US20060194486A1 - Composite material based on organic fibers for thermally mouldable shoe components - Google Patents

Composite material based on organic fibers for thermally mouldable shoe components Download PDF

Info

Publication number
US20060194486A1
US20060194486A1 US11/349,794 US34979406A US2006194486A1 US 20060194486 A1 US20060194486 A1 US 20060194486A1 US 34979406 A US34979406 A US 34979406A US 2006194486 A1 US2006194486 A1 US 2006194486A1
Authority
US
United States
Prior art keywords
composite material
approximately
thermoplastic
component
polymers
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.)
Abandoned
Application number
US11/349,794
Other languages
English (en)
Inventor
Ewald Wilka
Thomas Hieber
Albrecht Reiter
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.)
Ledertech GmbH
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
Assigned to LEDERTECH GMBH reassignment LEDERTECH GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HIEBER, THOMAS, REITER, ALBRECHT, WILKA, EWALD
Publication of US20060194486A1 publication Critical patent/US20060194486A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A43FOOTWEAR
    • A43BCHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/08Heel stiffeners; Toe stiffeners
    • A43B23/081Toe stiffeners
    • A43B23/086Toe stiffeners made of impregnated fabrics, plastics or the like
    • A43B23/087Toe stiffeners made of impregnated fabrics, plastics or the like made of plastics
    • AHUMAN NECESSITIES
    • A43FOOTWEAR
    • A43BCHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/08Heel stiffeners; Toe stiffeners
    • A43B23/081Toe stiffeners
    • A43B23/085Toe stiffeners made of leather
    • AHUMAN NECESSITIES
    • A43FOOTWEAR
    • A43BCHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/08Heel stiffeners; Toe stiffeners
    • A43B23/14Heel stiffeners; Toe stiffeners made of leather
    • AHUMAN NECESSITIES
    • A43FOOTWEAR
    • A43BCHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/08Heel stiffeners; Toe stiffeners
    • A43B23/16Heel stiffeners; Toe stiffeners made of impregnated fabrics, plastics or the like
    • A43B23/17Heel stiffeners; Toe stiffeners made of impregnated fabrics, plastics or the like made of plastics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/04Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/10Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
    • Y10T442/102Woven scrim
    • Y10T442/107Comprising at least two chemically different fibers

