EP2954073B1 - Verfahren zur behandlung von halbfabrikaten aus leder, kunstleder und/oder textilien und gegenstände, die die daraus entstandenen produkte beinhalten. - Google Patents

Verfahren zur behandlung von halbfabrikaten aus leder, kunstleder und/oder textilien und gegenstände, die die daraus entstandenen produkte beinhalten. Download PDF

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Publication number
EP2954073B1
EP2954073B1 EP14710971.4A EP14710971A EP2954073B1 EP 2954073 B1 EP2954073 B1 EP 2954073B1 EP 14710971 A EP14710971 A EP 14710971A EP 2954073 B1 EP2954073 B1 EP 2954073B1
Authority
EP
European Patent Office
Prior art keywords
silver
particles
salts
insoluble
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP14710971.4A
Other languages
English (en)
French (fr)
Other versions
EP2954073A1 (de
Inventor
Angelo Ramponi
Sandro RECCHIA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Conceria Stefania SpA
Universita degli Studi dell Insubria
Original Assignee
Conceria Stefania SpA
Universita degli Studi dell Insubria
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Filing date
Publication date
Application filed by Conceria Stefania SpA, Universita degli Studi dell Insubria filed Critical Conceria Stefania SpA
Publication of EP2954073A1 publication Critical patent/EP2954073A1/de
Application granted granted Critical
Publication of EP2954073B1 publication Critical patent/EP2954073B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • 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
    • C14C13/00—Manufacture of special kinds or leather, e.g. vellum
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/15—Proteins or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/125—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyamides
    • D06N3/126—Poly-amino acids, e.g. polyglutamates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/02—Natural macromolecular compounds or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2205/00—Condition, form or state of the materials
    • D06N2205/10—Particulate form, e.g. powder, granule
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/165—Odour absorbing, deodorizing ability
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/10—Clothing

Definitions

  • the present invention relates to an improved process for the treatment of leather, imitation leather or fabric semimanufactured products as well as to items comprising said semimanufactured products treated with said process.
  • the method covered by the previous patent application provides semimanufactured products made of leather or similar materials with a high degree of comfortableness as well as high transpiration and reduction of the odours caused by the perspiration of the user's skin.
  • a further advantage achieved with the treatment method envisaged in the previous international patent application is that, by using natural materials, such as proteins, in aqueous solutions for processing leather, so as improve their properties of softness and comfortableness, as well as high water vapour permeability, said use entails a limited environmental impact.
  • antiseptic, deodorant and antibacterial properties are provided to the leather or similar semimanufactured products by the use, in particular, of metal silver particles.
  • the Applicant found that, when using metal silver particles having an average size within a range of some tens of micron, antibacterial properties were indeed preserved at satisfactory levels (at lest 90% of antibacterial activity found on the leather as treated and submitted to protocol ASTM E2149 - 10 "Standard method for determining the antimicrobial activity of immobilized antimicrobial agent under dynamic contact condition") in the semimanufactured products as treated immediately after treatment, but said properties dropped with the passing of time, particularly in semimanufactured products as treated which were later submitted to accelerated wear testing.
  • the purpose of the present invention is therefore a process for the treatment of a leather, imitation leather or fabric semimanufactured product, said process comprising the steps of:
  • the process according to the present invention is aimed at the treatment of leathers, in particular cowhides of various kinds, but can also be used to treat fabrics similar to leather, such as imitation leather.
  • leathers in particular cowhides of various kinds
  • fabrics similar to leather such as imitation leather.
  • the process according to the present invention is further aimed at the treatment of fabric(s), meaning both natural fibre fabrics and artificial/synthetic fibre fabrics or fabric(s) deriving from a mixture of said fibres.
  • the kinds of natural textile fibres of vegetable origin included in the fabric(s) which can be treated with the process covered by the present invention are: cotton, flax, hemp, jute, ramie (or nettle yarn), sisal, coco, broom, hibiscus, manila hemp, straw, bamboo, cork.
  • the kinds of natural textile fibres of animal origin included in the fabric(s) which can be treated with the process covered by the present invention are: wools such as Merinos, Shetland, Bluefaiced Leicester, Corriedale, Crossed Wools, Lambswool, English, Asian, Mazamet, Regenerated Wools; hairwools such as Angora, Cachemire, Camel, Mohair, Alpaca, Lama, Vicugna or vicu ⁇ a, Bison, Quivut or Quivuk; Silks, Horsehair or Byssus.
