WO2005017004A1 - Matiere composite pour realiser des parties de chaussure thermoformables a base de fibres organiques - Google Patents

Matiere composite pour realiser des parties de chaussure thermoformables a base de fibres organiques Download PDF

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Publication number
WO2005017004A1
WO2005017004A1 PCT/EP2004/008697 EP2004008697W WO2005017004A1 WO 2005017004 A1 WO2005017004 A1 WO 2005017004A1 EP 2004008697 W EP2004008697 W EP 2004008697W WO 2005017004 A1 WO2005017004 A1 WO 2005017004A1
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WO
WIPO (PCT)
Prior art keywords
composite material
weight
component
polymers
thermoplastic
Prior art date
Application number
PCT/EP2004/008697
Other languages
German (de)
English (en)
Inventor
Ewald Wilka
Thomas Hieber
Albrecht Reiter
Original Assignee
Ledertech Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ledertech Gmbh filed Critical Ledertech Gmbh
Priority to BRPI0413447 priority Critical patent/BRPI0413447A/pt
Priority to EP04763755A priority patent/EP1654309A1/fr
Publication of WO2005017004A1 publication Critical patent/WO2005017004A1/fr
Priority to US11/349,794 priority patent/US20060194486A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/08—Heel stiffeners; Toe stiffeners
    • A43B23/081—Toe stiffeners
    • A43B23/086—Toe stiffeners made of impregnated fabrics, plastics or the like
    • A43B23/087—Toe stiffeners made of impregnated fabrics, plastics or the like made of plastics
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/08—Heel stiffeners; Toe stiffeners
    • A43B23/081—Toe stiffeners
    • A43B23/085—Toe stiffeners made of leather
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/08—Heel stiffeners; Toe stiffeners
    • A43B23/14—Heel stiffeners; Toe stiffeners made of leather
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/08—Heel stiffeners; Toe stiffeners
    • A43B23/16—Heel stiffeners; Toe stiffeners made of impregnated fabrics, plastics or the like
    • A43B23/17—Heel stiffeners; Toe stiffeners made of impregnated fabrics, plastics or the like made of plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
    • Y10T442/102—Woven scrim
    • Y10T442/107—Comprising at least two chemically different fibers

Definitions

  • the invention relates to a composite material for thermally formable shoe components, containing fiber materials, a thermoplastic binder and natural latex.
  • the invention further relates to a method for producing such a composite material for thermally formable shoe components based on organic fibers.
  • the invention also relates to a coating of the composite material with adhesive, which serves to connect the composite material for thermally formable shoe components during processing in shoe production.
  • Composite materials also called composite materials, are materials that are created by incorporating a base material, for example in the form of fibers, into a second material (the matrix). Certain properties (e.g. mechanical properties,
  • the quantity of the base material can vary widely in relation to the matrix surrounding it.
  • the matrix content in wood-based materials which include, for example, the known particle board, is usually only 10-15%.
  • the proportion of matrix in fiber-reinforced plastics, for example in glass-fiber reinforced plastics can be significantly higher, for example over 70 or over 80%.
  • the composite material it is often possible to give the composite material certain properties of the base material that are paired with certain properties of the matrix by a suitable choice of base material and matrix.
  • the use of glass or natural fibers in thermosetting plastics can cause the tensile strength of the fibers to be transferred to the plastic matrix in turn, contributed advantages in terms of shape, dimensional stability and processability to the composite material.
  • the production of composite materials is often used to produce a material from by-products that arise during the processing of a certain base material that has characteristic properties of the base material.
  • the corresponding composite material can then generally be used at least as a substitute material for the base material, and thus permits "material-related" recycling of the base material waste or by-products. This is the case, for example, when recycling wood waste in particle board.
  • Another example of a material-related recycling of by-products is the processing of trimming and punching residues from leather and shoe production into leather fiber materials.
  • LEFA leather fiber materials
  • LEFA is usually a single-layer sheet made of leather fibers and binders. LEFA sheets have been used in the shoe industry since the end of the 1930s, for example for the production of toe caps, toe caps, insoles and midsoles, outsoles, frames and heels.
  • thermal deformability in a rational process is provided by synthetic back and front cap materials made from thermoplastic materials based on plastic, which are reinforced by a textile fabric. Processing can be carried out using the hot-cold process.