Definitions

  • the invention relates to a composite material for thermally formable shoe components containing fiber materials, a thermoplastic binding agent and natural latex. Furthermore, the invention relates to a process for producing such a composite material for thermally formable shoe components on an organic fiber basis. A coating of the composite material with adhesive used to bind the composite material for thermally formable shoe components during processing in the manufacture of shoes is also subject matter of the invention.
  • Composite materials also called composites, are materials produced by the incorporation of a base material, present, e.g., in the form of fibers, into a second substance (the matrix). Certain properties (e.g., mechanical properties, surface properties or certain behavior under external influences) of the incorporated substance are used in this instance for the composite material.
  • the base material can vary greatly in its proportion of ingredients relative to the matrix surrounding it.
  • the matrix component in wooden materials, to which, e.g., the known pressboard plates belong is as a rule only 10-15%.
  • the matrix component in fiber-reinforced plastics e.g., in plastics reinforced with glass fibers, can be significantly greater, approximately over 70 or 80%.
  • the production of composites is frequently used to produce a material from byproducts accumulating during the processing of a certain base material with characteristic properties of the base material.
  • the corresponding composite material can then be used as a rule at least as replacement material for the base material and thus permits a “substance-related” utilization of the waste and/or byproducts of the base material. This is the case, e.g., in the utilization of wood waste in pressboard plates.
  • a further example for a substance-related utilization of byproducts is the processing of cutting and stamping remnants in the production of leather and shoes to leather fiber materials.
  • LEFA leather fiber materials
  • LEFA are as a rule single-layer areal structure consisting of leather fibers and binding agents.
  • LEFA plates have been used in the shoe industry since the end of the thirties already, e.g., for producing heel caps, toe caps, insoles and midsoles, outer soles, welts and heels.
  • thermal deformability in a rational process offers synthetic heel and toe cap materials consisting of thermoplastically deformable material based on plastic that are reinforced by a textile fabric.
  • the processing can take place in accordance with the hot-cold process.
  • the stamped-out and only slightly sharpened cap is thermally activated by heating with infrared light, that is, heated to a temperature above the flow transition boundary, formed above an ice-cooled form and sent to further processing in the production of shoes.
  • the cap material can also be supplied plane without pre-forming.
  • the actual, accurately-fitting deformation takes place in both processes in the shoe factory by thermal activation, that is, heating to a temperature above the flow transition boundary on the last.
  • the adhering of the cap to the lining material and the upper material also takes place during this time, since 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 boundary of the synthetic cap material.
  • LEFA caps are used with preference in high-quality shoes on account of their leather-like properties. Synthetic caps are processed primarily in economical shoes produced in great numbers on account of their high mechanical workability.
  • the use of leather substitute material in shoe components places special demands on the material used.
  • the material must have certain elastic properties, in particular a sufficient base- and long-lasting elasticity.
  • the material must have sufficient resistance to mechanical stresses, in particular to becoming brittle when cold.
  • the present invention therefore had the task of making a composite available that largely has the properties of high-quality LEFA buffer materials and on the other hand is suitable for processing in modem processes as in the use of synthetic heel- and toe cap materials and, in addition, can be processed in an even more rational manner.
  • thermoplastic composite in the context of the a preferred embodiment of the invention, it was further a task to provide the composite material with a thermally activatable adhesive with which the thermoplastic composite can be bound within the framework of a mechanical processing in a firm and permanent manner to a plurality of materials used in the production of shoes.
  • thermoplastic binding agent and a component of natural latex in the processing of the composite material in the hot-cold process ensures the thermal deformability as well as a necessary stability against cold of the composite material.
  • thermoplastic composite material with the desired properties can be obtained that contains organic fibers, especially leather fibers, and natural latex and the thermoplastic binding agent as matrix material if a thermoplastic binding agent is used as matrix material in addition to at least 2 wt % natural latex to at least 8 wt %, which consists of polymers selected from the group consisting of polyurethanes, polyolefins, polyvinylesters, polyethers, polystyrenes, styrene olefin copolymers, polyacrylates, vinylacetate polymers or ethylene vinylacetate copolymers or mixtures or copolymers of two or more of the cited polymers.
  • thermoplastic composite material positively influences the above-cited properties of base- and permanent elasticity as well as the resistance to becoming brittle when cold.
  • thermoplastic composite material obtainable from the cited polymers preferably has a flow transition boundary of approximately 70 to approximately 100° C.
  • thermoplastic composite material containing
  • any desired organic fiber material is suitable as component A of the thermoplastic composite material that imparts to the thermoplastic composite material the properties desired by the user, e.g., a certain appearance or certain grip.
