EP1259349A2 - Materiau composite thermoplastique - Google Patents

Materiau composite thermoplastique

Info

Publication number
EP1259349A2
EP1259349A2 EP00929457A EP00929457A EP1259349A2 EP 1259349 A2 EP1259349 A2 EP 1259349A2 EP 00929457 A EP00929457 A EP 00929457A EP 00929457 A EP00929457 A EP 00929457A EP 1259349 A2 EP1259349 A2 EP 1259349A2
Authority
EP
European Patent Office
Prior art keywords
composite material
component
thermoplastic
weight
material 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.)
Withdrawn
Application number
EP00929457A
Other languages
German (de)
English (en)
Inventor
Jürgen Lorenz
Ewald Wilka
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
Henkel Dorus GmbH and Co KG
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 Henkel Dorus GmbH and Co KG filed Critical Henkel Dorus GmbH and Co KG
Publication of EP1259349A2 publication Critical patent/EP1259349A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • 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
    • C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material

Definitions

  • the invention relates to a thermoplastic composite material containing an organic fiber material or a mixture of two or more organic fiber materials, and a thermoplastic binder.
  • the invention further relates to a method for producing such a thermoplastic composite material.
  • the invention relates to the use of such a composite material for coating surfaces of objects, and to the objects coated therewith.
  • the invention also relates to an adhesive which serves to connect the composite material to the object to be coated.
  • Composite materials also called composite materials, are materials that are created by incorporating a basic 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 proportion of matrix in wood-based materials which includes, for example, the known particle board, is usually only 10-15%.
  • the matrix proportion 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 material fibers in thermosetting plastics can be one Transfer the tensile strength of the fibers to the plastic matrix, which in turn contributes advantages in terms of shape, shape 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, which 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 boards.
  • Another example of material-related recycling of waste products is the processing of trimming and punching waste from leather and shoe production into leather fiber materials.
  • LEFA leather fiber materials
  • LEFA is usually a single-layer fabric made of leather fibers and binders.
  • LEFA sheets were already used in the shoe industry at the end of the 1930s, for example for the production of back caps, fire and midsoles, slippers, heels and frames. The LEFA materials were also used to a small extent for technical leather seals.
  • leather In addition to properties such as flexibility and durability, which qualify leather for use in the shoe or baggage goods industry, leather is increasingly being used in other areas in which the decorative features of the leather are mainly used.
  • leather is increasingly being used in other areas in which the decorative features of the leather are mainly used.
  • the use of leather as a surface material for furniture fronts, wall or ceiling panels or other commodities has so far been difficult or even impossible.
  • the use of leather as a surface material for objects with a three-dimensional relief structure could only be realized with considerable effort. Since leather has no thermoplastic properties, it can only be used to a limited extent as a surface coating material. In particular, it is difficult to provide changing smooth three-dimensional relief structures with a smooth leather surface in a rational process.
  • Such rational methods for coating relief-like surfaces of moldings are known, for example, from the film coating industry.
  • a shaped body (object) is coated with a thermoplastic plastic film by heating the shaped body and plastic film to a temperature above the flow transition limit of the plastic film and the film in a suitable manner (for example by applying a vacuum between the shaped body and the plastic film) onto the shaped body is drawn up (deep-drawing process).
  • a suitable manner for example by applying a vacuum between the shaped body and the plastic film
  • an adhesive ensures a permanent connection between the plastic film and the molded body.
  • thermoplastic film As the coating material. So far, however, it has not been possible to equip leather-like substitute materials, for example LEFA, so that on the one hand they have the thermoplastic properties that are necessary for use in deep-drawing processes, and on the other hand they still have leather-like surface properties.
  • WO 98/50617 relates to a thermoplastic composite material which contains, for example, leather and a binder, the binder containing polyacrylates composed of at least one aqueous anionic polyacrylate dispersion and at least one aqueous cationic polyacrylate dispersion.
  • the composite materials described have the disadvantage of limited cohesion, so that, for example when using the composite materials described in deep-drawing processes, only limited profile depths (radii) can be coated without tearing the composite material.
  • PCT / EPOO / 03852 PCT / EPOO / 03852
  • the object of the present invention was therefore to provide a composite material which largely has the properties of the natural fibers used as the base material, but on the other hand is suitable due to its thermoplastic properties for processing in modern deep-drawing processes, and has sufficient cohesion for crack-free coating and bridging large profile depths and, moreover, is as easy to manufacture as possible.
  • thermoplastic composite material can be firmly and permanently bonded to a large number of surfaces in the course of machine processing.