  • the punched-out and only slightly sharpened cap is thermally activated by infrared light heating, ie heated to a temperature above the flow transition limit and molded via an ice-cooled mold and sent for further processing in shoe production.
  • the cap material can also be delivered flat without preforming.
  • the actual, precise deformation takes place in both processes in the shoe factory through thermal activation, ie heating to a temperature above the flow transition limit on the last.
  • the cap is also glued to the lining material and the upper material because the thermally activatable adhesive is contained in the synthetic cap material and the thermal activation of the adhesive takes place in the temperature range above the flow transition limit of the synthetic cap material.
  • LEFA caps are preferably used in high-quality shoes. Due to their high machinability, synthetic caps are mainly processed in inexpensive shoes produced in large quantities.
  • leather substitute material in shoe components places special demands on the material used.
  • the material must have certain elastic properties, in particular sufficient basic and permanent elasticity.
  • the material must have sufficient resistance to mechanical loads, especially cold break. It was therefore an object of the present invention to provide a composite material which largely has the properties of high-quality LEFA kapper materials, but on the other hand, due to its thermoplastic properties, is suitable for processing in modern processes such as when using synthetic back and front cap materials and above can be processed even more efficiently.
  • thermoplastic composite material with a thermally activatable adhesive, with which the thermoplastic composite material can be firmly and permanently bonded to a large number of materials used in shoe production in the course of machine processing.
  • thermoplastic binder a portion of natural latex in the processing of the composite material in the hot-cold process ensures both the thermal deformability and the necessary low-temperature stability of the composite material.
  • thermoplastic composite material having the properties sought can be obtained which contains organic fibers, in particular leather fibers, and natural latex and a thermoplastic binder as matrix material if at least 8% by weight of natural latex is used as matrix material in addition to at least 2% by weight .-% a thermoplastic binder is used which is selected from polymers selected from the group consisting of polyurethanes, polyolefins, polyvinyl esters, polyethers, polystyrenes, styrene-olefin copolymers, polyacrylates, vinyl acetate polymers or ethylene-vinyl acetate copolymers or mixtures or copolymers consists of two or more of the polymers mentioned.
  • thermoplastic composite material obtainable from the polymers mentioned preferably has a flow transition limit of approximately 70 to approximately 100 ° C.
  • thermoplastic composite material is given in percent by weight (% by weight), unless otherwise stated, this information always relates to the total weight of the thermoplastic composite material.
  • thermoplastic composite material comprising a) at least 15% by weight of an organic fiber material or a mixture of two or more organic fiber materials as component A and b) at least 10% by weight of a component B consisting of at least 8% by weight. % of a thermoplastic binder and at least 2% by weight of natural latex,
  • thermoplastic binder from polymers selected from the group consisting of polyurethanes, polyolefins, polyvinyl esters, polyethers, polystyrenes, styrene-olefin copolymers, polyacrylates, vinyl acetate polymers or ethylene-vinyl acetate copolymers, or mixtures or copolymers of two or more of the above Polymers.
  • thermoplastic composite material Any organic fiber material which gives the thermoplastic composite the properties desired by the user, for example a specific one, is suitable as component A of the thermoplastic composite material
  • both naturally obtained or naturally obtainable fibers and synthetically produced fibers are understood as long as they are based on an “organic basis”.
  • fibers such as asbestos, glass fibers or carbon fibers are not included in the organic fiber material.
  • Plastic fibers, plant fibers or animal fibers are usually used in the context of the present invention.
  • Suitable natural fibers include, for example, animal fibers such as wool, hair or silk.
  • Plant fibers for example cotton, kapok, flax, hemp, jute, kenaf, ramie, gorse, manila, coconut or sisal, can also be used.
  • Suitable plastic fibers made from natural polymers are cupro, viscose, modal, acetate, triacetate and protein fibers or alginate fibers or mixtures of two or more of the fibers mentioned.
  • Suitable fibers made of synthetic polymers are, for example, polyacrylic, polymethacrylic, polyvinyl chloride, fluorine-containing polymer fibers, polyethylene, polypropylene, vinyl acetate, polyacrylonitrile, polyamide, polyester or polyurethane fibers.
  • leather fibers as the organic fiber material.
  • leather remnants are used with a suitable organic fiber material.
  • thermoplastic composite material with leather-like properties be used.