  • organic fiber material denotes in the sense of the present invention both naturally obtained or naturally obtainable fibers as well as synthetically produced fibers as long as they are based on an “organic basis”. Therefore, fibers such as, e.g., asbestos, glass fibers or carbon fibers are not organic fiber material.
  • Plastic fibers, vegetable fibers or animal fibers are normally used in the context of the present invention.
  • the suitable natural fibers include, e.g., animal fibers such as wool, hairs or silk. Vegetable fibers can also be used, e.g., cotton, kapok, flax, hemp, jute, kenaf, ramie, broom, manila, coconut or sisal. Suitable plastic fibers of natural polymers are cupro fibers, viscose fibers, modal fibers, acetate fibers, triacetate fibers as well as protein fibers or alginate fibers or mixtures of two or more of the cited fibers.
  • Suitable fibers of synthetic polymers are, e.g., polyacrylic fibers, polymethacrylic fibers, polyvinylchloride fibers, fluorine-containing polymeric fibers, polyethylene fibers, polypropylene fibers, vinylacetate fibers, polyacrylonitrile fibers, polyamide fibers, polyester fibers or polyurethane fibers.
  • leather fibers as organic fiber material.
  • leather remnants are comminuted with a suitable process and defibered so that the fibers obtained can be subsequently used within the context of the process according to the invention to obtain a thermoplastic composite material with leather-like properties.
  • Leather fibers can basically be obtained from any type of leather remnants. They can be chromium-tanned, vegetable-tanned or aldehyde-tanned leathers or their pre-products such as, e.g., shavings or split leather.
  • Leather types that can be used within the context of the invention are, e.g., upper leather, velour leather, crust leather, lower leather, lining leather, sleek leather as well as technical leather.
  • the organic fiber material is comminuted to a stretched length of approximately 0.1 to 20 mm as a function of the desired decorative or mechanical effect.
  • a length of approximately 0.5 to 20 mm, preferably approximately 1 to approximately 10 mm and especially preferably approximately 3 to approximately 8 mm fiber length is suitable in particular when using leather fibers.
  • the fiber length is measured in the stretched state of the fiber. It can of course occur, depending on the initial material and the type of comminution, that the fiber assumes an irregularly curved form without external influence.
  • Component A is contained in the thermoplastic composite material according to the invention in an amount of at least approximately 15 wt % as base material. As the portion of A rises, the thermoplastic composite material increasingly assumes the properties of the organic fiber material. It can therefore be advantageous, depending on the desired effect, to use, e.g., at least 20 wt % or at least approximately 25 wt % of component A in the thermoplastic composite material according to the invention.
  • the portion of the organic fiber material can also optionally be greater, e.g., approximately 30 wt %, 35 wt %, 40 wt %, 45 wt %, 50 wt %, 55 wt % or even more than approximately 60 wt %, portion of e.g., 65 wt % or even 70 wt % and more being possible.
  • the portion of fiber materials is especially preferably approximately 25 to approximately 65 wt % and quite especially preferably approximately 35 to approximately 55 wt %.
  • thermoplastic composite material according to the invention as component A.
  • thermoplastic composite material contains a thermoplastic binding agent as component B in addition to natural latex.
  • thermoplastic binding agent denotes in the context of the present text polymeric compounds that serve as matrix in the composite material in addition to the natural latex used.
  • polymeric materials with a molecular weight greater than approximately 1000 are used as thermoplastic binding agent but the molecular weight is preferably greater.
  • the molecular weight (M n ) of the polymers present in the binding agent is preferably between approximately 10,000 and approximately 1,000,000, especially preferably between approximately 20,000 and approximately 300,000 and in particular preferably between approximately 50,000 and approximately 150,000.
  • thermoplastic binding agent stands in the context of the present text for the totality of the thermoplastically reacting, polymeric matrix material, that is of that matrix component that constitutes, in addition to the natural latex, component B of the composite material independently of how many polymeric components it consists of and how many preparations containing the polymer(s) constituting the thermoplastic binding agent(s) were required for its production.
  • the thermoplastic binding agent can optionally also have a bi- or higher modal distribution.
  • thermoplastic binding agent consisting of polymers, selected from polyurethanes, polyolefins, polyvinylesters, polyethers, polystyrenes, styrene olefin copolymers, polyacrylates, vinylacetate polymers or ethylene vinyl acetate copolymers or mixtures or copolymers of two or more of the cited polymers.
  • thermoplastic binding agents containing at least two different polymers are used to produce the thermoplastic composite materials for component B.
  • the term “two different polymers” denotes in the context of the present invention two polymer types that differ in their chemical composition, that is, in the type of monomers participating in the structure of the polymers, or, if two or more monomers participated in the structure of the polymer, in the ratio of the monomers to one another, or in both. It is immaterial whether the individual polymer has thermoplastic properties as long as the mixture of two different polymers has an appropriate thermoplasticity.
  • polymers with at least two urethane groups in the polymer backbone are to be considered as polyurethanes.
