to a core material or the like with an adhesive.
  • Such a technique for production of leather articles has been traditionally used and is widely known.
  • Tanning is a technique for obtaining a durable leather by treating skin. Tannin acquired from plants had been used in the past; however, treatment with tannin fails to achieve sufficient heat resistance, flexibility, and elasticity. Recently, therefore, chrome tanning that uses a chromium tanning agent (basic chromium sulfate) and that can achieve high heat resistance, flexibility, and elasticity has become mainstream.
  • the chrome tanning is employed for more than 90% of tanning treatments performed throughout the world and has the greatest economical importance.
  • a hydrated chromium complex is embedded between carboxyl groups of glutamic acid and aspartic acid in a collagen peptide structure, so that a soft, durable leather is obtained.
  • the method for chrome tanning is widely well-known and is described, for example, in Non Patent Literature 1 (see below) and CN 104 593 527 A .
  • Chrome tanning agents for chrome tanning contain chromium; thus, a large amount of chromium remains in a leather or leather article subjected to tanning using a chrome tanning agent.
  • Chromium is trivalent in chrome tanning agents.
  • the trivalent chromium may be oxidized into hexavalent chromium through heating or bonding in the process of production of leathers or leather articles.
  • hexavalent chromium present as an impurity in chrome tanning agents may be incorporated in leathers or leather articles.
  • hexavalent chromium produced by the fact that trivalent chromium in the leathers or leather articles is oxidized, for example, by light, heat, or high temperature and humidity. The presence of hexavalent chromium can be examined by a measurement test.
  • Trivalent chromium is non-toxic, while hexavalent chromium is toxic. When contacting the skin or mucous membranes, hexavalent chromium can induce skin roughness or allergy and, in severe cases, cause dermatitis or tumor. Thus, hexavalent chromium significantly affects the human body. Even a small amount of hexavalent chromium is considered to have all hazard risks including carcinogenicity, mutagenicity, and reproductive toxicity. Due to its toxicity, hexavalent chromium is specified as a banned substance.
  • JP 2008-231388 A states in Example 2 that placement of a drop of an aqueous solution of ascorbic acid on a tanned leather detoxified hexavalent chromium contained in the leather.
  • US 2009/0249554 A1 proposes use of D-isoascorbic acid to reduce the amount of hexavalent chromium in leather.
  • Non Patent Literature 1 " Knowledge of Leather", the Japanese Association of Leather Technology, Internet URL: ⁇ http://www.hikaku-kyo.org/htdoc/hikakunochisiki-04.htm>
  • a leather in particular a reptile leather
  • a hexavalent chromium treatment agent containing a hexavalent chromium-reducing compound such as ascorbic acid the treatment may cause a change in the visual appearance of the leather.
  • a method for producing a reptile leather according to the present invention comprises: a chrome tanning step of performing chrome tanning on reptile skin to obtain a leather; a dyeing-fatliquoring step of performing dyeing and fatliquoring simultaneously on the leather subjected to the chrome tanning; and a finishing step of performing finishing on the leather subjected to the dyeing and fatliquoring, the method further comprising a hexavalent chromium treatment step of, prior to the finishing step, applying a hexavalent chromium-reducing compound as defined in claim 1 to the leather subjected to the chrome tanning in the chrome tanning step, the said compound being capable of reducing hexavalent chromium into trivalent chromium.
  • a leather can be treated with a hexavalent chromium treatment agent in the course of leather production without change in the visual appearance of the leather.
  • a method according to a preferred embodiment of the present invention comprises a chrome tanning step, dyeing-fatliquoring step, and finishing step.
  • the method according to the present embodiment further comprises a hexavalent chromium treatment step of applying a hexavalent chromium-reducing compound capable of reducing hexavalent chromium into trivalent chromium to the leather subjected to the chrome tanning in the chrome tanning step, and the dyeing-fatliquoring step and hexavalent chromium treatment step are simultaneously performed.
  • the chrome tanning step is a step of performing chrome tanning on reptile skin to obtain a leather.
  • the skin used in this step include the skin of reptiles such as sea turtles belonging to the family Cheloniidae of the order Testudines, monitor lizards belonging to the family Varanidae of the suborder Lacertilia, tegus belonging to the family Teiidae of the suborder Lacertilia, Python reticulatus and Python molurus belonging to the family Boidae of the suborder Serpentes, sea snakes such as Laticauda semifasciata belonging to the family Hydrophiidae of the suborder Serpentes, water snakes belonging to the family Homalopsidae of the suborder Serpentes, Freshwater crocodile belonging to the family Crocodylidae of the order Crocodilia, and American alligator and caiman belonging to the family Alligatoridae of the order Crocodilia.
  • the chrome tanning can
  • the method according to the present embodiment further comprises a hexavalent chromium treatment step of applying a hexavalent chromium-reducing compound to the leather. Through this step, hexavalent chromium which can be contained in the leather after the chrome tanning is converted to trivalent chromium.
  • the fact that performing the hexavalent chromium treatment step simultaneously with the dyeing-fatliquoring step offers the advantage of further reducing the number of processes.
  • finishing is performed on the leather subjected to the dyeing and fatliquoring.
  • the matte color resulting from the dyeing-fatliquoring step is changed to a glossy color, or so-called "scale", a three-dimensional appearance characteristic of reptile skin, is imparted to the leather.
  • the process performed include the process of polishing the grain side of the leather with agate or glass to impart gloss to the leather (glazing finish), the process of pressing a heated metal roller on the leather to impart gloss to the leather, or the process of rubbing the leather with a heated felt roller to impart gloss to the leather.
  • the side of the leather opposite to the grain side is shaved, and then the leather is placed on a hot plate typically set at 100°C or higher, preferably set at 120 to 130°C. This can impart the three-dimensional appearance called "scale" to the leather.
  • the finishing step generally involves heating the leather.
  • trivalent chromium contained in the leather after the chrome tanning may be changed into hexavalent chromium.
  • the hexavalent chromium thus produced can be reconverted to trivalent chromium by the action of the hexavalent chromium-reducing compound incorporated in the leather through the hexavalent chromium treatment step.
  • the hexavalent chromium treatment step precedes the finishing step, and thus the leather's visual appearance obtained by the finishing step can be maintained without being impaired.
  • reptile leathers which can be used in the present invention, leathers of animals (crocodiles) belonging to the order Crocodilia of the class Reptilia are expensive and have a delicate appearance, and are preferably not subjected to any other process after the finishing.
  • the method according to the present embodiment in which the hexavalent chromium treatment step precedes the finishing step is particularly suitable for use in production of crocodile leathers.
  • a hexavalent chromium treatment agent for simultaneously accomplishing the two steps.
  • the hexavalent chromium treatment agent used for simultaneously accomplishing the two steps is specifically referred to herein as a "simultaneous treatment agent".
  • the simultaneous treatment agent contains water, a color material commonly used in dyeing of leathers, and an oil commonly used in fatliquoring of leathers. Furthermore, a surfactant commonly used for simultaneously accomplishing dyeing and fatliquoring and a hexavalent chromium-reducing compound for accomplishing hexavalent chromium treatment are added to the simultaneous treatment agent.
  • the hexavalent chromium-reducing compound is a compound capable of reducing hexavalent chromium into trivalent chromium.
  • Suitable hexavalent chromium-reducing compounds for use in the invention have been proposed by the present inventors (International Application WO 2016/021461 A1 , international filing date: July 29, 2015) and can be used, as explained below, in addition to ascorbic acid described in JP 2008-231388 A .
  • the hexavalent chromium-reducing compound proposed by the present inventors will be described.
  • the first hexavalent chromium-reducing compound for use in the invention is thus a compound (A) represented by formula (1) below.