  • the leather fibers can basically be obtained from any type of leather residue. It can be both chrome-tanned, vegetable-tanned or aldehyde-tanned leather or their precursors such as Trade shavings or split leather.
  • Types of leather which can be used in the context of the invention are, for example, upper leather, suede leather, crust leather, lower leather, lining leather, bright leather, and also technical leather.
  • the organic fiber material is crushed to an extended length of about 0.1 to 20 mm.
  • a length of about 0.5 to 20 mm, preferably about 1 to about 10 mm and particularly preferably about 3 to about 8 mm fiber length is appropriate.
  • the fiber length is measured in the stretched state of the fiber.
  • Component A is contained in the thermoplastic composite material according to the invention in an amount of at least about 15% by weight as the base material.
  • the thermoplastic composite material increasingly takes on the properties of the organic fiber material.
  • the proportion of the organic fiber material can optionally also be greater, for example about 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight or even more than about 60% by weight, proportions of, for example, 65% by weight or even 70% by weight and more being possible.
  • the proportion of fiber materials is particularly preferably from approximately 25 to approximately 65% by weight, very particularly preferably from approximately 35 to approximately 55% by weight.
  • Leather fibers are preferably contained as component A in the thermoplastic composite material according to the invention.
  • thermoplastic composite material contains as component B, in addition to natural latex, a thermoplastic binder.
  • thermoplastic binder means polymeric compounds which, in addition to the natural latex used, serve as a matrix in the composite material. Polymeric materials with a molecular weight of more than about 1000 are generally used as the thermoplastic binder, but the molecular weight is preferably higher.
  • the molecular weight (M n ) of the polymers present in the binder is preferably between approximately 10,000 and approximately 1,000,000, particularly preferably between approximately 20,000 and approximately 300,000 and particularly preferably between approximately 50,000 and approximately 150,000.
  • thermoplastic binder stands for the entirety of the thermoplastic polymer matrix material, i.e. of the matrix portion which, in addition to the natural latex, represents component B of the composite material, regardless of how many polymeric components it consists of and how many different preparations containing the polymer (s) constituting the thermoplastic binder were required for its production.
  • thermoplastic binder made of polymers, selected from polyurethanes, polyolefins, polyvinyl esters, polyethers, polystyrenes, styrene-olefin copolymers, polyacrylates, vinyl acetate polymers or ethylene-vinyl acetate copolymers , or mixtures or copolymers of two or more of the polymers mentioned.
  • thermoplastic binders which contain at least two different polymers are used to produce the thermoplastic composite materials for component B.
  • two different polymers are understood to mean two types of polymer which differ in their chemical composition, ie in the type of the monomers involved in the structure of the polymer or, if two or more monomers are involved in the structure of the polymer, in Distinguish the ratio of the monomers to one another or to both. It is irrelevant whether the individual polymer has thermoplastic properties as long as the mixture of two different polymers has a corresponding thermoplasticity.
  • polyurethanes are to be understood as all polymers which have at least two urethane groups in the polymer backbone.
  • Suitable polyurethanes in the context of the present invention are all thermoplastic polyurethanes known to the person skilled in the field of polyurethane chemistry, in particular those polyurethanes which are usually used in the production of thermoplastic molded articles, in particular films, or for the thermoplastic coating of surfaces.
  • polyester polyurethanes or polyether polyurethanes are suitable, as are obtainable by reacting dicarboxylic acids with corresponding polyfunctional alcohols, in particular difunctional alcohols, for example difunctional polyethers such as polyethylene oxide, to give polyether or polyester polyols and subsequent reaction of the corresponding polyether or polyester polyols with di- or polyfunctional isocyanates ,
  • Polyolefins suitable in the context of the present invention can be obtained, for example, by free-radical or coordinative polymerization of ⁇ -olefins, in particular of ethylene or propylene.
  • the polymers of vinyl acetate are particularly suitable as polyvinyl esters.
  • Polyethers suitable for the purposes of the present invention are, for example, polyethylene oxide, polypropylene oxide, polybutylene oxide or polytetrahydrofuran, in particular with a molecular weight of more than about 5,000.
  • polystyrene or ⁇ -methylstyrene are suitable as polystyrenes.
  • thermoplastic binder of the thermoplastic composite material are also suitable as polymers for use in the thermoplastic binder of the thermoplastic composite material according to the invention.
  • styrene-olefin copolymers as can be obtained by copolymerizing styrene with mono- or diolefins, in particular butadiene.