  • thermoplastic polyurethanes known to those skilled in the art in the area of polyurethane chemistry are suitable as polyurethanes, in particular polyurethanes like those customarily used in the context of producing thermoplastic formed pieces, in particular from foils, or for the thermoplastic coating of surfaces.
  • polyesterpolyurethanes or polyetherpolyurethanes like those obtainable by reacting dicarboxylic acids with appropriate polyfunctional alcohols, especially difunctional alcohols, e.g., difunctional polyethers such as polyethylene oxide to polyether- or polyester polyols and subsequently reacting the appropriate polyether- or polyester polyols with di- or polyfunctional isocyanates are suitable.
  • Polyolefins suitable in the context of the present invention are obtainable, e.g., by radical or coordinative polymerization of ⁇ -olefins, especially of ethylene or propylene.
  • polymers of vinylacetate are suitable as polyvinylesters in the context of the present invention.
  • Polyethers suitable in the context of the present invention are, e.g., polyethylene oxide, polypropylene oxide, polybutylene oxide or polytetrahydrofuran, especially with a molecular weight of more than approximately 5,000.
  • Suitable polystyrenes are, e.g., the polymers of styrene or ⁇ -methylstyrene.
  • styrene olefin copolymers like those obtainable by copolymerization of styrene with mono- or diolefins, especially butadiene, are also suitable as polymers for use in the thermoplastic binding agent of the thermoplastic composite material according to the invention.
  • Suitable polyvinylesters are the polymerizates of the esters of unsaturated alcohols with appropriate carboxylic acids.
  • Suitable unsaturated alcohols are, e.g., the unsaturated, aliphatic alcohols with 2 to approximately 22 C-atoms, especially with 2 to approximately 8 C-atoms.
  • Suitable carboxylic acids are the linear and branched alkane acids with 2 to approximately 22 C-atoms, especially with 2 to approximately 8 C-atoms.
  • Polymers that are present in the form of an aqueous dispersion are preferably use for the production of composite substances according to the invention. They can be anionically stabilized or cationically stabilized polymer dispersions.
  • the stabilization of the dispersion can be effected, e.g., by self-emulsifiable polymers, that is, by polymers carrying appropriate hydrophilic groups, e.g., carboxylic acid groups or amino groups.
  • dispersions can also be used whose stability is affected by suitable anionic or cationic dispersants or emulsifiers.
  • polyacrylate or “polyacrylates” as they are used in the context of the present text refer in the following to polymers or copolymers of acrylic acid and/or its derivatives as well as to polymers or copolymers of methacrylic acid and/or its derivatives.
  • Polyacrylates can be produced in that acrylic acid and/or methacrylic acid and/or derivatives of acrylic acid and/or methacrylic acid, e.g., their esters, are polymerized either radically or ionically with mono-or polyfunctional alcohols alone or as a mixture of two or more of them in a known manner.
  • the polyacrylates in anionic dispersion like those obtainable, e.g., by emulsion polymerization of the appropriate monomers and comonomers are preferred.
  • Aqueous anionic dispersions contain as a rule, e.g., the sodium salts, potassium salts and/or ammonium salts of long-chain, aliphatic carboxylic acids and/or sulfonic acids for emulsification.
  • alkali-C 10-18 -alkyl sulfates, ethoxylated and sulfated and/or sulfonated long-chain, aliphatic alcohols or alkyl phenols as well as sulfodicarboxylic acid esters are also suitable.
  • Homopolymers or copolymers containing styrene, acrylonitrile, vinylacetate, vinylpropionate, vinyl chloride, vinylidene chloride and/or butadiene in addition to the acrylic acid esters (acrylates) can be used as polyacrylates in the context of the present invention.
  • methacrylate, ethylacrylate, n-butylacrylate, isobutylacrylate, tert.-butylacrylate, hexylacrylate, 2-ethylhexylacrylate or laurylacrylate can be considered as monomers in the production of polyacrylates.
  • acrylic acid, methacrylic acid, acrylamide or methacrylamide can also be added as further monomers in slight amounts during the polymerization.
  • acrylates and/or methacrylates with one or more functional groups can optionally also be present in the polymerization. They are, e.g., maleic acid, itaconic acid, butanediol diacrylate, hexanediol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethylacrylate, 2-hydroxymethylmethacrylate, hydroxypropylacrylate, propyleneglycolmethacrylate, butanediol monoacrylate, ethyldiglycolacrylate as well as a monomer carrying sulfonic acid, e.g., 2-acrylamido-2-methylpropane sulfonic acid.
  • maleic acid e.g., itaconic acid
  • butanediol diacrylate hexanediol diacrylate
  • the thermoplastic binding agent used in component B contains at least one of the above-cited polymers, the portion of the thermoplastic binding agent in the entire composite substance being at least approximately 8 wt %, e.g., at least approximately 10 wt %, at least approximately 20 wt %, at least approximately 30 wt % or at least approximately 40 wt % or more, e.g., at least approximately 50 to approximately 70 wt % or up to approximately 80 wt %.
  • the portion of thermoplastic binding agent contains at least one polymer selected from the group consisting of styrene olefin copolymers, vinylacetate polymers or ethylene vinylacetate copolymers or mixtures or copolymers of two or more of the cited polymers.
  • thermoplastic properties of the thermoplastic composite material according to the invention can be influenced by the selection of polymers for the thermoplastic binding agent, selected from the group consisting of styrene olefin copolymers, vinylacetate polymers or ethylene vinylacetate copolymers or mixtures or copolymers of two or more of the cited polymers with a suitable minimum film-formation temperature.