  • thermoplastic composite material which contains organic fibers, in particular leather fibers, and a thermoplastic binder as the matrix material if a thermoplastic binder is used as the matrix material which contains at least 10% by weight of a polymer selected from the group consisting of Group consisting of polyurethanes, polyesters, polyamides, polyolefins, polyvinyl esters, polyethers, polystyrenes, styrene-olefin copolymers, polyacrylates or ethylene-vinyl acetate copolymers, or mixtures or copolymers of two or more of the polymers mentioned, the matrix material not exclusively consisting of two polyacrylates.
  • a polymer selected from the group consisting of Group consisting of polyurethanes, polyesters, polyamides, polyolefins, polyvinyl esters, polyethers, polystyrenes, styrene-olefin copolymers, polyacrylates or ethylene-vinyl acetate copoly
  • thermoplastic composite material obtainable from the polymers mentioned preferably has a flow transition limit of approximately 70 to approximately 130 ° C.
  • the invention therefore relates to a thermoplastic composite material containing
  • the binder at least 10 wt .-% of a polymer selected from the group consisting of polyurethanes, polyesters, polyamides, polyolefins, polyvinyl esters, polyethers, polystyrenes, styrene-olefin copolymers, poly-acrylates or ethylene-vinyl acetate copolymers, or mixtures or copolymers of two or more of the polymers mentioned, the binder not being composed exclusively of two different polyacrylates.
  • a polymer selected from the group consisting of polyurethanes, polyesters, polyamides, polyolefins, polyvinyl esters, polyethers, polystyrenes, styrene-olefin copolymers, poly-acrylates or ethylene-vinyl acetate copolymers, or mixtures or copolymers of two or more of the polymers mentioned, the binder not being composed exclusively of two different polyacrylates.
  • organic fiber material is suitable as component A of the thermoplastic composite material which gives the thermoplastic composite material the properties desired by the user, for example a certain appearance or a certain handle.
  • organic fiber material is understood to mean both naturally obtained or naturally obtainable fibers and also synthetically produced fibers, as long as they are based on an “organic basis”. For example, 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. Vegetable fibers, for example cotton, kapok, flax, hemp, jute, kenaf, ramie, gorse, manila, coconut or can also be used Sisal. 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, flour-containing polymer fibers, polyethylene, polypropylene, vinyl acetate, polyacrylonitrile, polyamide, polyester or polyurethane fibers.
  • leather fibers as the organic fiber material.
  • leather waste is shredded and crushed using a suitable process, so that the fibers obtained can subsequently be used in the process according to the invention to obtain a thermoplastic composite material with properties similar to leather.
  • the leather fibers can basically be obtained from any kind of leather waste. It can be both chrome-tanned and vegetable-tanned leather.
  • Types of leather which can be used in the context of the invention are, for example, boxing leather, such as cow box, calf or mast box, sanding box, chevrou leather, suede leather, velvet goat leather, sandal leather, under leather, lining leather, nappa leather, suede leather, glove leather, suede, vachette leather, blank leather. as well as technical leather, cleaning leather, hat band leather or transparent leather.
  • the organic fiber material is crushed to an elongated length of approximately 0.1 to 15 mm.
  • a length of approximately 0.5 to 13 mm, preferably approximately 1 to approximately 10 mm and particularly preferably approximately 3 to approximately 8 mm fiber length is appropriate.
  • the fiber length is measured in the stretched state of the fiber, depending on the starting material and type of comminution it can of course happen that the fiber takes on an irregularly curved shape without external influences.
  • Component A is contained in the thermoplastic composite material according to the invention in an amount of at least about 10% by weight as the base material. With an increasing proportion of A, 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 or even more than about 50% by weight, with proportions of, for example, 55% by weight or even 60% by weight and more are possible.
  • the proportion of fiber materials is particularly preferably from approximately 15 to approximately 50% by weight, very particularly preferably from approximately 25 to less than approximately 45% by weight.
  • leather fibers are preferably contained as component A in the thermoplastic composite material according to the invention.
  • thermoplastic composite material contains a thermoplastic binder as component B.
  • binder is understood to mean polymeric compounds which serve as a matrix in the composite material. Polymeric materials with a molecular weight of more than about 1000 are generally used as binders, 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 ö about 50,000 and about 150,000.
  • binder stands for the entirety of the polymeric matrix material, irrespective of how many polymeric components it consists of and how many different preparations containing the polymers constituting the binder were required for its production.
  • the molecular weight distribution of the polymers does not have to be monomodal. If appropriate, the thermoplastic binder can also have a bimodal or higher-modal distribution.