  • the polymers of the esters of unsaturated alcohols with corresponding carboxylic acids are suitable as polyvinyl esters.
  • Suitable unsaturated alcohols are, for example, the unsaturated aliphatic alcohols with 2 to about 22 C atoms, in particular with 2 to about 8 C atoms.
  • the linear and branched alkanoic acids with 2 to about 22 C atoms, in particular with 2 to about 8 C atoms, are suitable as carboxylic acids.
  • Polymers which are in the form of an aqueous dispersion are preferably used to produce the composites according to the invention. These can be anionically stabilized or cationically stabilized polymer dispersions.
  • the dispersion can be stabilized, for example, by self-emulsifiable polymers, ie by polymers, the corresponding carry hydrophilic groups, for example carboxylic acid groups or amino groups.
  • dispersions can also be used whose stability is brought about by suitable anionic or cationic dispersants or emulsifiers.
  • polyacrylate or “polyacrylates” as used in the context of the present text refer below to both polymers or copolymers of acrylic acid and / or their derivatives and to polymers or copolymers of methacrylic acid and / or their derivatives ,
  • Polyacrylates can be prepared by acrylic acid and / or methacrylic acid and / or derivatives of acrylic acid and / or methacrylic acid, for example their esters with mono- or polyfunctional alcohols, in each case alone or as a mixture of two or more thereof, in a known manner, for example by radical means or ionic, polymerized.
  • polyacrylates in anionic dispersion as are obtainable, for example, by emulsion polymerization of the corresponding monomers and comonomers, are preferred.
  • Aqueous anionic dispersions generally contain, for example, the sodium, potassium and / or ammonium salts of long-chain aliphatic carboxylic acids and / or sulfonic acids for emulsification.
  • alkali-C 10 are also suitable.
  • homopolymers or copolymers can be used as polyacrylates which, in addition to the acrylic acid esters (acrylates), also contain styrene, acrylonitrile, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride and / or butadiene.
  • Monomers that can be used in the preparation of the polyacrylates are, in particular, methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate or lauryl acrylate.
  • Acrylic acid, methacrylic acid, acrylamide or methacrylic acid can also be added in small amounts as further monomers during the polymerization.
  • further acrylates and / or methacrylates with one or more functional groups can be present in the polymerization.
  • thermoplastic composite materials information on the content of natural latex in the thermoplastic composite materials is given in percent by weight (% by weight), this information relates to the proportions by weight of the natural latex polymer in the finished composite material.
  • the thermoplastic binder used in component B contains at least one of the abovementioned polymers, the proportion of the thermoplastic binder in the total composite totaling at least about 8% by weight, for example at least about 10% by weight, is at least about 20% by weight, at least about 30% by weight or at least about 40% by weight or more, for example at least about 50 to about 70% by weight or up to about 80% by weight
  • the thermoplastic binder fraction contains at least one polymer selected from the group consisting of styrene-olefin copolymers, vinyl acetate polymers or ethylene-vinyl acetate copolymers, or mixtures or copolymers of two or more of the polymers mentioned. It has also been shown that the thermoplastic properties of the thermoplastic composite material according to the invention by the choice of polymers for the thermoplastic binder, selected from the group consisting of styrene-olefin copolymers, vinyl acetate polymers or ethylene-vinyl acetate copolymers, or mixtures or copolymers can be influenced from two or more of the polymers mentioned with a suitable minimum film-forming temperature.
  • the minimum film formation temperature of a polymer is the lowest temperature at which a dispersion just forms a coherent film after the water has evaporated. It is close to the glass transition temperature T g of the polymer and, with the film formation, determines one of the most important technical properties of a polymer dispersion.
  • the minimum film forming temperature (MFT) is usually determined according to DIN 53787. A metal plate, to which a temperature gradient is applied, serves as the measuring device. It is observed at what temperature the film begins to crack or where the so-called white point is at which the cloudy film begins to become clear.
  • At least one of the polymers has an MFT of at least 20 ° C.
  • At least one of the polymers has an MFT of approximately 25 ° C. to approximately 35 ° C.
  • the total proportion of component B in the thermoplastic composite material is preferably at least about 10% by weight. It can be advantageous, for example for a targeted change in properties, if the thermoplastic composite material contains at least about 20% by weight or at least about 30% by weight or more of component B, for example at least about 40 to at least about 50% by weight. In a preferred embodiment of the invention, the proportion of component B in the total thermoplastic composite material is about 25 to about 40% by weight.