  • the minimum film-formation temperature of a polymer is the lowest temperature at which a dispersion is just able to form a cohesive film after evaporation of the water. It is close to the glass transition temperature T g of the polymer and determines with the film formation one of the most important application technology properties of a polymer dispersion.
  • the minimum film formation temperature is determined as a rule according to DIN 53787.
  • a metal plate to which a temperature gradient is applied serves as measuring apparatus. At which temperature the film begins to become cracked or where the so-called white point is located at which the opaque film begins to become clear is observed.
  • At least one of the polymers has an MFT of at least 20° C. in the framework of a preferred embodiment of the present invention.
  • At least one of the polymers has an MFT of approximately 25° C. to approximately 35° C.
  • the entire portion of component B in the thermoplastic composite material is preferably at least approximately 10 wt %. It can be advantageous, e.g., for a well-directed change of property, if the thermoplastic composite material contains at least 20 wt % or at least approximately 30 wt % or more of component B, e.g., at least approximately 40 to at least approximately 50 wt %. In a preferred embodiment of the invention the portion of component B in the entire thermoplastic composite material is approximately 25 to approximately 40 wt %.
  • thermoplastic composite material according to the invention can also contain further components, preferably in a portion up to approximately 20 wt %.
  • Salts of aluminum or of copper are preferably used as inorganic salts and aluminum sulfate is especially preferred.
  • the inorganic salts are used as a rule in the context of the production process, that will be described in the further course of the present text, for precipitating (coagulating) the polymeric binding agent.
  • the largest portion of the metal salt is removed with the aqueous phase from the composite but a small remnant can remain in the composite material.
  • preservative agents those preservative agents are especially preferred that have a fungicidal spectrum of action.
  • component B contains up to 70 wt % (relative to the total weight of component B) polymer, selected from the group consisting of styrene olefin copolymers, vinylacetate polymers or ethylene vinylacetate copolymers or mixtures or copolymers of two or more of the cited polymers.
  • thermoplastic composite material according to the invention should preferably serve for shoe components such as heel caps, toe caps, outer soles and especially preferably for manufacturing heel caps in the shoe industry and have the rational processing properties of high-quality synthetic heel cap material in addition to the desired leather-like properties of high-quality LEFA heel cap materials.
  • the thermoplastic composite material has a flow transition range of approximately 70° C. to 100° C.
  • thermoplastic composite material according to the invention can be subjected to changes of form, e.g., moldings with precise contours that retain a stable form after dropping below the flow transition range.
  • the thermoplastic composite material according to the invention has high tear resistance and elasticity in this case. The processing can take place in a more rational manner than with synthetic cap material on account of the material properties.
  • thermoplastic composite material according to the invention preferably takes place by bringing component A in contact with the components of component B, these components being preferably present in aqueous dispersion.
  • component B has more than one component, that is, more than one polymer
  • both polymers can be present in a dispersion at the same time.
  • both polymers are present in different dispersions.
  • Components A and the components of component B are mixed in one or more dispersions in the context of the production process according to the invention and the components of component B are coagulated at the same time, that is, during the mixing, or subsequently, that is, in their own process stage after the mixing.
  • the invention therefore also has as subject matter a process for producing a thermoplastic composite material containing
  • two or more different polymer 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 selected in such a manner that a substantially complete coagulation, that is, a substantially complete precipitation of the binding agent contained in the dispersion takes place. However, it is just as possible to proceed in such a manner that only a part of the binding agent is precipitated.
  • polymer dispersions are used that are substantially identically stabilized, at least as regards the charge of the stabilizing species.
  • dispersions can be used that are anionically or cationically stabilized.
  • anionically stabilized polymer dispersions are used.
  • the treatment of the mixture with an aqueous solution of an aluminum salt or copper salt takes place in such a manner that following the treatment substantially all polymer molecules present in the mixture are precipitated, that is, coagulated.
  • thermoplastic composite materials For producing the thermoplastic composite materials according to the invention, tanned leather remnants are comminuted (pre-cut) in knife mills to a size of approximately 1 cm 2 in area. The comminution takes place dry as a rule in this stage.
  • the leather remnants pre-comminuted in this manner are weighed and defibered wet by so-called disk refiners.
  • the addition of water is controlled in such a manner that a node-free fiber pulp is obtained consisting of approximately 5 wt % fibers and approximately 95 wt % water (corresponding to approximately 1000 kg fibers to 20 m 3 water).
  • the comminution is preferably carried out in such a manner that a part of the wastewater that is standing later in the process is returned at this location into the circuit. Proportions of wastewater of approximately 50% and preferably above can be achieved from the total water used during the comminution process.