  • the kinds of natural textile fibres of mineral origin included in the fabric(s) which can be treated with the process covered by the present invention are glass fibres.
  • the kinds of artificial textile fibres included in the fabric (s) which can be treated with the process covered by the present invention are: cellulose fibres such as Rayon, Modal, Cuprammonium Rayon, Acetate, Triacetate, Lyocell.
  • the kinds of synthetic textile fibres included in the fabric(s) which can be treated with the process covered by the present invention are: acrylic, polyamide (such as for example Nylon 6, Nylon 6,6), polyester, polypropylene, polyethylene, chlorovinyl, polyurethane, polytetrafluoroethylene, aramid fibres.
  • the process according to the invention firstly comprises a step to provide a semimanufactured product to be treated.
  • Said semimanufactured product can for example comprise a leather pre-tanned with known procedures. Or else, said semimanufactured product may comprise for example a cotton or polyester fabric prepared with known procedures.
  • the semimanufactured product is treated by applying thereto, according to procedures to be described, a special treatment solution which is prepared according to specific procedures.
  • the treatment solution is not necessarily applied to the entire semimanufactured product, but preferably only to a surface thereof or only to small spots or an area of the same.
  • only one side of the leather is treated with the process according to the invention.
  • the treatment is limited to the portion of the leather destined to come into contact with the user's skin.
  • the treated surface is that destined to delimit the seat for the user's foot and which therefore will come into contact therewith.
  • the treated surface is the inner surface of the watchstrap, i.e. the surface that will come into contact with the skin of the user's wrist.
  • particles comprising silver ions in the form of insoluble or slightly soluble salts according to the present invention means in particular:
  • a preferred embodiment of the present invention envisages the use of metal silver particles comprising on the surface insoluble or slightly soluble, inorganic or organic silver ion salts, wherein said surface has a minimum thickness of 50 nanometers. More advantageously said particles have a weight ratio between the salified surface and the metal silver mass amounting to at least 1%, preferably amounting to or exceeding 3%, more preferably amounting to or exceeding 20%.
  • the particles comprising silver ions in the form of insoluble or slightly soluble salts used in the process according to the present invention are preferably particles having a minimum diameter amounting to or exceeding 0.1 micron, preferably amounting to or exceeding 0.25 micron.
  • the particles used in the proceeding covered by the present invention can have any shape or morphology: for example, they can be spherical, scaly granular, powders or dispersions/suspensions of fine particulate, although powders of both silver salts and metal silver salified on the surface are the preferred shape and morphology.
  • metal silver particles comprising on the surface insoluble or slightly soluble, inorganic or organic silver ion salts are achieved through the method comprising the following steps:
  • step a) of oxidative aggression in aqueous acid medium of a portion of the surface of the metal silver with formation of silver ions said surface has a minimum thickness of 50 nanometers.
  • the metal silver particles comprising on the surface insoluble or slightly soluble, inorganic or organic silver ion salts are preferably used in the treatment of products to be used for manufacturing items which require a high degree of thermoregulation, preferably items which come into contact with the end user's foot, because they advantageously preserve a core of metal silver, namely the metal with the highest ever thermal conductivity.
  • the metal silver particles comprising on the surface insoluble or slightly soluble, inorganic or organic silver ion salts advantageously have a weight ratio between the salified surface and the metal silver mass preferably higher than 70%-80%.
  • inorganic salts selected from the group comprising silver chloride, silver iodide, silver bromide, silver sulphate, silver sulphide, silver iodate, silver phosphate, silver sulphite, or organic salts selected from the group comprising silver carbonate, silver oxalate, silver thiocyanate.
  • the natural proteins used in the binder solution can be of various type. Preferably, they are selected from the group consisting of casein, egg albumin, blood albumin.
  • the preferred binder used in the solution is in any case casein as this has the capacity to absorb moisture (which can, for example, derive from perspiration of the foot when the semimanufactured product is used to manufacture footwear).
  • Casein is a phosphoprotein which can be obtained from milk through appropriate treatment processes (e.g.: pressure, fermentation, acidification).
  • the binder solution it is possible for the binder solution to be provided with a combination of casein with albumin. In fact, this combination allows a sufficiently shiny film to be obtained on the leather
  • the binder solution can also comprise further additives suitable to give the leather specific characteristics.