  • the thermoplastic composite material according to the invention can also have further components, preferably in a proportion of up to about 20% by weight. These include, for example, inorganic salts, preservatives, dyes, natural and / or synthetic fats, paraffins, natural and / or synthetic oils, silicone oils and ionic and / or nonionic surfactants.
  • Salts of aluminum or copper are preferably used as inorganic salts; aluminum sulfate is particularly preferred.
  • the inorganic salts are generally used in the course of the production process, which will be described in the further course of the present text, for the precipitation (for coagulation) of the polymeric binder.
  • the precipitation for coagulation
  • most of the metal salt is removed from the composite with the aqueous phase, but a small remainder can remain in the composite.
  • Preservatives those preservatives which have a fungicidal spectrum of action are particularly preferred.
  • Preventol® AI ID a preservative sold by BAYER, Leverkusen, is particularly suitable for the purposes of the invention.
  • component B contains up to 70% by weight (based on the total weight of component B) of polymer selected from the group consisting of styrene-olefin copolymers, vinyl acetate polymers or ethylene-vinyl acetate copolymers, or Mixtures or copolymers of two or more of the polymers mentioned.
  • the thermoplastic composite material contains about 25 to about 65 weight percent organic fibers, about 2 to about 30 weight percent natural latex, about 8 to about 35 weight percent polymers selected from the group consisting of styrene-olefin copolymers, vinyl acetate polymers or ethylene Vinyl acetate copolymers, or mixtures or copolymers of two or more of the polymers mentioned, optionally up to 20% by weight of inorganic salts, preservatives, dyes, natural and / or synthetic fats, paraffins, natural and / or synthetic oils, silicone oils, ionic and / or non-ionic surfactants.
  • the thermoplastic composite material contains about 35 to about 55% by weight of organic fibers, about 10 to about 25% by weight of natural latex, and about 10 to about 30% by weight of polymers selected from the group consisting of styrene Olefin copolymers, vinyl acetate polymers or ethylene-vinyl acetate copolymers, or mixtures or copolymers of two or more of the polymers mentioned, optionally up to 20% by weight of inorganic salts, preservatives, dyes, natural and / or synthetic fats, paraffins , natural and / or synthetic oils, silicone oils, ionic and / or non-ionic surfactants.
  • polymers selected from the group consisting of styrene Olefin copolymers, vinyl acetate polymers or ethylene-vinyl acetate copolymers, or mixtures or copolymers of two or more of the polymers mentioned, optionally up to 20% by weight of inorganic salts, preservatives, dyes, natural and
  • thermoplastic composite material according to the invention should preferably be used for shoe components such as toe caps, toe caps and outsoles and very preferably for the production of toe caps in the shoe industry and, in addition to the desired leather-like properties of high-quality LEFA toe cap materials, also have the rational processing properties of high-quality synthetic toe cap material.
  • the thermoplastic composite material has a flow transition range from approximately 70 ° C. to 100 ° C.
  • thermoplastic composite material according to the invention can undergo shape changes, for example, contour-accurate recesses, which remain dimensionally stable after the flow transition area is undershot.
  • the thermoplastic composite material according to the invention has high tensile strength and elasticity. Due to the material properties, processing can be carried out more efficiently than with synthetic cap material.
  • thermoplastic composite material according to the invention is preferably produced by contacting component A with the components of component B, these components preferably being in aqueous dispersion.
  • component B has more than one constituent, i.e. more than one polymer
  • both polymers can coexist in a dispersion.
  • the two polymers are present in different dispersions.
  • component A and the constituents of component B are mixed in one or more dispersions and the constituents of component B are coagulated simultaneously, i.e. during the mixing, or subsequently, i.e. in a separate process step after the mixing.
  • the invention therefore also relates to a process for producing a thermoplastic composite material comprising a) at least 15% by weight of an organic fiber material or a mixture of two or more organic fiber materials as component A and b) at least 10% by weight of a component B consisting of at least 8% by weight of a thermoplastic binder and at least 2% by weight .-% natural latex,
  • a polymer dispersion or a mixture of two or more polymer dispersions selected from the group consisting of natural latex, polyurethanes, polyolefins, polyvinyl esters, Polyethers, polystyrenes, styrene-olefin copolymers, polyacrylates, vinyl acetate polymers or ethylene-vinyl acetate copolymers, or mixtures or copolymers of two or more of the polymers mentioned, are mixed to form a mixture, so that those contained in the dispersion or the dispersions Form polymer component B, and then the mixture is treated with an aqueous solution of an aluminum or a copper salt, dewatered and dried.