  • This compound is composed of at least C, O, H atoms capable of acting to reduce hexavalent chromium into trivalent chromium (having the ability to reduce hexavalent chromium into trivalent chromium), has a single bond and double bond among three carbon atoms, and has a hydroxy group linked to the central carbon atom.
  • the structure represented by formula (1) acts to reduce hexavalent chromium into trivalent chromium.
  • the structure contains in particular a hydroxyphenyl group.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are each independently a substituent composed of C, H and O, which preferably contain a carbonyl group having an unsaturated bond and which have no reactive functional groups such as an aldehyde group and a carboxyl group.
  • R 1 , R 2 , R 3 , R 4 , and R 5 have no functional groups including nitrogen-containing groups such as an amine group and an isocyanate group and sulfur-containing groups such as a sulfate group.
  • R 1 or R 2 and R 3 , R 4 , or R 5 may be linked together to form a ring.
  • the hexavalent chromium-reducing compound comprise, in addition to the organic compound (A), an organic compound (B) that has the structure represented by formula (1) and capable of acting to reduce hexavalent chromium into trivalent chromium and that has no hydroxyphenyl groups, no aldehyde groups, and no carboxyl groups.
  • the organic compound (B) preferably has no functional groups including nitrogen-containing groups such as an amine group and an isocyanate group and sulfur-containing groups such as a sulfate group.
  • the compound (B) having the structure represented by formula (1) may be a cyclic hydrocarbon or may be also an aromatic hydrocarbon having a monocyclic ring or fused ring.
  • the ⁇ bond is, in effect, delocalized without staying in the double bond between the carbon atoms 1 and 2 in formula (1).
  • the cyclic hydrocarbon or aromatic hydrocarbon may have a substituent.
  • Examples of the organic compound (A) or (B) include the following compounds (formulas (2) to (14)) and derivatives thereof. In the present invention, it is also preferable to use a mixture of two or more of these compounds and derivatives thereof.
  • the carbon atom 2 in formulas (2) to (12) and (14) corresponds, for example, to the carbon atom 2 in formula (1).
  • the hexavalent chromium-reducing compound is an organic compound acting on hexavalent chromium, which is toxic, to chemically convert it into a non-toxic compound.
  • this hexavalent chromium-reducing compound can detoxify hexavalent chromium by reducing it into trivalent chromium.
  • reducing agents include lithium aluminum hydride, sodium borohydride, hydrazine, dibutylaluminum hydride, oxalic acid, and formic acid.
  • the use of these typical reducing agents poses various problems.
  • the agent When lithium aluminum hydride is used as a reducing agent, the agent is a strong reducing agent in the form of a powder. This reducing agent is dangerous because it reacts vigorously with water to produce hydrogen which is flammable. Such an agent that produces a flammable substance in this manner is unsuitable for use in leathers or leather articles which, in general, are often brought into contact with the skin (sweat) or exposed to rain.
  • the agent When sodium borohydride is used as a reducing agent, the agent is somewhat hygroscopic and prone to degradation by water. The agent must therefore be stored in a sealed condition. An aqueous solution produced by contact of the agent with a water-containing substance such as sweat or rain is strongly basic, because the solution contains a degradation product of the agent. The agent can thus cause adverse effects on dermis (skin) and mucous membranes. When placed under acidic or neutral conditions, the agent is degraded to produce hydrogen; thus, the agent must be stored in an alkaline solution and cannot be contained in leathers or leather articles. The agent is also difficult to handle, because it is degraded by water to produce hydrogen.
  • Hydrazine is a colorless liquid with a pungent odor similar to that of ammonia, and releases white smoke when contacted with air. Hydrazine is therefore unsuitable for use. Additionally, hydrazine is difficult to handle because it is easily soluble in water, has high reducing capacity, is easily degradable, and is flammable.
  • the agent When dibutylaluminum hydride is used as a reducing agent, the agent is a colorless liquid but is susceptible to humidity. The agent should therefore be stored and used in an inert gas atmosphere and is difficult to use in an ordinary air atmosphere.
  • Oxalic acid When oxalic acid is used as a reducing agent, the agent is poisonous because it strongly binds to calcium ions in blood in the human body. Oxalic acid is designated as a non-medical deleterious substance under Poisonous and Deleterious Substances Control Law. The use of such a poisonous substance in leathers or leather articles is unsuitable for the intended purpose.
  • the formic acid solution or formic acid vapor is harmful to the skin and eyes and can, in particular, do irreparable damage to the eyes. Additionally, inhalation of formic acid can cause a disorder such as pulmonary edema. Formic acid is therefore unsuitable for use. Moreover, chronic exposure to formic acid is considered to adversely affect the liver and kidney, and formic acid is also considered as a possible allergen. Formic acid is therefore unsuitable for the purpose of the present invention.
  • the organic compounds (A) and (B) comprised as the hexavalent chromium-reducing compound not only have the primary ability to treat and detoxify hexavalent chromium, but also are free of toxicity and cause no disorder such as skin roughness when leathers or leather articles treated with these compounds is in contact with the skin.
  • the compounds (A) and (B) are preferably compounds that do not degrade each other by their reducing capacity and that are not reactive or interactive with each other.
  • Such an organic compound is preferably a compound having a basic skeleton represented by formula (1) above and more preferably a stable compound comprising C, H, O atoms.
  • the organic compound having the structure represented by formula (1) has no functional groups such as an aldehyde group and a carboxyl group. It is preferable that the organic compound have no functional groups including nitrogen-containing groups such as an amine group and an isocyanate group and sulfur-containing groups such as a sulfate group. These functional groups are reactive and can undergo an unexpected reaction during use of leathers or leather articles, thus being unsuitable for hexavalent chromium-reducing compounds.
  • the organic compound is capable of acting on hexavalent chromium to produce a compound not detected as a hexavalent chromium compound, thereby detoxifying hexavalent chromium.
  • the organic compound (A) has the structure represented by formula (1) above and further has a hydroxyphenyl group represented by formula (15) below.
  • the organic compound (A) when incorporated in leathers or leather articles, takes effect immediately, remains stable for a long time, maintains its reducing effect over a long period of time, and provides high heat resistance. Formation of hexavalent chromium is thus inhibited over a long period of time. Additionally, the organic compound (A) contained in leathers or leather articles is resistant to degradation by water-containing substances such as sweat and rain.
  • the organic compound (A) can remain for a long time, particularly thanks to the high interactivity of its hydroxyphenyl group with the collagen, while the organic compound (A) is incorporated in the collagen not completely but in such a manner that the organic compound (A) forms an island of a sea-island structure and is allowed a degree of freedom sufficient to exhibit the reducing capacity. Since the organic compound (A) is used in leathers or leather articles, a safe compound having low environmental impact is preferred as the organic compound (A).
  • R a is a monovalent group or a divalent group.
  • the monovalent group include a hydrogen atom, a hydrocarbon group, and an oxygen-containing group.
  • the divalent group include a divalent hydrocarbon group and a divalent oxygen-containing group.
  • a hydrogen atom, a monovalent hydrocarbon group, a divalent hydrocarbon group, or a hydroxy group is preferred to achieve higher compatibility with leathers or leather articles.
  • a plurality of R a are independent from each other and may be the same or different. Adjacent R a groups may be linked together to form an aromatic ring or aliphatic ring. R a may be linked to R a of another hydroxyphenyl group.
  • the organic compound (A) may take effect more immediately and exhibit higher reducing capacity stably over a long period of time in leathers or leather articles, the group represented by formula (15) is more preferably a dihydroxyphenyl group or trihydroxyphenyl group and even more preferably a 3,4,5-trihydroxyphenyl group.
  • the hydrocarbon group is a C 1 to C 20 hydrocarbon group, and specific examples thereof include a C 1 to C 20 alkyl group, a C 7 to C 20 arylalkyl group, or an unsubstituted or substituted C 6 to C 20 aryl group.
  • hydrocarbon group examples include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an allyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an amyl group, a n-pentyl group, a neopentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decanyl group, a 3-methylpentyl group, a 1,1-diethylpropyl group, a 1,1-dimethylbutyl group, a 1-methyl-1-propylbutyl group, a 1,1-dipropylbutyl group, a 1,1-dimethyl-2-methylpropyl group, a 1-methyl-1-is
  • hydrocarbon group further include hydrocarbon groups (an alkoxy group, for example) containing an oxygen-containing group such as a methoxy group, an ethoxy group, or a phenoxy group.
  • hydrocarbon group include hydrocarbon groups containing an unsaturated carboxylic acid ester such as methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, or (5-norbornen-2-yl) ester (when the unsaturated carboxylic acid is a dicarboxylic acid, the ester may be either a monoester or diester).
  • oxygen-containing group is a hydroxy group.
  • organic compound (A) examples include:
  • organic compound (A) examples include derivatives of the above substances, such as compounds having an alkoxy group and esterified products.
  • Specific examples of the derivatives include pyrogallol-1,3-dimethyl ether, pyrogallol-1,3-diethyl ether, and 5-propylpyrogallol-1-methyl ether.
  • Examples of the organic compound (A) include compounds with the structure represented by formula (2) above (1,2,3-trihydroxybenzene skeleton) and derivatives thereof. Such compounds have the ability to remove hexavalent chromium.
  • Examples of the derivatives include those having a substituent such as a hydrocarbon group or oxygen-containing group at the 4-, 5-, 6-positions of the compound represented by formula (2) above.
  • Preferred examples of the substituent include a C 1 to C 20 hydrocarbon group, a C 1 to C 20 alkoxy group, and a C 1 to C 20 esterified product, and more preferred examples include a C 1 to C 10 hydrocarbon group, a C 1 to C 20 alkoxy group, and a C 1 to C 10 esterified product. These groups are as described above. The same applies to derivatives of compounds described later.
  • Examples of the derivatives include: a gallic acid ester such as the compound represented by formula (3) above; and the compound represented by formula (4) above which has a plurality of the structures represented by formula (2) above per molecule and derivatives of the compound of formula (4).
  • Specific examples include catechol tannin, pyrogallol tannin, oak gall tannin, gallic tannin, and phlorotannin.
  • the substituents introduced at the 4-, 5-, 6-positions can be those suitable for the way in which the organic compound (A) is used.
  • an ester group can be introduced to increase the compatibility with the solvent.
  • the organic compound (A) preferably comprises (i) a gallic acid ester and (ii) at least one compound selected from tannic acid and a derivative thereof, and more preferably comprises (i) a gallic acid ester and (ii) tannic acid.
  • the gallic acid ester has a relatively low molecular weight and may therefore be considered likely to bleed out of leathers or leather articles.
  • the gallic acid ester can, due to having a structural moiety corresponding to tannic acid, favorably interact with the tannic acid or derivative thereof and become unlikely to bleed out while maintaining the reducing power.
  • the gallic acid ester has reducing power and takes effect immediately.
  • the reducing power of the gallic acid ester is not as high as that of ascorbic acid, but higher than that of tannic acid; thus, the gallic acid ester can continue to exhibit reducing power over a long period of time even after degradation and loss of reducing power of ascorbic acid (the gallic acid ester can again reduce hexavalent chromium ions newly produced by oxidation).
  • the gallic acid ester is resistant to water-containing substances such as sweat and rain and unlikely to be degraded.
  • the tannic acid and derivative thereof are bulky, and as seen from the fact that they are conventionally used in tanning, they have high affinity to collagen in leathers or leather articles and are unlikely to bleed out. When incorporated in leathers or leather articles, the tannin acid and derivative thereof can maintain their reducing power over a long period of time. They can therefore inhibit formation of hexavalent chromium over a longer period of time.
  • the tannic acid and derivative thereof have low potential to irritate humans (the skin) and are safe. As for the reducing power, the tannic acid and derivative thereof takes effect slowly as compared to ascorbic acid and the gallic acid ester.
  • the tannic acid and derivative thereof have high affinity to leather and leather articles and are resistant to degradation; therefore, the tannic acid and derivative thereof have a higher potential to maintain the reducing power until leather articles fulfil their function and purpose, than ascorbic acid and the gallic acid ester.
  • the organic compound (A) has a high ability to penetrate into leathers or leather articles and is capable of remaining in leathers or leather articles for a long time and continuing to reduce hexavalent chromium stably over a long period of time.
  • polyphenols can be considered to have a potential to cause browning or discoloration because of their high reducing capacity
  • the above compounds are incorporated in leathers or leather articles before discoloration and are therefore less likely to cause color fading or color change, thus posing a lower risk of impairing the color or texture of leathers or leather articles. This is also the reason why the above compounds are preferred.
  • hydroxy groups are present at the 1-, 2-, and 3-positions.
  • the same effect can be provided by compounds having a skeleton in which hydroxy groups are introduced at the 1-, 2-, and 4-positions (formula (5) above) or a skeleton in which hydroxy groups are introduced at the 1-, 3-, and 5-positions (formula (6) above). Derivatives of such compounds also have the same effect.
  • Compounds having a hydroxy group on a plurality of linked aromatic rings also have the same effect.
  • the compounds include those having one or more hydroxy groups on a naphthalene ring.
  • Examples of such compounds having two hydroxy groups are those represented by formulas (10) and (11) above. Derivatives of such compounds also have the hexavalent chromium removing ability like the compounds previously described.
  • Examples of the compound represented by formula (1) include compounds having a long-chain alkyl group and a heterocyclic ring. Such compounds have enhanced organic nature and decreased water solubility. However, these compounds have improved affinity for organic solvents and thus have the advantage of being soluble in hydrocarbon solvents.
  • An example of the compounds is that represented by formula (14) above.
  • catechins such as catechin, gallocatechin, catechin gallate, epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, procyanidin, and theaflavin and derivatives of the catechins. These catechins are superior in terms of safety and exhibit high reducing power in leathers or leather articles.
  • the organic compound (B) has the structure represented by formula (1) above and is devoid of the hydroxyphenyl group represented by formula (15). Being devoid of the hydroxyphenyl group, the organic compound (B) has difficulty in penetrating into leathers or leather articles; however, thanks to having the structure represented by formula (1), the organic compound (B) is capable of successfully detoxifying hexavalent chromium present at the surface of leathers or leather articles by reducing it into trivalent chromium. The use of the compound (B) can therefore provide an immediate effect on preventing hexavalent chromium ions from dissolving in a water-containing substance such as sweat or rain and leaching into the environment or contacting humans.
  • An example of the organic compound (B) is a compound having a hetero ring.
  • the hetero ring include furan, chromene, isochromene, and xanthene.
  • Examples of derivatives of such compounds include the compound having the structure represented by formula (13) above and derivatives thereof, erythorbic acid and derivatives thereof, and 4-hydroxyfuran-2(5H)-one. These compounds have the hexavalent chromium removing ability.
  • ascorbic acid esters examples include, but are not limited to, ascorbic acid esters, ascorbic acid phosphate, ascorbic acid sulfate, ascorbyl glucoside (2-O- ⁇ -D-glucopyranosyl-L-ascorbic acid), ascorbyl glucosamine, and dehydroascorbic acid.
  • Examples of the derivatives of erythorbic acid include erythorbic acid esters.
  • the organic compound (B) is preferably at least one compound selected from ascorbic acid and erythorbic acid and is more preferably ascorbic acid.
  • This compound is easily degradable, thus being unable to maintain its effect over a long period of time and likely to bleed out of leathers or leather articles.
  • this compound has low irritation potential on, and is safe for, humans (skin) and, in addition, it has high reducing power and takes effect immediately. Bringing a simultaneous treatment agent containing the compound (B) into contact with a leather or leather article can therefore effectively prevent hexavalent chromium ions from leaching into the environment and contacting humans.
  • the surface of the leather or leather article can be detoxified quickly, which makes it possible to successfully reduce the occurrence of skin roughness or allergy.
  • the compound (B) is unreactive and incompatible with the organic compound (A) and undegradable by the compound (A).
  • the compound (B) can therefore be well mixed in the simultaneous treatment agent. Additionally, when the compound (B) having strong reducing power is incorporated, browning or discoloration caused by the organic compound (A) can be prevented.
  • the compound (B) is also preferred in that the compound (B), due to being easily degradable, is unlikely to cause coloring and does not impair the color or texture of leathers or leather articles.
  • compounds having the basic skeleton represented by formula (1) in the molecule are capable of detoxifying and removing hexavalent chromium.
  • the hexavalent chromium-reducing compound is preferably at least one selected from a compound (A-i) represented by formula (A-i) below and a tannin (A-ii). It is more preferable to use the compound (A-i) represented by formula (A-i) below and the tannin (A-ii) in combination.
  • the compound (A-i) is represented by formula (A-i) below.
  • n 0, 1, or 2. That is, the compound (A-i) has a benzene, naphthalene, or anthracene structure.
  • R 11 to R 18 each independently represent a hydrogen atom, a hydroxy group, a C 1 to C 4 alkyl group, a C 1 to C 4 alkoxy group, or a group represented by formula (a-i) below.
  • R 19 is a C 1 to C 4 alkyl group.
  • Examples of the C 1 to C 4 alkyl group include a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, an i-butyl group, a s-butyl group, and a t-butyl group.
  • Examples of the C 1 to C 4 alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a s-butoxy group, and a t-butoxy group.
  • R 11 to R 14 , R 16 , and R 17 are a hydroxy group. It is preferable that two or three of R 11 to R 14 , R 16 , and R 17 be hydroxy groups, because in this case the ability to reduce hexavalent chromium is increased.
  • n is 1 or 2
  • at least one of R 11 to R 18 is a hydroxy group.
  • n is 1 or 2
  • a plurality of R 15 may be the same or different, and a plurality of R 18 may be the same or different.
  • R 16 and R 17 may be linked together to form a five-membered ring or a six-membered ring.
  • the atoms constituting the ring may include not only carbon atoms but also an oxygen atom.
  • the ring may have a C 1 to C 16 alkyl group as a substituent.
  • the C 1 to C 16 alkyl group may be linear or branched.
  • the compound (A-i) include the compounds represented by formulas (2), (3), (5) to (12), and (14) above and the compounds mentioned above as examples.
  • One compound (A-i) may be used alone, or two or more compounds (A-i) may be used in combination.
  • the tannin (A-ii) may be a hydrolyzable tannin or condensed tannin.
  • the hydrolyzable tannin include gallotannins such as tannic acid (the compound represented by formula (4) above) and ellagitannin.
  • gallotannins such as tannic acid (the compound represented by formula (4) above)
  • ellagitannin the compound represented by formula (4) above
  • a hydrolyzable tannin is suitably used.
  • One tannin (A-ii) may be used, or two or more tannins (A-ii) may be used in combination.
  • the carbon to which a hydroxy group is bonded corresponds, for example, to the carbon 2 in formula (1) above.
  • the hexavalent chromium-reducing compound to be used preferably comprises at least one selected from a compound (B-i) represented by formula (B-i) below and a compound (B-ii) represented by formula (B-ii) below together with the compound (A-i) and tannin (A-ii).
  • X is a group represented by any one of formulas (b-i) to (b-iii) below.
  • o is an integer of 0 to 3
  • p is an integer of 1 to 3
  • q is an integer of 1 to 17.
  • Specific examples of the compound (B-i) and compound (B-ii) include the above compound represented by formula (13) and the compounds mentioned above as examples.
  • One compound (B-i) may be used alone, or two or more compounds (B-i) may be used in combination.
  • One compound (B-ii) may be used alone, or two or more compounds (B-ii) may be used in combination.
  • the compounds (B-i) and (B-ii) may be used in combination.
  • the hexavalent chromium content can be more reliably kept below the limit by the Regulations until the leather or leather article fulfills its function and purpose.
  • the compound (B-i) and/or (B-ii) which has high reducing power and takes effect immediately is further combined with the compound (A-i) and/or (A-ii)
  • hexavalent chromium, particularly that present in the vicinity of the surface of the leather or leather article can be effectively reduced at the time of treatment.
  • a simultaneous treatment agent containing the hexavalent chromium-reducing compound is used.
  • the proportions of the organic compounds (A) and (B) in the simultaneous treatment agent are not particularly limited as long as the effect of the present invention is obtained.
  • the proportions are preferably such that the weight percentage ratio between the organic compounds (A) and (B) ((A):(B)) is 50 to 90:10 to 50, more preferably 50 to 80:20 to 50, and even more preferably 50 to 70:30 to 50 (it should be noted that the total amount of the compounds (A) and (B) is defined as 100% by weight).
  • the organic compound (B) has a high ability to take effect immediately, it has difficulty in penetrating into leathers or leather articles and thus cannot have high long-term stability.
  • the amount of the organic compound (B) is therefore preferably similar to or smaller than that of the organic compound (A). However, if the amount of the organic compound (B) is 10% by weight or less, there is a possibility that hexavalent chromium present in the surface of leathers or leather articles cannot be successfully reduced and detoxified into trivalent chromium.
  • the simultaneous treatment agent comprises (i) the gallic acid ester, (ii) the at least one compound selected from tannic acid and a derivative thereof, and the organic compound (B)
  • the proportions of these compounds are not particularly limited as long as the effect of the present invention is obtained.
  • the proportions are preferably such that the weight percentage ratio ((i):(ii):(B)) is 1 to 20:30 to 89:10 to 50, more preferably 3 to 17:33 to 77:20 to 50, and even more preferably 5 to 15:35 to 65:30 to 50 (it should be noted that the total amount of the compounds (i), (ii), and (B) is defined as 100% by weight).
  • the proportion of the organic compound (A) is as previously described.
  • the organic compound (B) is ascorbic acid and/or erythorbic acid, because ascorbic acid and erythorbic acid are incompatible with the compounds (i) and (ii) and are not incorporated in the compound (ii), thus being able to successfully reduce the surface of leathers or leather articles.
  • the primary effect of the compounds (i) and (ii) is to reduce hexavalent chromium present inside leathers or leather articles.
  • Ascorbic acid, propyl gallate, and tannic acid meet the international safety standards at concentrations thereof used in leather or leather articles regarding carcinogenicity, skin sensitization, and skin irritation as specified in the OECD Guidelines for the Testing of Chemicals.
  • the compound (i) has high reducing power and is relatively easily degradable.
  • the compound (ii) having a structural moiety corresponding to the compound (i) can be degraded to give the compound (i), and exhibits its reducing power more slowly than ascorbic acid and the gallic acid ester.
  • the amount of the compound (ii) is therefore preferably greater than that of the compound (i).
  • the compound (i) is pointed out as having somewhat higher potential to irritate humans (skin) than the compound (ii) and organic compound (B) and also has a relative risk of causing coloring.
  • the amount of the compound (i) used is therefore preferably smaller than those of the compound (ii) and organic compound (B).
  • hexavalent chromium in leathers or leather articles may not be quickly detoxified, and hexavalent chromium ions remaining untreated may leach on the surface of leather or leather articles upon failure of the organic compound (B) to fully treat hexavalent chromium or after inactivation of the organic compound (B).
  • Polyphenols can be considered to have a potential to cause browning or discoloration because of their high reducing capacity; however, when used in the above proportions, the compounds (i), (ii), and (B) can be successfully incorporated in leathers or leather articles before discoloration and are therefore less likely to cause color fading or color change, thus hardly impairing the color or texture of leathers or leather articles. This is a reason why the above proportions are preferred.
  • the above proportions are preferred also because when used in the proportions, the compounds (i), (ii), and (B) are easily soluble both in water and in organic solvents. Such a simultaneous treatment agent is preferred because it can exhibit high long-term reliability.
  • the proportions of the compound (A-i) and the tannin (A-ii) are not particularly limited as long as the effect of the present invention is obtained.
  • the proportions are preferably such that the weight percentage ratio ((A-i):(A-ii)) is 11 to 70:30 to 89, more preferably 23 to 67:33 to 77, and even more preferably 35 to 50:50 to 65 (it should be noted that the total amount of the compound (A-i) and tannin (A-ii) is defined as 100% by weight). With such proportions, the hexavalent chromium content can be kept low over a long period of time.
  • the simultaneous treatment agent comprises the compound (A-i), the tannin (A-ii), and the compound (B-i) and/or(B-ii)
  • the proportions of the compound (A-i), the tannin (A-ii), and the total of the compounds (B-i) and (B-ii) are not particularly limited as long as the effect of the present invention is obtained.
  • the proportions are preferably such that the weight percentage ratio ((A-i):(A-ii) : (B-i) + (B-ii)) is 1 to 20:30 to 89:10 to 50, more preferably 3 to 17:33 to 77:20 to 50, and even more preferably 5 to 15:35 to 65:30 to 50 (it should be noted that the total amount of the compound (A-i), the tannin (A-ii), and the compounds (B-i) and (B-ii) is defined as 100% by weight).
  • the amounts of the color material and oil contained with respect to 100% by mass of the simultaneous treatment agent are those in which they are used in ordinary cases.
  • the hexavalent chromium-reducing compound is contained, for example, in an amount of 0.01 to 10.0% by mass with respect to 100% by mass of the simultaneous treatment agent.
  • the total amount of the organic compound (A) contained in the simultaneous treatment agent is preferably, but not limited to, about 0.01 to 10.0% by weight, more preferably about 0.1 to 7.0% by weight, even more preferably about 0.3 to 5.0% by weight, still even more preferably about 0.5 to 3.0% by weight, and most preferably about 0.5 to 2.0% by weight, with respect to 100% by weight of the simultaneous treatment agent.
  • the reason why this amount of the organic compound (A) is preferred is that in this case the potential to cause color fading or color change is particularly decreased. Additionally, the hexavalent chromium content can be kept low over a long period of time.
  • the total amount of the organic compounds (A) and (B) contained in the simultaneous treatment agent is preferably, but not limited to, about 0.01 to 10.0% by weight, more preferably about 0.1 to 7.0% by weight, even more preferably about 0.3 to 5.0% by weight, still even more preferably about 0.5 to 3.0% by weight, and most preferably about 0.5 to 2.0% by weight with respect to 100% by weight of the simultaneous treatment agent.
  • the reason why this total amount of the organic compounds (A) and (B) is preferred that in this case the potential to cause color fading or color change is particularly decreased. Additionally, the hexavalent chromium content can be kept low over a long period of time.
  • the simultaneous treatment agent comprises the compound (A-i) and/or tannin (A-ii) and optionally the compound (B-i) and/or compound (B-ii)
  • the amounts of these compounds are as described above for the amounts of the compounds (A) and (B); namely, in the above description of the amounts of the components, the compound (A) can be replaced by the total of the compound (A-i) and tannin (A-ii), and the compound (B) can be replaced by the total of the compounds (B-i) and (B-ii).
  • the simultaneous treatment agent comprises the compound (A-i) and/or tannin (A-ii) and optionally the compound (B-i) and/or compound (B-ii); namely, in the foregoing descriptions, the (i) gallic acid ester can be replaced by the compound (A-i), the (ii) tannic acid can be replaced by the compound (A-ii), the compound (A) can be replaced by the compound (A-i) and tannin (A-ii), and the compound (B) can be replaced by the compounds (B-i) and (B-ii).
  • the method for preparing the simultaneous treatment agent is not particularly limited as long as the above components can be dissolved.
  • heating to 50 to 70°C is preferred.
  • the leather and simultaneous treatment agent are brought into contact.
  • the steps are carried out by placing the simultaneous treatment agent and the chrome-tanned leather together in a drum.
  • the proportions of the leather and simultaneous treatment agent can be those of a leather and a dyeing-fatliquoring agent in ordinary dyeing-fatliquoring.
  • the conditions such as the treatment temperature and treatment time can be appropriately selected depending on the color material.
  • the leather is colored and endowed with properties such as flexibility.
  • the hexavalent chromium-reducing compound having penetrated into the leather reduces hexavalent chromium present in the leather into trivalent chromium.
  • the leather comes to contain trivalent chromium and the remaining hexavalent chromium-reducing compound not consumed in the reduction.
  • the hexavalent chromium content in the leather is typically decreased to less than 3 ppm, preferably to 2 ppm or less.
  • the trivalent chromium content varies depending on the leather and is not particularly limited.
  • the trivalent chromium content is typically 4000 ppm or more, and may be 4500 ppm or more or even 5000 ppm or more.
  • the total chromium content remains unchanged before and after the treatment with the simultaneous treatment agent.
  • the hexavalent chromium-reducing compound can, even when nontoxic chromium is converted to hexavalent chromium which is toxic after the treatment, detoxify the hexavalent chromium produced after the treatment. Therefore, the leather treated with the simultaneous treatment agent can keep the hexavalent chromium content below the limit specified by the Regulations until the leather or leather article fulfills its function and purpose.
  • the method for producing a reptile leather according to the present invention is not limited to preferred embodiment [1] described above and may be implemented as embodiment [2] in which the hexavalent chromium treatment step is performed on the leather subjected to the chrome tanning in the chrome tanning step, the dyeing-fatliquoring step is then performed on the leather subjected to the hexavalent chromium treatment, and the finishing step is then performed on the leather subjected to the dyeing and fatliquoring.
  • the method for producing a reptile leather according to the present invention may also be implemented as embodiment [3] in which the dyeing-fatliquoring step is performed on the leather subjected to the chrome tanning, the hexavalent chromium treatment step is then performed on the leather subjected to the dyeing and fatliquoring, and the finishing step is then performed on the leather subjected to the hexavalent chromium treatment.
  • the hexavalent chromium treatment step precedes the finishing step as in embodiment [1], and thus the leather's visual appearance obtained by the finishing step can be maintained without being impaired.
  • Embodiment [1] is preferred in that the number of steps is smaller than those in embodiments [2] and [3]. If the dyeing-fatliquoring step is performed on the leather in a solvent after the hexavalent chromium treatment step, the hexavalent chromium-reducing compound incorporated in the leather may come out of the leather.
  • Embodiments [1] and [3] are free of such a problem and preferred in this regard.
  • the hexavalent chromium treatment step is performed first.
  • the hexavalent chromium treatment agent used in this step is preferably a treatment agent corresponding to the above simultaneous treatment agent from which the color material, oil, and surfactant are excluded (namely, a treatment agent containing the hexavalent chromium-reducing compound and water; this treatment agent may be referred to herein as a "hexavalent chromium-targeted treatment agent"). It should be noted that this treatment agent may contain a nonionic surfactant.
  • the solvent is not limited to water and may be a mixed solvent of water and an organic solvent.
  • the organic solvent include C 1 to C 3 alcohols (methanol, ethanol, propanol, and isopropanol (IPA)), butanol, acetone, methyl ethyl ketone (MEK), and N,N-dimethylformamide (DMF).
  • water alone or a mixed solvent of water and a C 1 to C 3 alcohol is preferably used, water alone or a mixed solvent of water and IPA is more preferably used, and water alone is even more preferably used. Since the hexavalent chromium treatment step in embodiment [2] is performed before fatliquoring, the treatment agent can easily penetrate into the leather even when the solvent is water.
  • the amount of the organic solvent used is preferably more than 0% by mass and 20% by mass or less with respect to 100% by mass of the total amount of water and the organic solvent in order to avoid impairing the texture of the leather.
  • the leather treatment with the hexavalent chromium treatment agent described above namely detoxification of hexavalent chromium
  • the method for making the contact is not particularly limited as long as the effect of the present invention is obtained. Examples of the method include spraying, atomizing, dipping, spreading, and immersion.
  • the treatment agent may be applied to the leather by spraying with a spray or by spreading with a brush.
  • the surface of the leather may be rubbed with a cloth impregnated with the treatment agent.
  • the agent When a delicate leather such as a reptile leather which has a very vulnerable surface susceptible to scratches is treated, it is preferable to apply the agent to the leather by spraying with a spray. Since the hexavalent chromium treatment step in embodiment [2] is performed before fatliquoring, the treatment agent can easily penetrate into the leather both from the grain side of the leather and from the opposite side.
  • the amount of the hexavalent chromium treatment agent to be used can be determined as appropriate in consideration of the size and density of the fibers of the leather.
  • the hexavalent chromium content can be kept below the limit specified by the Regulations until the leather or leather article fulfills its function and purpose.
  • the amount of the hexavalent chromium treatment agent to be used is determined in advance, it is preferable to use a leather whose properties such as the size and density of fibers are as close to those of the leather to be actually subjected to the hexavalent chromium treatment step as possible.
  • the dyeing-fatliquoring agent used in this step is preferably a treatment agent corresponding to the above simultaneous treatment agent from which the hexavalent chromium-reducing compound is excluded (namely a treatment agent containing the color material, oil, surfactant, and water).
  • the dyeing-fatliquoring step is performed first by an ordinary method.
  • the dyeing-fatliquoring agent used in this step is as described for embodiment [2].
  • the hexavalent chromium treatment step is performed.
  • the hexavalent chromium treatment agent used in this step is also as described for embodiment [2].
  • the method of treatment is also as described for embodiment [2].
  • the solvent used is preferably a mixed solvent of water and an organic solvent, more preferably a mixed solvent of water and a C 1 to C 3 alcohol, and even more preferably a mixed solvent of water and IPA.
  • the treatment agent penetrates into the leather more easily from the side opposite to the grain side than from the grain side, because the leather has been subjected to fatliquoring. It is therefore preferable to apply the treatment agent to the side of the leather opposite to the grain side.
  • the method for producing a reptile leather according to the present invention may be implemented as embodiment [1'] in which a simultaneous treatment agent containing water, a color material commonly used in dyeing of leathers, an oil prepared by solubilizing an oil commonly used in fatliquoring of leathers, and a hexavalent chromium-reducing compound is used instead of the simultaneous treatment agent used in embodiment [1].
  • the method for producing a reptile leather according to the present invention may be implemented as embodiment [2'] or [3'] in which a dyeing-fatliquoring agent containing water, a color material commonly used in dyeing of leathers, and an oil prepared by solubilizing an oil commonly used in fatliquoring of leathers is used instead of the dyeing-fatliquoring agent used in embodiment [2] or [3].
  • the method for producing a reptile leather according to the present invention is suitable also for use in production of fish leathers as well as in production of reptile leathers.
  • the reptile leather according to the present invention is a leather subjected to chrome tanning and comprises a hexavalent chromium-reducing compound without a concentration gradient from the grain side of the leather to the opposite side, the hexavalent chromium-reducing compound being as defined in claim 11 and being capable of reducing hexavalent chromium into trivalent chromium.
  • the leather according to the present invention maintains the visual appearance as imparted by the finishing step.
  • the leather according to the present invention is obtained, for example, by the above leather production method.
  • the method for producing a leather article according to the present invention comprises producing a leather by the above leather production method and further comprises a subsequent processing step of processing the leather. With the method for producing a leather article, the visual appearance as imparted to the leather by the finishing step in the course of production of the leather is maintained.
  • Examples of the leather article include shoes, clothes, hats, gloves, belts, wallets, business card cases, watchbands, bags, book covers, pen cases, mobile phone cases, personal planners, key cases, glasses cases, and tool cases.
  • the leather article can be obtained by cutting a sheet of leather into a desired shape and attaching the cut sheet to a core material or the cut sheets to each other by means of an adhesive or by sewing.
  • a watchband is obtained as follows: a sheet of leather cut in the shape of the band is attached to the periphery, namely the front and back sides, of a core material with an adhesive, and the core material with the sheet of leather is heated.
  • the article is finished, for example, by hemming for improving its texture.
  • the leather article according to the present invention comprises the leather described above.
  • Examples of the leather article (processed leather product) are as mentioned above.
  • the visual appearance as imparted to the leather by the finishing step in the course of production of the leather is maintained.
  • the leather article according to the present invention is obtained, for example, by the above method for producing a leather article.
  • a crocodile leather sheet (thickness: 1.5 mm) subjected to chrome tanning in the chrome tanning step was prepared.
  • the hexavalent chromium content in this leather as determined by the procedure according to ISO 17075:2008-02, was 8 ppm.
  • the total chromium content was quantified with a fluorescent X-ray analyzer (an energy-dispersive fluorescent X-ray analyzer, "JSX-3202EV ELEMENT ANALYZER", available from JEOL Ltd.) and determined to be 7141 ppm.
  • the reference samples used were JSX-3000 series reference sample 1, JSX-3000 series reference sample 2, and JSX-3000 series energy calibration reference sample which are available from JEOL Ltd.
  • the measurement was conducted using JSX starter and then Plastic D3 in accordance with Quick Manual (Nos. EY07007-J00 and J00 EY07007G, issued in August 2007) provided by JEOL Ltd.
  • the dyeing-fatliquoring step and the hexavalent chromium treatment step were simultaneously performed on this leather as follows.
  • a color material, an oil, a surfactant, 0.5 parts by weight of the compound represented by formula (3), 2.5 parts by weight of the compound represented by formula (4), and 2.0 parts by weight of the compound represented by formula (13) were mixed and dissolved in water to obtain a simultaneous treatment agent.
  • the water was used in an amount such that the total amount of the treatment agent was 500 parts by weight.
  • the leather sheet and simultaneous treatment agent were placed in a drum, and the leather sheet was treated by rotating the drum.
  • hexavalent chromium content was not more than the detection limit (2 ppm).
  • the total chromium content as quantified by the fluorescent X-ray analyzer remained unchanged before and after the treatment with the hexavalent chromium treatment agent.
  • Another portion of the leather was tested using the below-described testing liquid with which hexavalent chromium-reducing compounds can be detected. It was thus confirmed that the leather contained a hexavalent chromium-reducing compound without a concentration gradient from the grain side of the leather to the opposite side.
  • the testing liquid When a drop of the testing liquid is placed on a leather containing a hexavalent chromium-reducing compound, the testing liquid is colored blue. The greater the amount of the hexavalent chromium-reducing compound contained in the leather is, the more intensely the liquid is colored.
  • a drop of the testing liquid was placed on samples shaved from the grain side in increments of 0.5 mm in the thickness direction, namely a sample shaved from the grain side to a depth of 0.5 mm and a sample shaved from a depth of 0.5 mm to a depth of 1.0 mm, and also on the remaining sample. The liquid was colored with the same level of intensity for all the samples.
  • the leather having undergone the dyeing-fatliquoring step and hexavalent chromium treatment step was further subjected to glazing finish to obtain a glossy crocodile leather.
  • a leather treated with a simultaneous treatment agent was obtained by performing the dyeing-fatliquoring step and hexavalent chromium treatment step simultaneously in the same manner as in Example 1-1, except for using 1.5 parts by weight of the compound represented by formula (3) and 3.5 parts by weight of the compound represented by formula (4) instead of 0.5 parts by weight of the compound represented by formula (3), 2.5 parts by weight of the compound represented by formula (4), and 2.0 parts by weight of the compound represented by formula (13).
  • hexavalent chromium content was not more than the detection limit (2 ppm).
  • the total chromium content as quantified by the fluorescent X-ray analyzer remained unchanged before and after the treatment with the hexavalent chromium treatment agent.
  • the leather having undergone the dyeing-fatliquoring step and hexavalent chromium treatment step was further subjected to glazing finish to obtain a glossy crocodile leather.
  • a leather treated with a simultaneous treatment agent was obtained by performing the dyeing-fatliquoring step and hexavalent chromium treatment step simultaneously in the same manner as in Example 1-1, except for using 15 parts by weight of the compound represented by formula (4) instead of 0.5 parts by weight of the compound represented by formula (3), 2.5 parts by weight of the compound represented by formula (4), and 2.0 parts by weight of the compound represented by formula (13).
  • hexavalent chromium content was not more than the detection limit (2 ppm).
  • the total chromium content as quantified by the fluorescent X-ray analyzer remained unchanged before and after the treatment with the hexavalent chromium treatment agent.
  • the leather having undergone the dyeing-fatliquoring step and hexavalent chromium treatment step was further subjected to glazing finish to obtain a glossy crocodile leather.
  • a crocodile leather sheet (thickness: 1.5 mm) subjected to chrome tanning in the chrome tanning step was prepared.
  • the total chromium content as quantified by the fluorescent X-ray analyzer was 7141 ppm.
  • the hexavalent chromium treatment step was performed on this leather as follows. 0.5 parts by weight of the compound represented by formula (3), 2.5 parts by weight of the compound represented by formula (4), and 2.0 parts by weight of the compound represented by formula (13) were mixed and dissolved in water to obtain a hexavalent chromium treatment agent. The water was used in an amount such that the total amount of the treatment agent was 500 parts by weight.
  • the above crocodile leather was immersed in the obtained treatment agent and then dried to obtain a hexavalent chromium treatment agent-treated leather.
  • the dyeing-fatliquoring step was performed on the leather using a dyeing-fatliquoring agent containing a color material, an oil, and a surfactant.
  • hexavalent chromium content was not more than the detection limit (2 ppm).
  • the total chromium content as quantified by the fluorescent X-ray analyzer remained unchanged before and after the treatment with the hexavalent chromium treatment agent.
  • the leather having undergone the dyeing-fatliquoring step and hexavalent chromium treatment step was further subjected to glazing finish to obtain a glossy crocodile leather.
  • a crocodile leather sheet (thickness: 1.5 mm) subjected to chrome tanning in the chrome tanning step was prepared.
  • the total chromium content was quantified with a fluorescent X-ray analyzer and determined to be 7141 ppm.
  • the dyeing-fatliquoring step was performed on this leather using a dyeing-fatliquoring agent containing a color material, an oil, and a surfactant.
  • the hexavalent chromium treatment step was performed on the leather as follows. 0.5 parts by weight of the compound represented by formula (3), 2.5 parts by weight of the compound represented by formula (4), and 2.0 parts by weight of the compound represented by formula (13) were mixed and dissolved in a mixed solvent of water and IPA (50% by weight:50% by weight) to obtain a hexavalent chromium treatment agent.
  • the mixed solvent was used in an amount such that the total amount of the treatment agent was 500 parts by weight.
  • the above crocodile leather was immersed in the obtained treatment agent and then dried to obtain a hexavalent chromium treatment agent-treated leather.
  • hexavalent chromium content was not more than the detection limit (2 ppm).
  • the total chromium content as quantified by the fluorescent X-ray analyzer remained unchanged before and after the treatment with the hexavalent chromium treatment agent.
  • the leather having undergone the dyeing-fatliquoring step and hexavalent chromium treatment step was further subjected to glazing finish to obtain a glossy crocodile leather.

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Claims (21)

  1. Procédé de production de cuir pour produire un cuir de reptile, comprenant : une étape de tannage au chrome comprenant la mise en œuvre d'un tannage au chrome sur une peau de reptile pour obtenir un cuir; une étape de teinture-nourriture en bain comprenant la mise en œuvre simultanément d'une teinture et d'une nourriture en bain sur le cuir soumis au tannage au chrome ; et une étape de finition comprenant la mise en œuvre d'une finition sur le cuir soumis à la teinture et à la nourriture en bain,
    le procédé comprenant en outre une étape de traitement au chrome hexavalent comprenant, avant l'étape de finition, l'application d'un composé réduisant le chrome hexavalent capable de réduire le chrome hexavalent en chrome trivalent sur le cuir soumis au tannage au chrome dans l'étape de tannage au chrome,
    dans lequel le composé réduisant le chrome hexavalent comprend un composé organique (A) qui présente une structure représentée par la formule (1) suivante et capable d'agir pour réduire le chrome hexavalent en chrome trivalent, qui présente un groupe hydroxyphényle, et qui ne présente pas de groupe aldéhyde et pas de groupe carboxyle :
    Figure imgb0057
     dans laquelle R1, R2, R3, R4, et R5 sont chacun indépendamment un substituant composé de C, H, O et R1 ou R2 et R3, R4, ou R5 peuvent être liés ensemble pour former un cycle.
  2. Procédé de production de cuir selon la revendication 1, dans lequel l'étape de teinture-nourriture en bain et l'étape de traitement au chrome hexavalent sont effectuées simultanément sur le cuir soumis au tannage au chrome.
  3. Procédé de production de cuir selon la revendication 1, dans lequel le composé organique (A) présente une structure représentée par la formule (1) et capable d'agir pour réduire le chrome hexavalent en chrome trivalent, présente un groupe dihydroxyphényle ou un groupe trihydroxyphényle, et ne présente pas de groupe aldéhyde et pas de groupe carboxyle.
  4. Procédé de production de cuir selon la revendication 3, dans lequel le composé organique (A) présente une structure représentée par la formule (1) et capable d'agir pour réduire le chrome hexavalent en chrome trivalent, présente un groupe 3,4,5-trihydroxyphényle, et ne présente pas de groupe aldéhyde et pas de groupe carboxyle.
  5. Procédé de production de cuir selon la revendication 4, dans lequel le composé organique (A) comprend :
    (i) un ester d'acide gallique ; et
    (ii) au moins un composé sélectionné parmi l'acide tannique et un dérivé de celui-ci.
  6. Procédé de production de cuir selon la revendication 5, dans lequel le composé (ii) est l'acide tannique.
  7. Procédé de production de cuir selon l'une quelconque des revendications 1 à 6, dans lequel le composé réduisant le chrome hexavalent comprend en outre un composé organique (B) qui présente une structure représentée par la formule (1) et capable d'agir pour réduire le chrome hexavalent en chrome trivalent et qui ne présente pas de groupe hydroxyphényle, pas de groupe aldéhyde, et pas de groupe carboxyle.
  8. Procédé de production de cuir selon la revendication 7, dans lequel le composé organique (B) est au moins un composé sélectionné parmi l'acide ascorbique, un dérivé de l'acide ascorbique, l'acide érythorbique, et un dérivé de l'acide érythorbique.
  9. Procédé de production de cuir selon la revendication 1 ou 2, dans lequel le composé réduisant le chrome hexavalent comprend au moins l'un sélectionné parmi un composé (A-i) représenté par la formule (A-i) suivante et un tanin (A-ii) :
    Figure imgb0058
     dans laquelle
    n représente 0, 1, ou 2,
    R11 à R18 représentent chacun indépendamment un atome d'hydrogène, un groupe hydroxy, un groupe alkyle en C1 à C4, un groupe alcoxy en C1 à C4, ou un groupe représenté par la formule (a-i) suivante,
    quand n est 0, au moins l'un parmi R11 à R14, R16, et R17 est un groupe hydroxy,
    quand n est 1 ou 2, au moins l'un parmi R11 à R18 est un groupe hydroxy,
    quand n est 2, une pluralité de R15 peuvent être identiques ou différents, et une pluralité de R18 peuvent être identiques ou différents,
    R16 et R17 peuvent être liés ensemble pour former un cycle à cinq chaînons ou un cycle à six chaînons, et le cycle peut présenter un groupe alkyle en C1 à C16 en tant que substituant :
    Figure imgb0059
     dans laquelle R19 représente un groupe alkyle en C1 à C4.
  10. Procédé de production de cuir selon la revendication 9, dans lequel le composé réduisant le chrome hexavalent comprend en outre au moins l'un sélectionné parmi un composé (B-i) représenté par la formule (B-i) suivante et un composé (B-ii) représenté par la formule (B-ii) suivante :
    Figure imgb0060
    Figure imgb0061
     dans lesquelles X représente un groupe représenté par l'une quelconque des formules (b-i) à (b-iii) suivantes :
    Figure imgb0062
    Figure imgb0063
    Figure imgb0064
     dans laquelle o représente un nombre entier allant de 0 à 3, p représente un nombre entier allant de 1 à 3, et q représente un nombre entier allant de 1 à 17.
  11. Cuir de reptile soumis à un tannage au chrome, le cuir comprenant un composé réduisant le chrome hexavalent sans gradient de concentration depuis le côté grain du cuir vers le côté opposé, le composé réduisant le chrome hexavalent étant capable de réduire le chrome hexavalent en chrome trivalent,
    dans lequel le composé réduisant le chrome hexavalent comprend un composé organique (A) qui présente une structure représentée par la formule (1) suivante et capable d'agir pour réduire le chrome hexavalent en chrome trivalent, qui présente un groupe hydroxyphényle, et qui ne présente pas de groupe aldéhyde et pas de groupe carboxyle :
    Figure imgb0065
     dans laquelle R1, R2, R3, R4, et R5 sont chacun indépendamment un substituant composé de C, H, O, et R1 ou R2 et R3, R4, ou R5 peuvent être liés ensemble pour former un cycle.
  12. Cuir selon la revendication 11, dans lequel le composé organique (A) présente une structure représentée par la formule (1) et capable d'agir pour réduire le chrome hexavalent en chrome trivalent, présente un groupe dihydroxyphényle ou un groupe trihydroxyphényle, et ne présente pas de groupe aldéhyde et pas de groupe carboxyle.
  13. Cuir selon la revendication 12, dans lequel le composé organique (A) présente une structure représentée par la formule (1) et capable d'agir pour réduire le chrome hexavalent en chrome trivalent, présente un groupe 3,4,5-trihydroxyphényle, et ne présente pas de groupe aldéhyde et pas de groupe carboxyle.
  14. Cuir selon la revendication 13, dans lequel le composé organique (A) comprend :
    (i) un ester d'acide gallique ; et
    (ii) au moins un composé sélectionné parmi l'acide tannique et un dérivé de celui-ci.
  15. Cuir selon la revendication 14, dans lequel le composé (ii) est l'acide tannique.
  16. Cuir selon l'une quelconque des revendications 11 à 15, dans lequel le composé réduisant le chrome hexavalent comprend en outre un composé organique (B) qui présente une structure représentée par la formule (1) et capable d'agir pour réduire le chrome hexavalent en chrome trivalent et qui ne présente pas de groupe hydroxyphényle, pas de groupe aldéhyde, et pas de groupe carboxyle.
  17. Cuir selon la revendication 16, dans lequel le composé organique (B) est au moins un composé sélectionné parmi l'acide ascorbique, un dérivé de l'acide ascorbique, l'acide érythorbique, et un dérivé de l'acide érythorbique.
  18. Cuir selon la revendication 11, dans lequel le composé réduisant le chrome hexavalent comprend au moins l'un sélectionné parmi un composé (A-i) représenté par la formule (A-i) suivante et un tanin (A-ii) :
    Figure imgb0066
     dans laquelle
    n représente 0, 1, ou 2,
    R11 à R18 représentent chacun indépendamment un atome d'hydrogène, un groupe hydroxy, un groupe alkyle en C1 à C4, un groupe alcoxy en C1 à C4, ou un groupe représenté par la formule (a-i) suivante,
    quand n est 0, au moins l'un parmi R11 à R14, R16, et R17 est un groupe hydroxy,
    quand n est 1 ou 2, au moins l'un parmi R11 à R18 est un groupe hydroxy,
    quand n est 2, une pluralité de R15 peuvent être identiques ou différents, et une pluralité de R18 peuvent être identiques ou différents,
    R16 et R17 peuvent être liés ensemble pour former un cycle à cinq chaînons ou un cycle à six chaînons, et le cycle peut présenter un groupe alkyle en C1 à C16 en tant que substituant :
    Figure imgb0067
     dans laquelle R19 représente un groupe alkyle en C1 à C4.
  19. Cuir selon la revendication 18, dans lequel le composé réduisant le chrome hexavalent comprend en outre au moins l'un sélectionné parmi un composé (B-i) représenté par la formule (B-i) suivante et un composé (B-ii) représenté par la formule (B-ii) suivante :
    Figure imgb0068
    Figure imgb0069
     dans lesquelles X représente un groupe représenté par l'une quelconque des formules (b-i) à (b-iii) suivantes :
    Figure imgb0070
    Figure imgb0071
    Figure imgb0072
     dans laquelle o représente un nombre entier allant de 0 à 3, p représente un nombre entier allant de 1 à 3, et q représente un nombre entier allant de 1 à 17.
  20. Procédé de production d'un article en cuir, comprenant la production d'un cuir par le procédé de production de cuir selon l'une quelconque des revendications 1 à 10, et comprenant en outre une étape de traitement ultérieur comprenant le traitement du cuir.
  21. Article en cuir comprenant le cuir selon l'une quelconque des revendications 11 à 19.
EP17744370.2A 2016-01-29 2017-01-27 Cuir ou article en cuir de reptile mettant en oeuvre un agent de traitement au chrome hexavalent, et procédé de fabrication de ceux-ci Active EP3409795B1 (fr)

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DE10143948A1 (de) * 2001-09-07 2003-03-27 Basf Ag Polyisobuten als Austauschstoff für Wollfett in Fettungsmitteln für die Ledererzeugung, die Fettungsmittel, ihre Verwendung und die erzeugten Leder
DE602006014722D1 (de) * 2005-11-29 2010-07-15 Tfl Ledertechnik Gmbh Lederbehandlung und mittel
US20120231249A1 (en) * 2009-11-19 2012-09-13 Midori Hokuyo Co., Ltd. Car-seat split crust leather and method for manufacturing the same, and car-seat leather using the car-seat split crust leather and method for manufacturing the same
KR101248083B1 (ko) * 2011-05-06 2013-03-27 한국신발피혁연구소 천연피혁의 제조방법
CN103374634A (zh) * 2012-04-19 2013-10-30 咸阳银河无机材料有限公司 一种能够去除和防止皮革中生成六价铬的助剂及制备方法
WO2014112404A1 (fr) * 2013-01-17 2014-07-24 協伸株式会社 Stratifié de cuir et son procédé de fabrication
CN104593527B (zh) * 2015-01-28 2016-08-24 陕西科技大学 鳄鱼腹部皮制革加工方法
JP6605881B2 (ja) * 2015-08-21 2019-11-13 一般財団法人日本皮革研究所 クロム鞣し革用六価クロム生成抑制剤、およびクロム鞣し革の製造方法
CN105155307B (zh) * 2015-08-27 2018-08-28 兴业皮革科技股份有限公司 一种基于锆铝钛配合物的皮革湿态染整固色方法

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CN108463563B (zh) 2020-10-30
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EP3409795A1 (fr) 2018-12-05
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