  • the suspension of leather fibers in water obtainable in this manner is subsequently transferred into a suitable vessel, preferably a preparation vat.
  • the transferred amount is measured in such a manner that the concentration of leather fibers is between approximately 1.5 and approximately 2.5 wt % relative to the total batch amount provided.
  • the leather fibers contain a high proportion of chrome-tanned leather or if the leather fibers consist exclusively of chrome-tanned leather, at first vegetable tanning substances, e.g., chestnut wood extract, quebracho, mimosa or valonia are added.
  • first vegetable tanning substances e.g., chestnut wood extract, quebracho, mimosa or valonia are added.
  • fatting agents are added. All leather fatting agents emulsifiable in water are suitable as fatting agents.
  • dyes can be added to the batch. This usually involves quantitatively attaching iron oxide dyes.
  • the batch can be compounded with preservative agents, natural and/or synthetic fats, natural and/or synthetic oils, silicone oils and/or ionic and/or non-ionic surfactants.
  • the polymer dispersion or the mixture of two or more different polymer dispersions is subsequently added.
  • polymer dispersions If two or more different polymer dispersions are to be used, they can be added either at the same time or successively in any desired sequence to the mixture.
  • the anionically stabilized polymer dispersion or the anionically stabilized polymer dispersions is/are added separately from the cationically stabilized polymer dispersion or the cationically stabilized dispersions.
  • the sequence is not relevant here.
  • the mixture is compounded with a solution of an aluminum salt or copper salt.
  • Aluminum sulfate is preferably used and approximately 40 to 300 1, preferably approximately 100 to approximately 250 1, and especially preferably approximately 120 to approximately 200 1 of an approximately 20 to preferably 60 wt % aluminum sulfate solution are added per 100 kg batch.
  • the batch is freed of excess water with the aid of a suitable dewatering device.
  • dewatering equipments are available that operate in the so-called batch process, e.g., a so miller press; however, a continuous processing of a long-sieve dewatering machine is preferred.
  • the batch is dewatered on the long-sieve watering machine to a residual water content of approximately 70 wt %.
  • the material obtained is dewatered mechanically to a residual water content of approximately 50 wt % with the aid of a suitable press device.
  • the material treated in this manner is now conducted through a suitable thermal drying equipment where it is dried to a residual water content of approximately 10 wt % and subsequently wound onto rollers. It is also possible, depending on the application striven for, to dry the material to lower residual water contents.
  • the material can subsequently be further refined (grinding, calendering, trimming) and cut into plates or rolls.
  • the composite substance obtained in this manner has, e.g., a flow transition range of approximately 70° C. to approximately 100° C.
  • the composite material is provided with a thermally activatable adhesive in order to achieve a durable fastening of the composite material with lining and upper material in a rational process when used as heel cap material or toe cap material.
  • the thermal activation of the adhesive takes place in the flow transition range of the composite substance.
  • adhesives are non-metallic, preferably organic substances that bind the joint parts by surface attachment and inner strength.
  • Adhesives include, e.g., glues, dispersion adhesives, solvent-containing adhesives, hot-melt adhesives and/or contact adhesives.
  • Organic adhesives are preferably used in the context of the present invention that can be either physically hardening adhesives or chemically reacting adhesives or a combination of both.
  • the physically hardening adhesives that can be used in the sense of the present invention include, e.g., adhesives present in solution or dispersion, contact adhesives or hot-melt adhesives.
  • those adhesives that impart a sufficient adhesion to the surfaces to be adhered without spitting off volatile components can be used as chemically reacting adhesives.
  • adhesives can also be used that achieve the required adhesion while splitting off volatile components.
  • the adhesives can be cold-hardening as well as also hot-hardening, exhibit a thermoplastic, duromer or elastomeric final state and be used in a single-component, two-component or multicomponent manner.
  • Hot-melt adhesives whose softening point is approximately 60° C. to approximately 120° C. are used in one embodiment. In a special embodiment hot-melt adhesives are used whose softening point is approximately 80° C. to approximately 100° C. In a quite special embodiment 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 onto the thermoplastic composite material in a hot process, e.g., by extruder application with slit nozzle or rollercoater application.
  • the adhesive can also be applied by powder application and be subsequently sintered on thermally. These processes are cold-hardening processes.
  • hot-melt adhesives are applied by extruder slit-nozzle application between approximately 50 to approximately 100 g/m 2 .
  • hot-melt adhesive powder coatings are applied between approximately 30 to approximately 80 g/m 2 .
  • hot-melt adhesive powder coatings are applied between approximately 40 to approximately 70 g/m 2 .
  • thermoplastic composite materials according to the invention are suitable for numerous other applications in addition to the manufacture of thermally formable shoe components, e.g., for coating the surface of objects such as, e.g., furniture fronts with or without inner radii, for the surface coating of parts in the inner spaces of motor-driven automobiles, or for jacketing the profile of wall-, floor- and ceiling panels.