  • a polymer dispersion or a mixture of two or more polymer dispersions selected from the group consisting of natural latex, polyurethanes, polyolefins, polyvinyl esters, Polyethers, polystyrenes, styrene-olefin cop
  • dispersions can be used in the context of the present invention.
  • an anionically stabilized dispersion and a cationically stabilized dispersion can be used.
  • the dispersions can be chosen so that there is essentially complete coagulation, i.e. essentially complete precipitation of the binders contained in the dispersion. However, it is also possible to proceed in such a way that only a part of the binder is precipitated.
  • polymer dispersions are used which are essentially, at least with regard to Charge of the stabilizing species, are stabilized identically.
  • dispersions can be used which are anionically or cationically stabilized.
  • anionically stabilized polymer dispersions are used.
  • the treatment of the mixture with an aqueous solution of an aluminum or a copper salt is carried out in such a way that essentially all polymer molecules present in the mixture precipitate after the treatment, i.e. are coagulated.
  • thermoplastic composite materials To produce the thermoplastic composite materials according to the invention, tanned leather residues are comminuted (precut) in knife mills to a size of approximately 1 cm 2 . The crushing is usually carried out dry at this stage.
  • the pre-shredded leather residues are weighed and wet defibrated using so-called disc refiners.
  • the water addition is controlled in such a way that a knot-free fiber pulp is obtained which consists of approximately 5% by weight of fibers and approximately 95% by weight of water (corresponding to approximately 1000 kg of fibers per 20 m 3 of water).
  • the comminution is preferably carried out in such a way that part of the wastewater later in the process is returned to the circuit at this point. In this way, waste water proportions of about 50%, preferably above, of the total water used during the shredding process can be achieved.
  • the suspension of leather fibers in water thus obtainable is then transferred into a suitable vessel, preferably an attachment chest.
  • the amount transferred is dimensioned such that the concentration of leather fibers is between about 1.5 and about 2.5% by weight, based on the total amount intended.
  • the leather fibers contain a high proportion of chrome-tanned leather or if the leather fibers consist exclusively of chrome-tanned leather, vegetable tannins, for example chestnut wood extract, quebracho, mimosa or valonea, are first added.
  • Dyes can also be added to the batch. These are usually quantitative iron oxide paints.
  • Preservatives natural and / or synthetic fats, natural and / or synthetic oils, silicone oils and or ionic and / or nonionic surfactants can also be added to the batch.
  • the polymer dispersion or the mixture of two or more different polymer dispersions is then added.
  • polymer dispersions If two or more different polymer dispersions are to be used, they can be added to the mixture either simultaneously or in any order.
  • the anionically stabilized polymer dispersion or the anionically stabilized polymer dispersions become separate from the cationic stabilized polymer dispersion or the cationically stabilized polymer dispersions added. The order does not matter.
  • the mixture is mixed with a solution of an aluminum or a copper salt.
  • Aluminum sulfate is preferably used, with about 40 to 300 1, preferably about 100 to about 2501, particularly preferably about 120 to about 2001, of an about 20 to preferably about 60% by weight aluminum sulfate solution being added per 1000 kg batch.
  • the batch After stirring for about an hour, the batch is freed of excess water with the aid of a suitable dewatering device.
  • a suitable dewatering device for this purpose, there are drainage devices that work in the so-called batch process, for example a so-called mill press, but continuous processing on a four-wire dewatering machine is preferred.
  • the batch is dewatered on the four-wire dewatering machine to a residual water content of about 70% by weight.
  • the material obtained is dewatered mechanically with the aid of a suitable press device to a residual water content of about 50% by weight.
  • the material treated in this way is then passed through a suitable thermal drying device, and is dried here to a residual water content of about 10% by weight and then wound up on rolls. Depending on the intended use, it is also possible to dry the material to a lower residual water content.
  • the material can then be further processed (grinding, calendering, trimming) and cut into sheets or rolls.
  • the composite material obtained in this way has, for example, a flow transition range from approximately 70 ° C. to approximately 100 ° C.