  • a binder which contains at least 10% by weight of a polymer selected from polyurethanes, polyesters, polyamides, polyolefins, polyvinyl esters, polyethers, polystyrenes, styrene-olefin copolymers, polyacrylates or ethylene-vinyl acetate copolymers. Contains copolymers, or mixtures or copolymers of two or more of the polymers mentioned, wherein the binder does not consist exclusively of two polyacrylates.
  • binders which contain at least two different polymers are used to produce the thermoplastic composite materials.
  • two different polymers are understood to mean two types of polymer, which differ in their chemical composition, ie in the type of monomers involved in the structure of the polymers or, if two or more monomers are involved in the structure of the polymer of the monomers with one another or in 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 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 .
  • polyester is to be understood as meaning all polymers which have at least two ester groups and no urethane groups in the polymer backbone.
  • All thermoplastic polyesters known to the person skilled in the art are suitable as polyesters in the context of the present invention, in particular those polyesters as are usually used in the production of thermoplastic molded articles, in particular films, or for thermoplastic coating of surfaces.
  • polyesters as are obtainable by reacting dicarboxylic acids with corresponding polyfunctional alcohols, in particular difunctional alcohols, for example difunctional polyethers such as polyethylene oxide, are suitable.
  • thermoplastic polyamides as are obtainable by reacting suitable di- or polycarboxylic acids with corresponding amines are suitable as polyamides.
  • 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.
  • styrene-olefin copolymers are also suitable as polymers for use in the binder of the thermoplastic composite material according to the invention.
  • styrene-olefin copolymers are used, such as, for example, under the name Kagetex LBS 3565 or Kagetex LBS 3060 from the company Kautschukgesellschaft or under the name Intex 131 from the company Enichem or under the name 28 W 20 from are available from Synthomerchemie.
  • 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.
  • polyvinyl acetate is used.
  • Suitable polyvinyl acetates are available for example under the name Vinnapas D50 from Wacker, Mowilith D 60 from Clariant or Vinnamul 60 044, Vinnamul 9300, Vinnamul 9960 or Vinnamul 84125 from Vinnamul (NL).
  • 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, i.e. by polymers which carry corresponding hydrophilic groups, for example carboxylic acid groups or amino groups.
  • 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 using 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 free-radical or ionically be polymerized.
  • polyacrylates in anionic dispersion as can be obtained, 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.
  • Suitable monomers 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. If necessary, small amounts of acrylic acid, methacrylic acid, acrylamide or methacrylamide can be added as further monomers during the polymerization.
  • acrylates and / or methacrylates with one or more functional groups can be present in the polymerization.
  • these are maleic acid, itaconic acid, butanediol diacrylate, hexanediol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate,
  • Acrylic ester-vinyl ester copolymers, acrylic ester-styrene copolymers or acrylic ester-methacrylic ester copolymers are particularly preferred.
  • Particularly preferred and suitable for use in the thermoplastic composite materials according to the invention are polyacrylate dispersions, such as those sold under the brand name Acronal ® by BASF AG, Ludwigshafen, in particular the products Acronal ® 500 D and Acronal ® S312 D.
  • anionic polyacrylate dispersions have only one type of polymer. If two different polyacrylates from anionic dispersions are to be used, it is generally necessary to use two different anionic dispersions, which contain the respective polymer in dispersed form I included. In the context of the present invention, however, it is irrelevant whether the various polyacrylates preferably contained in the matrix are present in a single dispersion or whether they are obtained from two or more different dispersions.
  • the binder used as component B contains at least two of the abovementioned polymers, the proportion of the two polymers in the total binder, that is to say in total component B, in total at least about 10% by weight, for example 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 binder used as component B contains, in addition to two of the above-mentioned types of polymers, only one polyacrylate or no polyacrylate.
  • the binder contains at least one polyvinyl acetate and at least one styrene-butadiene copolymer, in particular such a block copolymer.
  • thermoplastic properties of the thermoplastic composite material according to the invention can be influenced by the choice of polyacrylates 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 formation of the film, determines one of the most important application properties of a polymer dispersion.
  • the minimum film forming temperature (MFT) is usually determined according to DIN 53787.
  • At least one of the polymers has an MFT of up to 30 ° C.
  • At least one of the polymers has an MFT of approximately up to 5 ° C. and at least one further polymer has an MFT of approximately 15 ° C. to approximately 25 ° C.