  • additives can include one or more of the following additives: linseed mucilage, cellulose derivatives, such as carboxymethyl cellulose, gelatin, lac, soaps.
  • the binder solution contains plasticizers suitable to reduce the stiffness, fragility and elasticity of the film of protein solution once this has been applied to the leather.
  • the plasticizers are preferably selected from the group consisting of: sodium sulphoricinate, higher alcohols, glycols, glycerines, natural oils, natural waxes, both of vegetable and of animal origin.
  • a particularly advantageous embodiment of the present invention envisages the optional use, in combination with protein products, also of binders based on resins (normally polyurethane, polyamides) in suspension or in aqueous solution, for the preparation of the treatment solution, depending on the kind of semimanufactured product to be treated and the use the latter is meant for.
  • resins normally polyurethane, polyamides
  • the use of said resins, in combination with the treatment solution according to the present invention does not bring detriment to the antibacterial capabilities related to the use of the particles comprising silver ions in the form of insoluble or slightly soluble salts according to the present invention.
  • the absence of chemical solvents limits the overall environmental impact of the treatment.
  • the items produced from semimanufactured products treated with the process according to the invention ensure high ecological quality standards.
  • a further advantage linked to a binder solution of this type is that the presence of natural proteins ensures that the possibility of causing undesired allergies in the end user is low.
  • a further advantage linked to the use of an aqueous binder solution is the possibility of producing very thin, transparent and shiny finishes, which allow the leather to retain its natural water vapour permeability , while offering a high degree of comfort.
  • the antiseptic properties of particles comprising silver ions in the form of insoluble or slightly soluble salts are increased by the fact that it is immersed in a vapour permeable substance.
  • the binder solution has anionic charge and, preferably, a pH of 8.
  • the percentage of casein in the binder solution is preferably between 6% and 12%, even more preferably equal to 8% (said percentages are referred to the solution weight, which means % in weight of the binder solution).
  • Preparation of the treatment solution from the binder solution and from the particles comprising silver ions in the form of insoluble or slightly soluble salts with the aforesaid properties comprises a series of successive steps.
  • the particles comprising silver ions in the form of insoluble or slightly soluble salts to be used in the process according to the present invention are particles of insoluble or slightly soluble, inorganic or organic silver salts, preferably silver salts selected from the group comprising silver chloride, silver iodide, silver bromide, silver sulphate, silver sulphide, silver iodate, silver phosphate, silver sulphite, silver carbonate, silver oxalate, silver thiocyanate, said salts can be found on the market; if needed, they can be submitted to granulometric selection.
  • the particles comprising silver ions in the form of insoluble or slightly soluble salts to be used in the process according to the present invention are metal silver particles comprising on the surface insoluble or slightly soluble, inorganic or organic silver ion salts, said particles are best prepared by a separate process, according to the procedure as described above, before they are mixed with the binder solution.
  • the binder solution and the particles comprising silver ions in the form of insoluble or slightly soluble salts are mixed, preferably in a ratio of 1:10 (i.e. with one part of powdered particles comprising silver ions in the form of insoluble or slightly soluble salts and ten parts of binder), dispersing the particles comprising silver ions in the form of insoluble or slightly soluble salts in the binder solution.
  • the suspension thus obtained is then mixed until obtaining a substantially homogenous paste.
  • the step of preparing the treatment solution comprises the following steps:
  • Providing the particles comprising ionic silver in the form of insoluble or slightly soluble salts, when said particles are metal silver particles whose surface comprises insoluble or slightly soluble silver ion salts, means to implement the method, as described above, of preparation of said metal silver particles coated with insoluble or slightly soluble silver ion salts.
  • the step to apply the treatment solution to the semimanufactured product to be treated can be performed in several manners: by way of example, it can be applied by spraying, roller, transfer, screen printing or hand pressing.
  • the choice of the application method depends on the chemical and physical features of the substrate of the semimanufactured product to be treated.
  • Water is subsequently added to the paste of casein and particles comprising silver ions in the form of insoluble or slightly soluble salts described above, in such a way as to obtain a diluted solution.
  • water is added in such a quantity that in the treatment solution the particles comprising silver ions in the form of insoluble or slightly soluble salts reach a concentration of between 7 and 12 g/l, preferably equal to 10 g/l.
  • the solution thus obtained is then kept under stirring, for example using a blade stirrer.
  • the maintenance speed is preferably between 250 and 350 rpm, even more preferably equal to 300 rpm.
  • the treatment process includes a step to apply the treatment solution to the semimanufactured product to be treated, in particular to the surface destined to come into contact with the skin of the end user.
  • the treatment solution is applied to leather or imitation leather or fabric semimanufactured products by spraying, preferably by means of compressed air guns.
  • the spray pressure is preferably maintained between 0.4 and 0.7 atm.
  • the treatment solution is sprayed through nozzles having a diameter between 0.5 and 1.3 mm, even more preferably equal to 0.8 mm.
  • the treatment solution is applied at low pressure and high volume, with reference to the pressures and to the volumes which are normally used to treat leathers (for example, when applying dyes).
  • the step to apply the treatment solution takes place according to a plurality of successive application operations.
  • the treatment solution is applied in four subsequent application operations, each preferably applying between 40 and 60 grams of treatment solution per square metre of surface of the semimanufactured product.
  • the quantity of treatment solution applied is equal to 50 grams per square metre of surface of the semimanufactured product.
  • the treatment solution applied is therefore equal to 200 g per square metre of surface of semimanufactured product, which, according to a preferred embodiment, corresponds to 2 grams of particles comprising silver ions in the form of insoluble or slightly soluble salts per square metre of semimanufactured product to be treated.
  • the treatment solution can be applied to leather, imitation leather or fabric semimanufactured products by means of a roller, preferably by using engraved cylinder machines of the roller coating kind.
  • Further organic binder is preferably added to the paste of casein and particles comprising silver ions in the form of insoluble or slightly soluble salts in order to obtain a mixture with optimal viscosity for application by roller.
  • the solution thus obtained is then kept under stirring, for example using a blade stirrer.
  • the maintenance speed is preferably between 250 and 350 rpm, even more preferably equal to 300 rpm.
  • Viscosity is measured by an equipment consisting of a Ford viscosity cup with a 4-mm-nozzle.
  • the mixture viscosity must range between 30 and 60 seconds, preferably 50.
  • the concentration of the particles comprising silver ions in the form of insoluble or slightly soluble salts must range between 10 and 50 gr/litre, preferably 30.
  • the solution is applied only to one side of the leather, namely the one which will come into contact with the user's skin.
  • the treatment solution is applied by using a properly engraved cylinder which can distribute a predetermined amount of mixture on the leather.
  • the depth and the distribution of the engravings on the cylinder determine the amount which can be transferred.
  • the applied amount can be further increased or decreased also by acting on the leather entrainment speed in the roller coating as well as on the number of rotations of the distributing cylinder.
  • the treatment solution is distributed on the cylinder through a diaphragm pump which draws the solution from the container where it is kept under stirring.
  • the solution in excess, sent to the cylinder, is reclaimed by a device placed on the apparatus.
  • the amount of solution applied by the cylinder ranges between 30 and 90 gr/m 2 and can be obtained with several successive steps depending on the absorption capability of the substrate.
  • the treatment solution comprising a binder solution and particles comprising silver ions in the form of insoluble or slightly soluble salts can be applied to a sheet, for example a polyester or silicone paper sheet, and then transferred on the leather, imitation leather or fabric(s) by hot-pressing.
  • a sheet for example a polyester or silicone paper sheet
  • hot-pressing machines developing temperatures above 90°C, even up to 150°C, pressures ranging between 2 and 3 bar and contact times from 0.5-2 sec up to even 15-30 sec must be used.
  • the treatment solution according to the present invention can also be applied to any semimanufactured product also using techniques similar to printing by a screen-print frame and hand pressing, without any change of procedure compared to said techniques, applicable according to the relevant well-known procedures from the state of the art.
  • the step to apply the solution to the semimanufactured product by any of the above techniques can in its turn be followed by the successive steps to fix and/or to dry and/or to buff, which are described below.
  • the treatment process according to the invention also comprises a step to fix the treatment solution to the surface of the semimanufactured product.
  • the fixing step has the purpose of insolubilizing the natural proteins of the binder solution, so as to make them swell less in water and thus obtain stability to wet treatments.
  • the fixing step takes place according to a plurality of successive fixing operations.
  • each application operation is followed by a fixing operation suitable to fix the treatment solution applied in the specific application operation to the surface of the semimanufactured product.
  • each of the fixing operations comprises the application of a fixing substance to the surface of the semimanufactured product (to which the treatment solution has been previously applied).
  • the fixing substance contains aldehydes suitable for crosslinking the natural proteins of the binder solution (and of the treatment solution).
  • the fixing substance contains glyoxal, which is suitable for crosslinking casein. Glyoxal is preferably included in the fixing substance in a percentage between 3% and 5%.
  • the process according to the invention comprises a step to dry the semimanufactured product on which the treatment solution has been applied, which can be performed with a plurality of successive operations.
  • the single drying operations can be implemented by placing the semimanufactured product in an environment which has a predetermined drying temperature, for example in a drying oven.
  • the drying temperature is preferably between 30°C and 90°C, even more preferably equal to 60 °C.
  • the time of the drying operations preferably varies from 20 to 120 seconds.
  • the process according to the invention also comprises a final buffing step.
  • This buffing step can, for example, be obtained through hot stretching using heated rollers that press the semimanufactured product on the treated side. This process allows a leather with a high level of smoothness and shine to be obtained.
  • the semimanufactured product treated according to the procedures described can advantageously be used to manufacture a particular item, such as an article of clothing, footwear, a watchstrap, a small leather article (wallet, purse), a covering for objects (for eyewear, for seats), or the like.
  • the leather of the shoe Due to the treatment to which the semimanufactured product is subjected, based on an aqueous binder solution, the leather of the shoe is soft and elastic, as well as sufficiently breathable. Moreover, the presence of the particles comprising silver ions in the form of insoluble or slightly soluble salts limits the production of unpleasant odours linked to perspiration of the foot due to the antiseptic, antibacterial and odour-preventing action of the particles comprising silver ions in the form of insoluble or slightly soluble salts dispersed on the internal surface of the shoe.
  • aqueous binder solution and the particles comprising silver ions in the form of insoluble or slightly soluble salts, especially when applied to leather, provides products with a high level of permeability to perspiration and the capacity to limit the occurrence of unpleasant odours.
  • the three solutions for application by roller were prepared by keeping the same concentrations in weight of the products which make up the solution, namely: natural proteins (including casein), plasticizers, organic binders and water in order to have solutions at 30 g/l of metal silver particles (No. PCT/IT/2009/000445 ), silver salt particles and metal silver particles coated by silver salt, respectively.
  • Each of the three solutions was kept under stirring during application (250 - 350 rpm using a blade stirrer), after checking viscosity with a Ford viscosity cup -with a 4-mm-nozzle.
  • the roller coating machine was set to apply 35 g/m 2 of binder solution for each of the different samples.
  • the antibacterial activity of all the three specimens obtained at the end of the respective treatments was tested using the method/protocol ASTM E2149 - 10 "Standard method for determining the antimicrobial activity of immobilized antimicrobial agent under dynamic contact condition" wherein the antibacterial activity is tested by putting the leather samples into contact with known amounts of bacterial strains of Escherichia coli and counting progressively in time the residual bacterial charge.
  • the sampled antibacterial activity remained at satisfactory levels of least 90%. In the case of the other two leather specimens, the sampled antibacterial activity ranged between 98 and 100%.
  • the abrasion testing equipment is a machine named "Martindale” ensuring the formation of the Lissajous figure during movement between the sample holders, on which a leather specimen is mounted, and the abrading plane coated with wool fabric, submitted to a constant pressure of (12 ⁇ 0,2) kPa.
  • the device is provided with a revolution counter: each revolution corresponds to an ellipse of the Lissajous figure.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microbiology (AREA)
  • Biochemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Claims (19)

  1. Verfahren zur Behandlung von Halbfabrikaten aus Leder, Kunstleder oder Textilien, wobei das Verfahren folgende Schritte umfasst:
    - Bereitstellen des Halbfabrikats, das behandelt werden soll;
    - Zubereiten einer Behandlungslösung, die ein Bindemittel und Partikel umfasst, die Silberionen in Form nicht löslicher oder schwer löslicher Salze umfasst;
    - Auftragen der Behandlungslösung auf wenigstens eine Oberfläche des Halbfabrikats, das behandelt werden soll,
    - wobei die Bindemittellösung natürliche Proteine in wässriger Lösung umfasst.
  2. Verfahren nach Anspruch 1, wobei die natürlichen Proteine Casein und/oder Eieralbumin und/oder Blutalbumin umfassen.
  3. Verfahren nach Anspruch 1 oder 2, wobei die Bindemittellösung natürliche Proteinweichmacher umfasst, wobei die Weichmacher aus der Gruppe ausgewählt sind, umfassend: Natriumsulphoricinat, höhere Alkohole, Glykole, Glyzerine, natürliche Öle, natürliche Wachse, entweder pflanzlichen oder tierischen Ursprungs.
  4. Verfahren nach einem der vorangehenden Ansprüche, wobei die Bindemittellösung weitere Zusatzstoffe umfasst, die ausgewählt sind aus der Gruppe umfassend: Leinsamenschleimstoffe, Zellulosederivate, Gelatine, Schellack, Seifen.
  5. Verfahren nach einem der vorangehenden Ansprüche, wobei die natürlichen Proteine in der Bindemittellösung mit einer Prozentzahl von 8 Gewichtsprozent der Bindemittellösung vorhanden sind.
  6. Verfahren nach einem der vorangehenden Ansprüche, wobei die Bindemittellösung eine anionische Ladung und einen pH-Wert gleich 8 aufweist.
  7. Verfahren nach Anspruch 1, wobei die Partikel, die Silberionen in Form von nicht löslichen oder schwer löslichen Salzen umfassen, Partikel nicht löslicher oder schwer löslicher Silbersalze sind, entweder anorganischer oder organischer Art.
  8. Verfahren nach Anspruch 7, wobei die Partikel nicht löslicher oder schwer löslicher Silbersalze Partikel anorganischer Salze sind, ausgewählt aus der Gruppe umfassend Silberchlorid, Silberiodid, Silberbromid, Silbersulfat, Silbersulfid, Silberiodat, Silberphosphat, Silbersulfit oder organische Salze ausgewählt aus der Gruppe umfassend Silbercarbonat, Silberoxalat.
  9. Verfahren nach Anspruch 1, wobei die Partikel Silberionen in Form von nicht löslichen oder schwer löslichen Salzen umfassen, Metallsilberpartikel sind, die auf der Oberfläche nicht lösliche oder schwer lösliche Silberionensalze umfassen, entweder anorganischer oder organischer Art.
  10. Verfahren nach Anspruch 9, wobei die Salze auf der Oberfläche der Metallsilberpartikel anorganische Salze sind, ausgewählt aus der Gruppe umfassend Silberchlorid, Silberiodid, Silberbromid, Silbersulfat, Silbersulfid, Silberiodat, Silberphosphat, Silbersulfit oder organische Salze ausgewählt aus der Gruppe umfassend Silbercarbonat, Silberoxalat.
  11. Verfahren nach Anspruch 9, wobei die Metallsilberpartikel, die auf der Oberfläche nicht lösliche oder schwer lösliche Silberionensalze umfassen, durch ein Verfahren erhalten werden, das die folgenden Schritte umfasst:
    a) oxidative Aggression in wässrigem Säuremedium eines Teils der Oberfläche des Metallsilbers mit Bildung von Silberionen;
    b) Fixieren von Silberionen auf der Oberfläche der Metallsilberpartikel, die in Schritt a) behandelt wurden, in Form von nicht löslichen oder schwer löslichen anorganischen und organischen Salzen durch Hinzufügen eines ausfällenden Reagens, das dem nicht löslichen oder schwer löslichen anorganischen oder organischen Silbersalz von Interesse entspricht;
    c) Trocknen der Partikel, die in Schritt b) erhalten wurden.
  12. Verfahren nach Anspruch 11, wobei in Schritt a) der oxidativen Aggression in wässrigem Säuremedium eines Teils der Oberfläche des Metallsilbers mit Bildung von Silberionen die Oberfläche eine minimale Dicke von 50 Nanometer aufweist.
  13. Verfahren nach Anspruch 11, wobei Schritt b) des Fixierens der Silberionen in Form von Salzen auf der Oberfläche der Metallsilberpartikel die Bildung von Salzen beinhaltet, die ausgewählt sind aus der Gruppe umfassend: Silberchlorid, Silberiodid, Silberbromid, Silbersulfat, Silbersulfid, Silberiodid, Silberphosphat, Silbersulfit, Silbercarbonat, Silberoxalat.
  14. Verfahren nach einem der vorangehenden Ansprüche, wobei der Schritt des Zubereitens der Behandlungslösung folgende Schritte umfasst:
    - Bereitstellen der Bindemittellösung;
    - Bereitstellen der Partikel, die ionisches Silber in Form von nicht löslichen oder schwer löslichen Salzen umfassen;
    - Mischen der Bindemittellösung und der Partikel, die Silberionen in Form von nicht löslichen oder schwer löslichen Salzen umfassen;
    - Mischen der Bindemittellösung und der Partikel, die Silberionen in Form von nicht löslichen oder schwer löslichen Salzen umfassen, bis eine im Wesentlichen homogene Paste erhalten wird.
  15. Verfahren nach einem der vorangehenden Ansprüche, wobei der Schritt des Auftragens der Behandlungslösung auf das Halbfabrikat, das behandelt werden soll, Folgendes umfasst:
    - einen Sprühschritt oder
    - einen Rollenauftragungsschritt oder
    - einen Übertragungsauftragungsschritt oder
    - einen Siebdruckauftragungsschritt oder
    - einen Handdruckauftragungsschritt
    der Behandlungslösung auf die Oberfläche des Halbfabrikats.
  16. Verfahren nach einem der vorangehenden Ansprüche, ferner umfassend einen Schritt des Fixierens der aufgetragenen Behandlungslösung auf der wenigstens einen Oberfläche des Halbfabrikatproduktes, das behandelt werden soll.
  17. Verfahren nach einem der vorangehenden Ansprüche, ferner umfassend einen Schritt des Trocknens des Halbfabrikats.
  18. Verfahren nach einem der vorangehenden Ansprüche, umfassend einen Polierschritt, vorzugsweise durch Warmstreckung.
  19. Gegenstand aus einem Halbfabrikat aus Leder, Kunstleder oder Textilien, das mit dem Verfahren nach einem der vorangehenden Ansprüche behandelt wurde.
EP14710971.4A 2013-02-11 2014-02-04 Verfahren zur behandlung von halbfabrikaten aus leder, kunstleder und/oder textilien und gegenstände, die die daraus entstandenen produkte beinhalten. Not-in-force EP2954073B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000187A ITMI20130187A1 (it) 2013-02-11 2013-02-11 Procedimento migliorato per il trattamento di semilavorati in pelle, similpelle e/o tessuto/i nonché articoli comprendenti tali semilavorati trattati con tale procedimento
PCT/IB2014/058771 WO2014122573A1 (en) 2013-02-11 2014-02-04 Process for treatment of semimanufactured products made of leather, imitation leather and/or fabric/s and items comprising said semimanufactured products resulting thereof

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EP2954073A1 EP2954073A1 (de) 2015-12-16
EP2954073B1 true EP2954073B1 (de) 2016-11-02

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EP14710971.4A Not-in-force EP2954073B1 (de) 2013-02-11 2014-02-04 Verfahren zur behandlung von halbfabrikaten aus leder, kunstleder und/oder textilien und gegenstände, die die daraus entstandenen produkte beinhalten.

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EP (1) EP2954073B1 (de)
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Publication number Priority date Publication date Assignee Title
IT202100030317A1 (it) * 2021-11-30 2023-05-30 Conceria Nuvolari Srl Miscela e metodo per il trattamento del pellame

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DK148492D0 (de) * 1992-12-10 1992-12-10 Novo Nordisk As
CN1627901A (zh) * 2002-06-03 2005-06-15 深圳市清华源兴生物医药科技有限公司 银质纳米复合材料
CN100344824C (zh) * 2004-10-18 2007-10-24 香港理工大学 一种织物功能整理助剂及其制备和应用方法
DE102005020889A1 (de) * 2005-05-04 2006-11-09 Fritz Blanke Gmbh & Co.Kg Verfahren zur antimikrobiellen Ausrüstung von textilen Flächengebilden
CN100553769C (zh) * 2008-05-26 2009-10-28 山东大学 钨酸/氯化银可见光光催化剂及其制备方法
UA100959C2 (uk) * 2009-10-01 2013-02-11 Кончериа Стефаниа Ес.Пи.А Спосіб обробки напівфабрикату, виготовленого зі шкіри або аналогічного матеріалу, і виріб з нього

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202100030317A1 (it) * 2021-11-30 2023-05-30 Conceria Nuvolari Srl Miscela e metodo per il trattamento del pellame
WO2023100047A1 (en) * 2021-11-30 2023-06-08 Conceria Nuvolari Srl Mixture and method for leather treatment

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ITMI20130187A1 (it) 2014-08-12
EP2954073A1 (de) 2015-12-16
CN105102640A (zh) 2015-11-25
WO2014122573A1 (en) 2014-08-14

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