  • the composite material is equipped with a thermally activatable adhesive in order to achieve a permanent fastening of the composite material with lining material and upper material in a rational process when used as a rear or front cap material.
  • the adhesive is thermally activated in the flow transition area of the composite.
  • adhesives are understood to mean non-metallic, preferably organic, substances which connect parts to be joined by surface adhesion and internal strength.
  • the adhesives include, for example, glues, dispersion adhesives, solvent-based adhesives, hot melt adhesives, and / or contact adhesives.
  • Organic adhesives are preferably used in the context of the present invention, which can either be physically setting adhesives or chemically reacting adhesives or a combination of the two.
  • the physically setting adhesives which can be used for the purposes of the present invention include, for example, adhesives, contact adhesives or hot melt adhesives present in solution or dispersion.
  • chemically reacting adhesives e.g. Adhesives are used which impart sufficient adhesion of the surfaces to be bonded to one another without the elimination of volatile constituents.
  • adhesives which achieve the required adhesion by eliminating volatile constituents.
  • the adhesives can be both cold-curing and heat-retaining, have a thermoplastic, thermoset or elastomeric final state and can be used in one or two or more components.
  • hot melt adhesives are used, the softening point of which is approximately 60 ° C. to approximately 120 ° C.
  • hot melt adhesives are used, the softening point of which is approximately 80 ° C to approximately 100 ° C.
  • hot-melt adhesives are used whose softening point is approximately 80 ° C. to approximately 100 ° C. and the adhesive is based on polyesters, polyamides or polycarbonates.
  • the adhesive is applied to the thermoplastic composite material in a hot process, for example by extruder application with a slot die or RoÜercoater application.
  • the resin can also be applied by powder application followed by thermal sintering. These processes are cold-curing processes.
  • hot melt adhesives are applied between about 50 to about 100 gm 2 by means of extruder slot die application.
  • hot-melt adhesive powder coatings of between approximately 30 and approximately 80 g / m 2 are applied.
  • hot-melt adhesive powder coatings of between about 40 to about 70 g / m 2 are applied.
  • thermoplastic composite materials according to the invention are suitable, in addition to the production of thermally formable shoe components, for numerous other applications, for example for coating the surface of objects, such as for example furniture fronts with or without internal radii, for the surface coating of parts in the interior of motor-driven motor vehicles, or for profile coating of walls, Floor and ceiling panels.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne une matière composite pour réaliser des parties de chaussure thermoformables à base de fibres organiques, contenant une matière à fibres organiques ou un mélange d'au moins deux matières à fibres organiques, et un liant qui consiste en un polymère thermoplastique et un mélange d'au moins deux polymères thermoplastiques et latex naturel. L'invention a également pour objet un procédé pour produire une matière thermoplastique de ce type, et la mise en place d'un adhésif thermoactivable dans le domaine de transition à l'état liquide de la matière composite.
PCT/EP2004/008697 2003-08-08 2004-08-03 Matiere composite pour realiser des parties de chaussure thermoformables a base de fibres organiques WO2005017004A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BRPI0413447 BRPI0413447A (pt) 2003-08-08 2004-08-03 material composto para componentes de sapato moldáveis a quente à base de fibra orgánica
EP04763755A EP1654309A1 (fr) 2003-08-08 2004-08-03 Matiere composite pour realiser des parties de chaussure thermoformables a base de fibres organiques
US11/349,794 US20060194486A1 (en) 2003-08-08 2006-02-08 Composite material based on organic fibers for thermally mouldable shoe components

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10336509.5 2003-08-08