Landscapes

  • 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)
US11/349,794 2003-08-08 2006-02-08 Composite material based on organic fibers for thermally mouldable shoe components Abandoned US20060194486A1 (en)

Applications Claiming Priority (3)

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
PCT/EP2004/008697 WO2005017004A1 (de) 2003-08-08 2004-08-03 Verbundmaterial für thermisch formbare schuhkomponenten auf organischer faserbasis

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2004/008697 Continuation WO2005017004A1 (de) 2003-08-08 2004-08-03 Verbundmaterial für thermisch formbare schuhkomponenten auf organischer faserbasis

Publications (1)

Publication Number Publication Date
US20060194486A1 true US20060194486A1 (en) 2006-08-31

Family

ID=34112062

Family Applications (1)

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

Country Status (5)

Country Link
US (1) US20060194486A1 (de)
EP (1) EP1654309A1 (de)
BR (1) BRPI0413447A (de)
DE (1) DE10336509A1 (de)
WO (1) WO2005017004A1 (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
US20150292148A1 (en) * 2012-12-18 2015-10-15 North Carolina State University Methods of forming an artificial leather substrate from leather waste and products therefrom
CN113661202A (zh) * 2019-04-15 2021-11-16 纳波雷公司 热塑性复合材料
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
WO2023094456A1 (de) 2021-11-24 2023-06-01 Rhenoflex Gmbh Flächengebilde aus einer polymermatrix und darin eingebetteten textilpartikeln

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK1931702T3 (da) 2005-10-05 2013-04-15 Commw Scient Ind Res Org Silkeproteiner
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
KR20170054542A (ko) 2009-08-26 2017-05-17 커먼웰쓰 사이언티픽 앤드 인더스트리얼 리서치 오가니제이션 실크 도프의 제조 방법
JP6317258B2 (ja) 2011-11-16 2018-04-25 コモンウェルス サイエンティフィック アンド インダストリアル リサーチ オーガナイゼーション コラーゲン様絹遺伝子
EP2850191A4 (de) 2012-03-26 2016-03-23 Commw Scient Ind Res Org Seidenpolypeptide
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
EP3532533A2 (de) * 2016-10-28 2019-09-04 Cambond Limited Bioverbund und biokunststoffe sowie verfahren zur verwendung
DE102021119799A1 (de) * 2021-07-29 2023-02-02 Nabore GmbH Thermoplastisches Verbundmaterial
DE102021119798A1 (de) * 2021-07-29 2023-02-02 Nabore GmbH Verbundmaterial