  • the total proportion of component B in the thermoplastic composite material is preferably at least about 20% by weight. It can be advantageous, for example for a targeted change in properties, if the thermoplastic composite material contains at least approximately 30% by weight or at least approximately 40% by weight or more of component B, for example at least approximately 50 to at least approximately 80% by weight. In a preferred embodiment of the invention, the proportion of component B in the total thermoplastic composite material is about 50 to about 75% by weight.
  • 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, cationic polymers, 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.
  • Cationic polymers or cationically charged polymers are polymers which carry positive charges on the polymer backbone or on side groups covalently bonded to the polymer backbone.
  • Cationic charges can be applied to a polymer by attaching suitable cationic groups.
  • “Cationic groups” are understood to mean groups which either carry a positive charge or can be converted into a group carrying a cationic charge by a simple reaction, for example quaternization. As a rule, these are amines or ammonium groups.
  • a “quaternization” is understood to mean a reaction in which a primary, secondary or tertiary amine is converted into the tetravalent, positively charged form by reaction with a suitable reagent.
  • suitable reagents are, for example, alkyl halides, especially alkyl chlorides, alkyl bromides and alkyl iodides, and protonic acids, for example mineral acids, such as hydrohalic acid, phosphoric acid, sulfuric acid, or strong organic acids, such as formic or acetic acid.
  • Suitable polymers carrying cationic groups can be suitably modified polyacrylates, polyesters, polyurethanes or other polymers which carry at least one primary, secondary or tertiary nitrogen atom. In the context of the present invention, preference is given to using polyacrylates which carry cationic groups.
  • Such polyacrylates can be prepared, for example, by the monomers described above (with the exception of the monomers bearing free acid groups) are copolymerized together with a suitable ethylenically unsaturated compound bearing a primary, secondary or tertiary amino group.
  • Suitable ethylenically unsaturated, primary, secondary or tertiary amino groups are, for example, dimethylaminoethyl methacrylate, dimethylaminoneopentyl acrylate, dimethylaminopropyl methacrylate, aminoethyl methacrylate, 2-N-morpholinoethyl acrylate, tert.-butylaminoethyl methyl acrylate, 2,2-methacrylate, 4-methacrylate din,
  • the cationically charged polymers preferably have a pH of about 3 to about 8, but particularly preferably the pH of the cationically charged polymers is neutral, i.e. between about 6.5 and about 7.5.
  • the charge density i.e. the number of cationic groups per unit weight of polymer is preferably about 2 to about 6 meq / g, more preferably about 2.5 to about 5 meq / g, and more preferably about 3.5 to about 4.5 meq / g.
  • the cationic polymer generally has a molecular weight from about 1,000 to about 500,000, with molecular weights from about 50,000 to about 150,000, in particular from about 80,000 to about 120,000, being preferred.
  • preservatives those preservatives which have a fungicidal spectrum of action are particularly preferred.
  • Preventol ® A11 D a preservative sold by BAYER, Leverkusen, is particularly suitable for the purposes of the invention.
  • component B contains at least 50% by weight of polyvinyl acetate. In a further preferred embodiment of the invention, component B contains at least 20% by weight of a copolymer of butadiene and styrene.
  • thermoplastic composite material contains
  • Paraffins natural and / or synthetic oils, silicone oils, ionic and / or non-ionic surfactants.
  • thermoplastic composite material according to the invention is preferably used to coat surfaces with a relief structure. Such coatings are usually applied in the so-called deep-drawing process.
  • the thermoplastic composite material has a flow transition range of approximately 70 to 130 ° C.
  • thermoplastic composite materials according to the invention can be subjected to irreversible changes in shape, for example stretching.
  • the thermoplastic composite material according to the invention due to its special tear strength combined with good flowability, can also coat reliefs with large height differences (radii) without cracks in the coating and while maintaining the original surface structure.
  • thermoplastic composite material according to the invention is preferably produced by contacting component A with the constituents component B, these constituents preferably being in aqueous dispersion.
  • component B has more than one component, i.e. more than one polymer
  • the two polymers can coexist in a dispersion.
  • both 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
  • the dispersion or the dispersions do not consist exclusively of two different polyacrylates, are mixed to form a mixture so that the polymers contained in the dispersion or the dispersions form component B, and then the mixture is treated with an aqueous solution of an aluminum or a copper salt, dewatered and is dried.
  • 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 identically stabilized, at least with regard to the charge of the stabilizing species.
  • 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 waste is comminuted in knife mills to a size of approximately 1 cm 2 (pre-cut). The shredding is usually carried out dry at this stage.
  • the pre-shredded leather waste is 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 it is possible to achieve a waste water content of approximately 50%, preferably above, of the total water used during the comminution process.
  • the suspension of leather fibers in water thus obtainable is then transferred to 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 proportion of chrome-tanned leather or if the leather fibers consist exclusively of chrome-tanned leather, vegetable tannins, for example chestnut extract, quebracho, mimosa or valonea, are first added.
  • Fatliquors are then added. All leather greasing agents which are emulsifiable in water are suitable as greasing agents.
  • This sulfated fish oils are preferably used, for example Licrol ® DM 10 from Eberle, Coriatol U6 by the company Polychemie or CORIPOL 2397 by the company WO 00/67937 _ .. PCT / EP00 / 03852
  • Dyes can also be added to the batch. These are usually quantitative iron oxide paints, for example Bayferrox ® 960 (BAYER company).
  • Preservatives for example Preventol A11D (from BAYER), 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.
  • additives are not water-soluble or self-emulsifiable in water, they are generally added to the batch in the form of emulsions.
  • 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 are added separately from the cationically stabilized polymer dispersion or the cationically stabilized polymer dispersions. The order does not matter.
  • Aluminum sulfate is preferably used, with about 40 to 300 l, preferably about 100 to about 250 l, particularly preferably about 120 to about 200 per 1000 kg batch I an about 20 to preferably about 60 wt .-% aluminum sulfate solution are added.
  • the mixture can be treated with a solution of a cationically charged polymer.
  • the cationically charged polymer preferably has a molecular weight that does not exceed about 150,000, advantageously from about 80,000 to about 120,000.
  • the charge density of the cationically charged polymer is about 2.00 to 5.00 meq / g, preferably about 2.50 to about 4.50 meq / g and particularly preferably about 3.00 to about 4.00 meq / g.
  • the amount of the cationically charged polymer is approximately 0.1 to 10% by weight, based on the total dry mass in the batch, preferably approximately 1 to 8% by weight and particularly preferably approximately 2 to 6% by weight.
  • 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 On the one hand, 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 pressed with the aid of a suitable pressing device, preferably a cycle press, at a pressure of about 1000 to about 3000 t, preferably about 1500 to about 2500 l.
  • a suitable pressing device preferably a cycle press
  • the material treated in this way is then passed through a suitable thermal drying device, and here to a residual water content of approximately 10% by weight dried and then wound up on rolls.
  • the films obtained in this way have, for example, a flow transition range from approximately 70 to approximately 130 ° C. and are therefore suitable for modern surface coating processes, preferably so-called deep-drawing processes.
  • an adhesive is generally used.
  • 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 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. those 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-curing, have a thermoplastic, thermoset or elastomeric final state and can be used in one or two or more components.
  • the surfaces to be bonded are subjected to increased pressure after the joining.
  • adhesives are therefore used in the context of the present invention which, after pressure has been exerted on the surfaces to be joined, result in improved adhesion compared to pressure-free processing.
  • the adhesives used in the context of the present invention advantageously have at least three different macromolecular compounds as adhesion promoters.
  • adhesion promoters are understood to mean macromolecular substances which mainly contribute to the development of the adhesion and cohesion forces between the surfaces to be bonded.
  • a combination of polyurethane, polyacrylate and ethylene vinyl acetate copolymer (EVA copolymer), in the form of aqueous dispersions or as a hot melt adhesive is used as the adhesion promoter.
  • EVA copolymer ethylene vinyl acetate copolymer
  • the adhesive contains about 30 to 120 parts by weight of a preferably anionic polyester polyurethane dispersion.
  • Polyester polyurethanes can be obtained by generally reacting relatively low molecular weight polyesters with OH end groups with at least divalent isocyanates with the formation of urethane linkages.
  • the polyesters generally have a molecular weight of at least about 400, preferably at least about 500. Both aromatic and aliphatic polyesters can be used, whereby aromatic polyesters are usually not suitable as the sole polyester component due to the high tendency to crystallize and the low flexibility.
  • Aliphatic dicarboxylic acids such as butane-1, 4-dicarboxylic acid, pentane-1, 5-dicarboxylic acid, hexane-1, 6-dicarboxylic acid, heptane-1,7-dicarboxylic acid or, for example, are usually involved as acid components in the structure of the polyester 2.0 further, higher homologues with increasing number of carbon atoms.
  • Aromatic dicarboxylic acids for example terephthalic acid or isophthalic acid, can also be used.
  • all aliphatic dialcohols with 2 to about 20 carbon atoms can be used as the diol component for the production of the polyesters.
  • the polyesters can also have been produced using acid or alcohol components which have a functionality different from 2.
  • acid or alcohol components which have a functionality different from 2.
  • 1, 2,3-propane tricarboxylic acid, hemimellitic acid, trimellitic acid, trimesic acid or 1, 2,4,5-benzenetetracarboxylic acid can be used as the 3 or higher acid components.
  • Trivalent or higher alcohol components are, for example, glycerol, trimethylolpropane, pentaerythritol or carbohydrates, such as the monomeric sugar compounds, especially glucose.
  • reaction products of two or higher alcohols with ethylene oxide and / or propylene oxide can also be used as the diol component.
  • the reaction generally takes place with a stoichiometry which, on the one hand, allows the desired molecular weight to be set (generally about 400 to about 10,000, preferably about 500 to about 5,000) and at the same time ensures that the polyester has at least one hydroxyl group in the molecule, preferably as End group.
  • polyesters described are then reacted with di- or higher-valent, for example tri or tetraisocyanates.
  • di- or higher-valent for example tri or tetraisocyanates.
  • all aliphatic or aromatic polyisocyanates can be used for this purpose.
  • Preferred polyisocyanates are, for example, 1,6-hexamethylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, and 4,4'-diisocyanatodiphenylmethane (MDI).
  • MDI 4,4'-diisocyanatodiphenylmethane
  • tolylene diisocyanate it is preferably an isomer mixture which has the 2,4- and the 2,6-isomer in a ratio of about 80 to about 20.
  • the polyurethanes are, for example, in dispersed form, water being preferred as the continuous phase.
  • anionic emulsifiers are used.
  • the polyurethane dispersions have a solids content of about 35 to about 65%, a viscosity (according to DIN 53019) of less than about 1000 mPas, preferably about 100 to about 900 mPas and particularly preferably about 200 to about 800 mPas .
  • the pH is preferably in a range from about 5 to about 9, particularly preferably from about 6.5 to about 7.5.
  • the minimum film-forming temperature (DIN 53787) of the preferred polyurethane dispersions is between approximately 2 and approximately 10 ° C., preferably approximately 4 to approximately 6 ° C. and particularly preferably approximately 5 ° C.
  • the softening point of the films obtainable from these polyurethane dispersions can be more than 100 ° C., but it is preferred if the softening point is about 80 ° C. or below, for example about 60 ° C.
  • polyurethane dispersions are Dispercoll U 42 ®, ® Dispercoll U 53, Dispercoll U 54 ®, ® Dispercoll KA 8481 from BAYER, Quilastic ® DEP-172 and / or Quilastic ® 144-66.
  • Dispercoll ® U 53 is particularly preferred.
  • Polyolefins or polyamides can also be used as adhesives, these being used in particular as hot melt adhesives.
  • the polyacrylic acid esters are also preferably used as an aqueous dispersion. It is particularly preferred if the dispersion is based on anionic emulsifiers.
  • the polyacrylate dispersions are preferably polymer dispersions which in themselves can be used as adhesives, so-called acrylate adhesives.
  • Polyacrylates are preferably based on acrylic acid esters, preferably methyl, ethyl, n-butyl, isobutyl or 2-ethylhexyl esters of acrylic acid. It is also possible to use the corresponding esters of methacrylic acid together with or instead of the acrylic acid esters.
  • the acrylic acid esters and / or methacrylic acid esters can be copolymerized with other substances which have an olefinically unsaturated double bond. These are preferably, for example, vinyl esters of carboxylic acids, for example vinyl acetate, or styrene.
  • the polyacrylates can have functional groups that allow subsequent crosslinking, for example by increasing the temperature. These are preferably functional groups which can be crosslinked by adding a small amount of a catalytically active substance by increasing the temperature. It is particularly preferred if an acid is used as the catalyst or another compound which can release an acid by increasing the temperature in a suitable environment, for example in an aqueous environment. Compounds such as oxalic acid, ammonium chloride, magnesium chloride and / or diammonium phosphate are preferred.
  • the polyacrylate dispersions preferably have a viscosity (DIN 53019) of approximately 20 to approximately 5,000 mPas at 23 ° C.
  • the pH of the preferred dispersions is generally about 2 to about 9, preferably about 2.5 to about 8.
  • the minimum film-forming temperature (DIN 53787) is below about 1 ° C., preferably below about 0 °, for all polyacrylate dispersions used C.
  • the polyacrylates generally have a glass transition temperature of less than about -20 ° C, preferably less than -30 ° C and particularly preferably less than -35 ° C, for example -40 ° C or -45 ° C.
  • the average particle size of the dispersed polyacrylate particles is preferably less than about 70 ⁇ m, preferably less than about 65 ⁇ m.
  • EVA copolymers are copolymers of ethylene and vinyl acetate.
  • the two monomers can be copolymerized by free radicals in any desired proportions. This results in copolymers with a statistical arrangement of the monomer units in the polymer chains.
  • the properties of the EVA copolymers can be varied within wide limits via the molar ratio of ethylene to vinyl acetate. For example, products with an ethylene content of less than 30% by weight are partially crystalline and thermoplastic, those with a vinyl acetate of about 40 to about 70% by weight are largely amorphous.
  • the EVA copolymers are usually produced by bulk, emulsion or solution polymerization.
  • the molecular weight of the EVA copolymers used in the invention is between about 10,000 and about 1,500,000.
  • the EVA copolymers are preferably in the form of an aqueous dispersion with a solids content of between about 40 and about 70% by weight, preferably about 50 to about 60% by weight.
  • the viscosity (according to ISO 2555 at 23 ° C, Brookfield (RVT), 20 rpm, spindle 4) is about 2,000 to about 13,000 mPas, for example, dispersions with a viscosity of about 4,000 to about 6,000 mPas, about 6,000 to about 12,000 mPas or about 2,500 to about 4,000 mPas can be used.
  • the pH of the dispersions is between about 3 and about 6, preferably between about 3.8 and about 4.8.
  • the dispersions produce opaque, transparent or clear films and generally have a minimum film-forming temperature of less than 5 ° C., preferably less than about 3 ° C. and particularly preferably about 0 ° C.
  • the films have a tensile strength (standard climate 23 ° C / 50% RH, according to DIN 50014) of between about 2.5 and about 9 N / mm 2 .
  • dispersions can be used which give films with a tensile strength of about 3 N / mm 2 , 6 N / mm 2 or about 8 N / mm 2 .
  • the elongation at break (determined according to DIN 50014 at a standard climate of 23 ° C./50% RH) should be about 500 to about 900% for the films produced from the dispersions.
  • the films should have a cold break temperature (DIN 53372) of at most about 4 ° C.
  • the adhesive according to the invention can also contain further components, for example wetting agents, thickeners, preservatives or defoamers.
  • wetting agents are used to improve the substrate wetting in aqueous systems.
  • wetting agents improve the wetting of the thermoplastic composite material and the surface to be bonded to it.
  • all surfactants which do not adversely affect the stability of the adhesive dispersion can be used as wetting agents, but polyether-modified dimethylpolysiloxanes are preferably used as wetting agents.
  • the commercially available BYK ® -346 product from BYK-Chemie GmbH or Lumiten ® IRA is particularly suitable.
  • Natural thickeners such as agar-agar, carrageen, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin or casein can be used as thickeners.
  • Modified natural substances such as, for example, carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether can also be used.
  • Organic synthetic thickeners such as polycarboxylic acids, polyethers, polyimines, polyamides and some vinyl polymers can also be used and are preferred in the context of the present invention, thickeners such as polyvinyl alcohol or polycarboxylic acids, for example those containing carboxyl groups Acrylic ester copolymers, or vinyl pyrrolidone copolymers, are preferred.
  • the thickeners are used as an aqueous solution or aqueous dispersion with a solids content of generally about 20 to about 40% by weight, preferably about 25 to about 30% by weight.
  • Commercially available thickening agents which are usable in the context of the invention are, for example, Collacral ® VL by BASF or Latekoll D ® by the company BASF.
  • Agitan ® 281 (Münzing Chemie) can be used as a defoamer.
  • Aktizid ® RS (Thorchemie), for example, is suitable as a preservative.
  • the above-mentioned adhesives are used as hot-melt adhesives in a corresponding formulation.
  • the adhesive is applied to the base to be coated with the thermoplastic composite material, preferably a particle board, by means of a spray gun or another suitable tool.
  • the sections of the thermoplastic composite material according to the invention are placed on the substrate to be coated and pressed at a temperature of about 80 to about 100 ° C.
  • the pressing time is between about 10 and about 240, preferably between about 30 and about 120 seconds, depending on the thickness of the section.
  • the pressure is about 2 to about 10, preferably about 3 to about 6 bar.
  • hot melt adhesives are used as hot melt adhesives, the drying time mentioned does not apply. Depending on the open time of the hot melt adhesive, the sections should be brought into contact with the base and pressed as quickly as possible.
  • hot melt adhesives is particularly appropriate, for example, if strand materials, for example extruded profiles, are to be coated discontinuously or continuously with the thermoplastic composite material according to the invention.
  • Another object of the invention is a method for the surface coating of objects with the thermoplastic composite material according to the invention, in which the connection between the composite material according to the invention and the object takes place by means of hot melt adhesive.
  • the invention furthermore relates to the use of a thermoplastic composite material according to the invention or a thermoplastic composite material produced according to the invention for the surface coating of objects, in particular for profile coating of wall, floor and ceiling panels, furniture fronts with or without inner radii, for edge banding, or for surface coating of the interior of motor-driven motor vehicles , for example of dashboards, door mirrors, columns, moldings, gear levers, hat racks, trunk applications and the like.
  • thermoplastic composite material is preferably applied in a deep-drawing process with the application of a vacuum.
  • the thermoplastic composite material is preferably in the form of foils with a thickness of approximately 0.5 mm to approximately 1.0 mm, preferably approximately 0.6 mm to approximately 0.8 mm.
  • the thermoplastic composite material according to the invention has a surface coating which can be used, for example, to seal the material.
  • Suitable surfaces are, for example, thin foils made of polyurethane, polyester, polyolefins or the like, which are laminated onto the surface of the thermoplastic composite material according to the invention with a suitable adhesive.
  • the present invention thus also relates to a thermoplastic composite material according to the invention which laminates on at least one surface with a polymer film, in particular made of polyurethane, polyester or polyolefins is.
  • the film contains dyes or pigments.
  • the film has a surface profile, for example scars or knobs.

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

Abstract

L'invention concerne un matériau composite thermoplastique renfermant un matériau fibreux organique et un mélange d'au moins deux matériaux fibreux organiques et d'un liant thermoplastique. L'invention concerne en outre un procédé de fabrication d'un tel matériau composite thermoplastique, ainsi que l'utilisation dudit matériau composite thermoplastique pour le revêtement superficiel d'objets.
EP00929457A 1999-05-07 2000-04-28 Materiau composite thermoplastique Withdrawn EP1259349A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19921209 1999-05-07
DE1999121209 DE19921209A1 (de) 1999-05-07 1999-05-07 Thermoplastisches Verbundmaterial
PCT/EP2000/003852 WO2000067937A2 (fr) 1999-05-07 2000-04-28 Materiau composite thermoplastique

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EP1259349A2 true EP1259349A2 (fr) 2002-11-27

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EP (1) EP1259349A2 (fr)
AU (1) AU4752900A (fr)
BR (1) BR0010357A (fr)
DE (2) DE19921209A1 (fr)
WO (1) WO2000067937A2 (fr)

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DE20110683U1 (de) * 2001-06-27 2002-11-07 Gedore Werkzeugfab O Dowidat Drehmomentschlüssel mit nicht leitendem Griff
DE10336509A1 (de) * 2003-08-08 2005-03-03 Ledertech Gmbh Verbundmaterial für thermisch formbare Schuhkomponenten auf organischer Faserbasis
DE102005028465A1 (de) * 2005-06-20 2006-12-28 Ledertech Gmbh Schallisolierendes Material
DE102009050546A1 (de) * 2009-10-23 2011-05-12 Biowert Ag Verfahren zur Herstellung eines Kunststoffmaterials mit erhöhter Feuerbeständigkeit, Kunststoffmaterial mit erhöhter Feuerbeständigkeit sowie Kunststoffartikel aus einem solchen Kunststoffmaterial
ITCS20110036A1 (it) * 2011-11-24 2013-05-25 Consorzio Per Le Tecnologie Biomedi Che Avanzate Materiali compositi ottenuti da fibre estratte da due varieta' di ginestra e processo per ottenerli
DE102021119799A1 (de) * 2021-07-29 2023-02-02 Nabore GmbH Thermoplastisches Verbundmaterial

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Publication number Priority date Publication date Assignee Title
FR2451962A1 (fr) * 1979-03-22 1980-10-17 Ato Chimie Materiau composite a base de fibres de cuir et procede pour sa fabrication
JPS63305169A (ja) * 1987-06-05 1988-12-13 Marubishi Yuka Kogyo Kk 難燃性合成樹脂組成物
ATE229101T1 (de) * 1997-05-02 2002-12-15 Henkel Dorus Gmbh & Co Kg Thermoplastisches verbundmaterial

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DE20023654U1 (de) 2005-06-09
AU4752900A (en) 2000-11-21
BR0010357A (pt) 2002-02-13
WO2000067937A2 (fr) 2000-11-16
WO2000067937A3 (fr) 2002-09-12

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