DE2003136509 DE10336509A1 (de) 2003-08-08 2003-08-08 Verbundmaterial für thermisch formbare Schuhkomponenten auf organischer Faserbasis

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/349,794 Continuation US20060194486A1 (en) 2003-08-08 2006-02-08 Composite material based on organic fibers for thermally mouldable shoe components

Publications (1)

Publication Number Publication Date
WO2005017004A1 true WO2005017004A1 (fr) 2005-02-24

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US (1) US20060194486A1 (fr)
EP (1) EP1654309A1 (fr)
BR (1) BRPI0413447A (fr)
DE (1) DE10336509A1 (fr)
WO (1) WO2005017004A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2395014A2 (fr) 2005-10-05 2011-12-14 Commonwealth Scientific and Industrial Research Organization Protéines de soie
WO2013142901A1 (fr) 2012-03-26 2013-10-03 Commonwealth Scientific And Industrial Research Organisation Polypeptides de soie
US8674077B2 (en) 2009-08-26 2014-03-18 Commonwealth Scientific And Industrial Research Organisation Processes for producing silk dope
ITCS20130027A1 (it) * 2013-11-30 2015-05-31 Consorzio Per Le Tecnologie Biomedi Che Avanzate Materiali compositi ottenuti da fibre estratte da fibre vegetali di ginestra e polimeri e processo per ottenerli
US9394348B2 (en) 2011-11-16 2016-07-19 Commonwealth Scientific And Industrial Research Organisation Collagen-like silk genes
WO2018078391A3 (fr) * 2016-10-28 2018-06-14 Cambond Limited Matériaux biocomposites et bioplastiques et procédé
WO2023006520A1 (fr) * 2021-07-29 2023-02-02 Nabore GmbH Matériau composite thermoplastique
WO2023006507A1 (fr) * 2021-07-29 2023-02-02 Nabore GmbH Matériau composite

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US20090302241A1 (en) * 2005-04-26 2009-12-10 Seiji Abe X-ray opaque filament, x-ray opaque covered filament and fiber structure using said x-ray opaque filament and/or x-ray opaque covered filament
DE102008017960A1 (de) * 2008-04-08 2009-10-15 Bader Gmbh & Co. Kg Flachmaterialbahn mit einer Faserschicht aus Lederfaser und Bindemittel sowie Verfahren zu deren Herstellung
US20100130946A1 (en) * 2008-11-25 2010-05-27 Geraldine Price Medley Heel cap for skin treatment
DE102009020036A1 (de) * 2009-05-05 2010-11-11 Bk Giulini Gmbh Thermoplastische Versteifungsmaterialien
WO2014099884A1 (fr) * 2012-12-18 2014-06-26 North Carolina State University Procédés de fabrication d'un substrat de cuir artificiel à partir de déchets de cuir et produits fabriqués avec ceux-ci
DE102019109954A1 (de) * 2019-04-15 2020-10-15 S.M.B.-Equity GmbH Thermoplastisches Verbundmaterial
IT202100027722A1 (it) * 2021-10-28 2023-04-28 Sciarada Ind Conciaria S P A Uso di fibre di cuoio come agenti antiscivolamento in composizioni polimeriche ed articoli con esse ottenuti
CN118103433A (zh) 2021-11-24 2024-05-28 雷诺有限责任公司 聚合物基体的平面结构和嵌入其中的纺织颗粒

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2395014A2 (fr) 2005-10-05 2011-12-14 Commonwealth Scientific and Industrial Research Organization Protéines de soie
US8481681B2 (en) 2005-10-05 2013-07-09 Commonwealth Scientific And Industrial Research Organisation Silk proteins
US9409959B2 (en) 2005-10-05 2016-08-09 Commonwealth Scientific And Industrial Research Organisation Silk proteins
US8674077B2 (en) 2009-08-26 2014-03-18 Commonwealth Scientific And Industrial Research Organisation Processes for producing silk dope
US9394348B2 (en) 2011-11-16 2016-07-19 Commonwealth Scientific And Industrial Research Organisation Collagen-like silk genes
WO2013142901A1 (fr) 2012-03-26 2013-10-03 Commonwealth Scientific And Industrial Research Organisation Polypeptides de soie
ITCS20130027A1 (it) * 2013-11-30 2015-05-31 Consorzio Per Le Tecnologie Biomedi Che Avanzate Materiali compositi ottenuti da fibre estratte da fibre vegetali di ginestra e polimeri e processo per ottenerli
WO2018078391A3 (fr) * 2016-10-28 2018-06-14 Cambond Limited Matériaux biocomposites et bioplastiques et procédé
WO2023006520A1 (fr) * 2021-07-29 2023-02-02 Nabore GmbH Matériau composite thermoplastique
WO2023006507A1 (fr) * 2021-07-29 2023-02-02 Nabore GmbH Matériau composite

Also Published As

Publication number Publication date
EP1654309A1 (fr) 2006-05-10
BRPI0413447A (pt) 2006-10-17
US20060194486A1 (en) 2006-08-31
DE10336509A1 (de) 2005-03-03

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