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3981741A (en) * 1972-11-16 1976-09-21 Hirokazu Iino Fibrous cleaning materials impregnated with a latex-mixture
US6482875B2 (en) * 1997-05-02 2002-11-19 Dorus Klebetechnik Gmbh & Co. Kg Thermoplastic composite material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE756874C (de) * 1939-03-26 1953-03-16 Degussa Verfahren zur Herstellung von Lederersatz
GB1498064A (en) * 1975-03-10 1978-01-18 Boer Mueboer Cipoeipari Kut Process for the production of fibre-based artificial leather
HU212122B (en) * 1988-06-29 1996-02-28 Volk Polimer compositions containing waste rubber and/ore waste leather as filler
DE3932904A1 (de) * 1989-10-03 1991-04-11 Bayer Ag Waessrige dispersionen enthaltend kautschuk und thermoplastisches polymerisat
DE19921209A1 (de) * 1999-05-07 2000-11-16 Dorus Klebetechnik Gmbh & Co K Thermoplastisches Verbundmaterial

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3981741A (en) * 1972-11-16 1976-09-21 Hirokazu Iino Fibrous cleaning materials impregnated with a latex-mixture
US6482875B2 (en) * 1997-05-02 2002-11-19 Dorus Klebetechnik Gmbh & Co. Kg Thermoplastic composite material

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
US20150292148A1 (en) * 2012-12-18 2015-10-15 North Carolina State University Methods of forming an artificial leather substrate from leather waste and products therefrom
US9822481B2 (en) * 2012-12-18 2017-11-21 North Carolina State University Methods of forming an artificial leather substrate from leather waste and products therefrom
CN113661202A (zh) * 2019-04-15 2021-11-16 纳波雷公司 热塑性复合材料
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
EP4173516A1 (de) * 2021-10-28 2023-05-03 Sciarada Industria Conciaria S.p.A. Verwendung von lederfasern als rutschhemmende mittel in polymer-zusammensetzungen und damit hergestellte gegenstände
WO2023094456A1 (de) 2021-11-24 2023-06-01 Rhenoflex Gmbh Flächengebilde aus einer polymermatrix und darin eingebetteten textilpartikeln

Also Published As

Publication number Publication date
EP1654309A1 (de) 2006-05-10
WO2005017004A1 (de) 2005-02-24
DE10336509A1 (de) 2005-03-03
BRPI0413447A (pt) 2006-10-17

Similar Documents

Publication Publication Date Title
US20060194486A1 (en) Composite material based on organic fibers for thermally mouldable shoe components
US6482875B2 (en) Thermoplastic composite material
JP6971039B2 (ja) 複合材料をバイオファブリケートするための方法
US11352497B2 (en) Layered collagen materials and methods of making the same
US20220204707A1 (en) Thermoplastic composite material
US20080271344A1 (en) Goat Skin for Shoe and Apparel Manufacture
US3985929A (en) Fabric for use in making footwear
CN1399030A (zh) 一种超细纤维沙发革的制备方法
CN105400444A (zh) 高强度低温热熔胶的制备方法
US2381774A (en) Method of making cork substitute
WO1983003224A1 (en) Reconstituted leather product from fibrillated leather fibers
GB1209312A (en) Improvements in and relating to cross-linkable coating compositions
GB2241716A (en) A composite non-woven fabric for one-piece shoe counters
DE19921209A1 (de) Thermoplastisches Verbundmaterial
JPS60215879A (ja) 皮革状材料及びその製造方法
MXPA02001170A (es) Material de refuerzo para el calzado, metodo de preparacion y su uso.
KR101570979B1 (ko) 천연 피혁 유사 시트의 제조방법
JPH02107203A (ja) 靴用しん材
Weixing et al. Modification of fatliquored split by in-situ polymerization of n-butyl-methacrylate
KR100322139B1 (ko) 천연 피혁 유사 소재의 제조 방법 및 그 소재.
JPH10120842A (ja) エチレン共重合体組成物およびその用途
JPS60215876A (ja) 皮革状材料及びその製造方法
JPS60215875A (ja) 皮革状材料及びその製造方法
Finch Latices in Leather Finishing
Träubel Leather board

Legal Events

Date Code Title Description
AS Assignment

Owner name: LEDERTECH GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WILKA, EWALD;HIEBER, THOMAS;REITER, ALBRECHT;REEL/FRAME:017577/0642

Effective date: 20060427

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION