EP1106724B1 - Process for pre-binding fibrous materials - Google Patents
Process for pre-binding fibrous materials Download PDFInfo
- Publication number
- EP1106724B1 EP1106724B1 EP20000124328 EP00124328A EP1106724B1 EP 1106724 B1 EP1106724 B1 EP 1106724B1 EP 20000124328 EP20000124328 EP 20000124328 EP 00124328 A EP00124328 A EP 00124328A EP 1106724 B1 EP1106724 B1 EP 1106724B1
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- EP
- European Patent Office
- Prior art keywords
- process according
- fibre material
- fiber
- pulverulent
- fibre
- 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.)
- Expired - Lifetime
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Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4218—Glass fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4242—Carbon fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/4334—Polyamides
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/60—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in dry state, e.g. thermo-activatable agents in solid or molten state, and heat being applied subsequently
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/273—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having epoxy groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/08—Processes in which the treating agent is applied in powder or granular form
Definitions
- the invention relates to a method for Manufacture of molded plastic parts made of fiber-reinforced, unsaturated polyester resins or epoxy resins by laying out the pre-bonded fiber material, Soak the fiber material with the unsaturated polyester resin or epoxy resin and molding the molded part.
- UP resins unsaturated Polyester resins
- the textile structures into the molds draped and impregnated with the reaction resin the in of the fiber mat existing prebinder by the existing in the UP resin Styrene is dissolved or dissolved. Consequently the mats lose their inherent stiffness and become adapt better to the tool contours, while at the same time the impregnation of the fiber mats with the resin is accelerated becomes.
- thermoplastic materials have been used in the production process mentioned Polyester powder, in particular polyester powder based Bisphenol-A, used as a pre-binder for the fiber mats.
- polyester powder in particular polyester powder based Bisphenol-A
- the bisphenol A polyester powder is placed on a previously deposited one Sprinkled glass fleece and at the subsequent Furnace run melted, so that the glass fibers at their crossing points bound by the molten polymer powder become.
- the pre-bound glass mats then become Reinforcement of UP resins used.
- the prebinder is, for certain applications, insufficient kinetics of solubility in monomeric styrene.
- the main thing here is to minimize the fraying of the assembled fiber mat, the dimensional stability of an optionally preformed fiber mat to ensure and incompatibility between preform binders and to avoid injection resin.
- AU-A 36659/89 describes a process for the production of pre-bonded fiber materials in the glass fibers with two different Lengths with a triple combination as a binder which styrene-soluble polyester powder, Contains polystyrene powder and polyvinyl acetate dispersion.
- styrene-soluble binders are unsuitable Binder for the consolidation of fiber materials described, which is further processed with a thermoplastic melt become.
- Binder for this application the use of hydroxyl groups or polyacrylates containing carboxyl groups recommended, which by means of solvent or bulk polymerization getting produced.
- Emulsion polymers become explicit discouraged, as the surface-active contained therein Substances contaminate the binder and lead to undesirable side effects such as discoloration or thermal degradation.
- EP-A 894888 discloses textile binders based on carboxyl-functional ones Polymers, which in combination with Epoxy or isocyanate crosslinkers are used, known. On processes for the preparation of pre-bound, styrene-soluble Molded fiber parts are not received.
- the task was to use a powdery prebinder To provide, which is in a styrene-containing UP resin resolves as quickly as possible, but also for pre-binding in processes is suitable, especially where the tolerance of the prebinder with the polyester resin in the foreground.
- the invention relates to a method for Manufacture of fiber reinforced Plastic molded parts made of reactive resins such as Epoxy resins or unsaturated polyester resins.
- Suitable copolymers are those based on one or more monomers from the group comprising vinyl esters of unbranched or branched alkyl carboxylic acids 1 to 15 carbon atoms, methacrylic acid ester and acrylic acid ester of Alcohols with 1 to 10 carbon atoms, vinyl aromatics such as styrene and Vinyl chloride.
- Preferred vinyl esters are vinyl acetate, vinyl propionate, Vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate, vinyl pivalate and vinyl ester of alpha-branched Monocarboxylic acids with 5 to 11 carbon atoms, for example VeoVa5 or VeoVa9.
- Preferred methacrylic acid esters or acrylic acid esters are methyl acrylate, methyl methacrylate, Ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate.
- the composition of the copolymer be chosen so that a glass transition temperature Tg or a melting point of greater than 35 ° C, preferably from 55 ° C to 150 ° C results.
- the glass transition temperature Tg and the melting point of the polymers can be determined in a known manner by means of differential scanning calorimetry (DSC).
- Tg n the glass transition temperature in degrees Kelvin of the homopolymer of the monomer n. Tg values for homopolymers are listed in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).
- Vinyl ester copolymers, styrene copolymers are preferred and acrylic acid ester copolymers.
- Especially preferred copolymers are vinyl acetate / ethylene copolymers, Vinyl acetate / vinyl chloride-, vinyl acetate / VeoVa5-, Vinyl acetate / VeoVa9 copolymers, each of 0.01 to 25% by weight of the above-mentioned monomer units containing carboxyl groups contain, and the composition of which is chosen so that the above-mentioned glass temperatures Tg or melting points result.
- Methyl methacrylate / butyl acrylate are also particularly preferred.
- Suitable ethylenically unsaturated monomers containing carboxyl groups are ethylenically unsaturated mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid.
- the content of carboxyl groups is preferably Comonomer units containing 0.01 to 10 wt .-%, based on the total weight of the copolymer.
- the copolymers 0.01 to 10.0 %
- the copolymers each 0.01 to 2 wt .-% acrylic acid and / or acrylamide.
- the copolymers are prepared in a manner known per se Way after the emulsion polymerization process in Presence of emulsifier, as for example in WO-A 94/20661, the disclosure of which is part of the present application.
- To make the powder the resulting polymer dispersion is dried. Drying can be done by spray drying, drum drying, Freeze drying or by coagulation of the dispersion and subsequent Fluid bed drying take place. To be favoured spray drying and roller drying. Preferably done the preparation of the copolymer and its drying without Protection colloid added.
- Suitable crosslinkers are powdered compounds which contain two or more reactive groups with carboxylic acid groups form a covalent bond with a melting point from 40 ° C to 150 ° C.
- Compounds which are two or more reactive are preferred Groups from the group of epoxides, isocyanates or primides contain.
- Suitable epoxy crosslinkers are those from Bisphenol A type, that is, condensation products of bisphenol A and epichlorohydrin or methylepichlorohydrin.
- Epoxy crosslinkers are commercially available, for example under the trade names Epicote or Eurepox available.
- Suitable diisocyanates are also common commercial products, for example m-tetramethylxylene diisocyanate (TMXDI), methylene diphenyl diisocyanate (MDI).
- TXDI m-tetramethylxylene diisocyanate
- MDI methylene diphenyl diisocyanate
- the crosslinker content is generally from 0.1 to 25% by weight, preferably from 4 to 12% by weight, based on the powdery copolymer.
- Combinations of the copolymer a) are usually and the crosslinker b) used. This is especially true for applications in which high mechanical strength is required. In contrast, in applications where the styrene solubility is paramount can also be used without the addition of a crosslinker.
- the powdered Binder composition still a crosslinking catalyst based on organic compounds, which are quaternary Groups of elements of the 5th main group of the PSE included.
- Powdered catalysts are preferred, which differ from Triphenylphosphonium halides or quaternary ammonium compounds derived. Examples include methyl, ethyl, Propyl, butyl triphenylphosphonium bromide or the corresponding Iodides and chlorides.
- Triphenylphosphonium halides are also suitable with substituted alkyl radical such as 2-carboxyethyl, 3-bromopropyl or formylmethyl triphenylphosphonium bromide.
- Suitable quaternary ammonium compounds are tetrabutylammonium, Benzyltrimethylammonium, methyltributylammonium salts.
- the compounds mentioned are commercially available and are preferably obtained in amounts of 0.1 to 5% by weight on the powdery copolymer, used.
- polymers In applications where it depends on the melt flow characteristics arrives, have proven as polymers a) those which have a molecular weight Mw of 60,000 to 300,000.
- Mw molecular weight
- the molecular weight can be known in the art and Way by means of regulators, such as dodecyl mercaptan, during the polymerization can be set.
- the preparation of the powdered binder composition is done by mixing the powdered components in the specified mixing ratios.
- the known Devices for mixing powders are used.
- All fibers which are usually suitable, are suitable as fiber material used to reinforce fiber-reinforced plastics become. These include in particular glass fibers, polyamide fibers and carbon fibers.
- the polyamide fibers are aramid fibers prefers.
- the fiber materials can be used as single filaments or as yarns, so-called rovings, or as fleeces, tangles or scrim can be used.
- the fibers can both both individually and in the form of combinations with each other are used, for example in the form of blended yarns or blended fabrics.
- the powder composition is generally used for fiber binding in an amount of 1 to 50% by weight, preferably 4 to 15% by weight, particularly preferably 3 to 8 wt .-%, each based on the Fiber weight used.
- the molded parts or fabrics can be proceeded so that the fiber materials with the powder composition be mixed and the mixture of fiber and powder before solidification by the usual methods nonwoven technology, for example by means of an air laying, Wet laying, direct spinning or carding device becomes.
- the fiber / powder mixture can optionally be carded become.
- temperature increase preferably to 130 ° C to 250 ° C, if necessary using Pressure and / or superheated steam bound the fiber material.
- the fiber-powder mixture can still be carded if necessary, or a fiber scrim, fabric or fleece is laid out. Subsequently is the powder mixture in the laid fiber material interspersed; powder spreaders, roller application systems and electrostatic spraying methods are preferred. Then, if necessary, by increasing the temperature by means of infrared radiation source or microwave, preferably to 130 ° C to 250 ° C, if necessary using pressure and / or superheated steam, the fiber material bound.
- the pre-bonded fiber materials available in this way are suitable to manufacture fiber reinforced Plastics, which is particularly characterized by a good and characterized by rapid solubility in styrene.
- this application is used to manufacture plastic molded parts from fiber-reinforced, unsaturated polyester resins the pre-bonded fiber material designed, then with the unsaturated polyester resin soaked and finally molded the molded part,
- Another preferred area of application is solidification of glass, aramid or carbon fiber mats in the form of laid or woven fabrics, mixed beds or mixed fabrics by means of the powder composition, analogous to the process description above can be worked.
- RTM Resin Transfer Molding
- SMC Sheet Molding Composites
- a commercial polyester powder based on an unsaturated Ester A commercial polyester powder based on an unsaturated Ester.
- a commercial polyester powder based on a bisphenol A fumarate A commercial polyester powder based on a bisphenol A fumarate.
- a commercial polyester powder based on an unsaturated Bisphenol polyester is provided.
- glass rovings were statistical spread out on a carrier plate and evenly with a powder from the examples or comparative examples sprinkled.
- the powder application was 5% by weight in each case, based on the fiber weight.
- the carrier plate was used for solidification with the fiber / powder mixture for 3 minutes at 210 ° C heated, melting the powder, soaking the fibers and joined together at the crossing points.
- the received with it Fiber mats showed no discoloration.
- the fiber mats were used to test the styrene solubility cut a test specimen of size 10 x 15 cm, with 100 g weight and hung vertically in monomeric styrene dipped.
- the styrene solubility was characterized by the time span (in seconds) from the time of immersion to to tear off the fiber mat.
- the table shows that the procedure according to the invention is clear better styrene solubility is obtained than with conventional Vorbindern.
- a carbon fiber fabric was laid out, grounded and the powder from example 1 by means of electrostatic spray application in an amount of 5 wt .-%, based on fiber weight, applied.
- the mat was pre-consolidated. Then the pre-consolidated Mat in a crimping tool into a hemispherical Formed.
- the pre-bound and pre-formed scrims or fabrics were dimensionally stable and can be easily integrated without loss of shape Transfer the appropriately shaped injection tool.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Kunststoff-Formteilen aus faserverstärkten, ungesättigten Polyesterharzen oder Epoxidharzen mittels Auslegen des vorgebundenen Fasermaterials, Tränken des Fasermaterials mit dem ungesättigten Polyesterharz oder Epoxidharz und Ausformen des Formteils.The invention relates to a method for Manufacture of molded plastic parts made of fiber-reinforced, unsaturated polyester resins or epoxy resins by laying out the pre-bonded fiber material, Soak the fiber material with the unsaturated polyester resin or epoxy resin and molding the molded part.
Die Herstellung hochfester, flächiger Kunststoffteile, wie beispielsweise Automobilkarosserieteile, Bootsschalen, Flugzeugrümpfe, erfolgt bekanntlich häufig aus sogenannten ungesättigten Polyesterharzen (UP-Harzen), die mittels Glas-, Aramid- oder Kohlenstoff-Fasern mechanisch verstärkt werden. Die Fasern werden dabei in Form von Geweben, Gelegen oder vorgebundenen Fasermatten (= Vliesstoffe) eingesetzt. Beim Herstellprozeß werden die textilen Gebilde in die Formwerkzeuge drapiert und mit dem Reaktionsharz durchtränkt, wobei der in der Fasermatte vorhandene Vorbinder durch das im UP-Harz vorhandene Styrol angelöst oder aufgelöst wird. Infolgedessen verlieren die Matten ihre Eigensteifigkeit und lassen sich besser an die Werkzeugkonturen anpassen, wobei gleichzeitig das Durchtränken der Fasermatten mit dem Harz beschleunigt wird.The production of high-strength, flat plastic parts, such as for example automotive body parts, boat shells, aircraft fuselages, is known to occur frequently from so-called unsaturated Polyester resins (UP resins), which are made of glass, aramid or carbon fibers are mechanically reinforced. The Fibers are in the form of woven, laid or pre-tied Fiber mats (= nonwovens) used. In the manufacturing process the textile structures into the molds draped and impregnated with the reaction resin, the in of the fiber mat existing prebinder by the existing in the UP resin Styrene is dissolved or dissolved. Consequently the mats lose their inherent stiffness and become adapt better to the tool contours, while at the same time the impregnation of the fiber mats with the resin is accelerated becomes.
Bei dem genannten Herstellprozeß wurden bislang thermoplastische Polyesterpulver, insbesondere Polyesterpulver auf Basis von Bisphenol-A, als Vorbinder für die Fasermatten eingesetzt. Die Bisphenol-A-Polyester-Pulver werden dazu auf ein zuvor abgelegtes Glasvlies aufgestreut und bei der anschließenden Ofenfahrt aufgeschmolzen, so daß die Glasfasern an deren Kreuzungspunkten durch das geschmolzene Polymerpulver gebunden werden. Die derartig vorgebundenen Glasmatten werden dann zur Verstärkung von UP-Harzen verwendet. Nachteilig bei diesen Vorbindern ist allerdings deren, für bestimmte Anwendungen, unzureichende Löslichkeitskinetik in monomerem Styrol. So far, thermoplastic materials have been used in the production process mentioned Polyester powder, in particular polyester powder based Bisphenol-A, used as a pre-binder for the fiber mats. For this purpose, the bisphenol A polyester powder is placed on a previously deposited one Sprinkled glass fleece and at the subsequent Furnace run melted, so that the glass fibers at their crossing points bound by the molten polymer powder become. The pre-bound glass mats then become Reinforcement of UP resins used. A disadvantage of these However, the prebinder is, for certain applications, insufficient kinetics of solubility in monomeric styrene.
Ein weiterer wichtiger Anwendungsbereich für Polymerpulver ist die Vorbindung von textilen Flächengebilden zum Zweck der Formgebung von Fasermatten bevor Injektionsharz appliziert wird, beispielsweise zum Preforming vor einem RTM-Prozeß (= Resin Transfer Molding). Hier kommt es vor allem darauf an, das Ausfranzen der konfektionierten Fasermatte zu minimieren, die Formstabilität einer gegebenenfalls vorgeformten Fasermatte zu gewährleisten, und Unverträglichkeiten zwischen Preformbinder und Injektionsharz zu vermeiden.Another important area of application for polymer powder is the pre-binding of textile fabrics for the purpose of Shaping fiber mats before applying injection resin is used, for example, for preforming before an RTM process (= Resin Transfer Molding). The main thing here is to minimize the fraying of the assembled fiber mat, the dimensional stability of an optionally preformed fiber mat to ensure and incompatibility between preform binders and to avoid injection resin.
Die AU-A 36659/89 beschreibt ein Verfahren zur Herstellung von vorgebundenen Fasermaterialien bei dem Glasfasern mit zwei unterschiedlichen Längen mit einer Dreifach-Kombination als Bindemittel gebunden werden, welche styrollösliches Polyesterpulver, Polystyrolpulver und Polyvinylacetat-Dispersion enthält.AU-A 36659/89 describes a process for the production of pre-bonded fiber materials in the glass fibers with two different Lengths with a triple combination as a binder which styrene-soluble polyester powder, Contains polystyrene powder and polyvinyl acetate dispersion.
In der DE-A 2604544 werden styrollösliche Bindemittel als ungeeignete Bindemittel zur Verfestigung von Fasermaterialien beschrieben, welche mit einer Thermoplastschmelze weiterverarbeitet werden. Für diese Anwendung wird die Verwendung von Hydroxylguppen oder Carboxylgruppen enthaltenden Polyacrylaten empfohlen, welche mittels Lösemittel- oder Substanzpolymerisation hergestellt werden. Von Emulsionspolymerisaten wird explizit abgeraten, da die darin enthaltenen oberflächenaktiven Substanzen den Binder verunreinigen und zu unerwünschten Nebeneffekten wie Verfärbung oder thermischem Abbau führen können.DE-A 2604544 styrene-soluble binders are unsuitable Binder for the consolidation of fiber materials described, which is further processed with a thermoplastic melt become. For this application the use of hydroxyl groups or polyacrylates containing carboxyl groups recommended, which by means of solvent or bulk polymerization getting produced. Emulsion polymers become explicit discouraged, as the surface-active contained therein Substances contaminate the binder and lead to undesirable side effects such as discoloration or thermal degradation.
Aus der EP-A 894888 sind Textilbinder auf der Basis von carboxylfunktionellen Polymerisaten, welche in Kombination mit Epoxid- oder Isocyanat-Vernetzer eingesetzt werden, bekannt. Auf Verfahren zur Herstellung von vorgebundenen, styrollöslichen Faserformteilen wird nicht eingegangen.EP-A 894888 discloses textile binders based on carboxyl-functional ones Polymers, which in combination with Epoxy or isocyanate crosslinkers are used, known. On processes for the preparation of pre-bound, styrene-soluble Molded fiber parts are not received.
Es bestand die Aufgabe, einen pulverförmigen Vorbinder zur Verfügung zu stellen, der sich in einem styrolhaltigen UP-Harz möglichst rasch löst, aber sich auch zur Vorbindung in Prozessen eignet, bei denen vor allem die Verträglichkeit des Vorbinders mit dem Polyesterharz im Vordergrund steht.The task was to use a powdery prebinder To provide, which is in a styrene-containing UP resin resolves as quickly as possible, but also for pre-binding in processes is suitable, especially where the tolerance of the prebinder with the polyester resin in the foreground.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von faserverstärkten Kunststoffformteilen aus Reaktionsharzen wie Epoxidharzen oder ungesattigten Polyesterharzen. The invention relates to a method for Manufacture of fiber reinforced Plastic molded parts made of reactive resins such as Epoxy resins or unsaturated polyester resins.
Geeignete Mischpolymerisate sind solche auf der Basis von einem oder mehreren Monomeren aus der Gruppe umfassend Vinylester von unverzweigten oder verzweigten Alkylcarbonsäuren mit 1 bis 15 C-Atomen, Methacrylsäureester und Acrylsäureester von Alkoholen mit 1 bis 10 C-Atomen, Vinylaromaten wie Styrol und Vinylchlorid. Bevorzugte Vinylester sind Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinyl-2-ethylhexanoat, Vinyllaurat, 1-Methylvinylacetat, Vinylpivalat und Vinylester von alpha-verzweigten Monocarbonsäuren mit 5 bis 11 C-Atomen, beispielsweise VeoVa5 oder VeoVa9. Bevorzugte Methacrylsäureester oder Acrylsäureester sind Methylacrylat, Methylmethacrylat, Ethylacrylat, Ethylmethacrylat, Propylacrylat, Propylmethacrylat, n-Butylacrylat, n-Butylmethacrylat, 2-Ethylhexylacrylat.Suitable copolymers are those based on one or more monomers from the group comprising vinyl esters of unbranched or branched alkyl carboxylic acids 1 to 15 carbon atoms, methacrylic acid ester and acrylic acid ester of Alcohols with 1 to 10 carbon atoms, vinyl aromatics such as styrene and Vinyl chloride. Preferred vinyl esters are vinyl acetate, vinyl propionate, Vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate, vinyl pivalate and vinyl ester of alpha-branched Monocarboxylic acids with 5 to 11 carbon atoms, for example VeoVa5 or VeoVa9. Preferred methacrylic acid esters or acrylic acid esters are methyl acrylate, methyl methacrylate, Ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate.
Wesentlich ist, daß die Zusammensetzung des Mischpolymerisats so gewählt wird, daß eine Glastemperatur Tg oder ein Schmelzpunkt von größer 35°C, vorzugsweise von 55°C bis 150°C resultiert. Die Glasübergangstemperatur Tg und der Schmelzpunkt der Polymerisate kann in bekannter Weise mittels Differential Scanning Calorimetry (DSC) ermittelt werden. Die Tg kann auch mittels der Fox-Gleichung näherungsweise vorausberechnet werden. Nach Fox T. G., Bull. Am. Physics Soc. 1, 3, page 123 (1956) gilt: 1/Tg = x1/Tg1 + x2 /Tg2 + ... + xn/Tgn, wobei xn für den Massebruch (Gew.-%/100) des Monomers n steht, und Tgn die Glasübergangstemperatur in Grad Kelvin des Homopolymers des Monomer n ist. Tg-Werte für Homopolymerisate sind in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) aufgeführt.It is essential that the composition of the copolymer be chosen so that a glass transition temperature Tg or a melting point of greater than 35 ° C, preferably from 55 ° C to 150 ° C results. The glass transition temperature Tg and the melting point of the polymers can be determined in a known manner by means of differential scanning calorimetry (DSC). The Tg can also be roughly predicted using the Fox equation. According to Fox TG, Bull. Am. Physics Soc. 1 , 3, page 123 (1956) applies: 1 / Tg = x 1 / Tg 1 + x 2 / Tg 2 + ... + x n / Tg n , where x n for the mass fraction (% by weight / 100 ) of the monomer n, and Tg n is the glass transition temperature in degrees Kelvin of the homopolymer of the monomer n. Tg values for homopolymers are listed in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).
Bevorzugt sind Vinylester-Mischpolymerisate, Styrol-Mischpolymerisate und Acrylsäureester-Mischpolymerisate. Besonders bevorzugte Mischpolymerisate sind Vinylacetat/Ethylen-Mischpolymerisate, Vinylacetat/vinylchlorid-, Vinylacetat/VeoVa5-, Vinylacetat/VeoVa9-Mischpolymerisate, welche jeweils 0.01 bis 25 Gew.-% der genannten carboxylgruppenhaltigen Monomereinheiten enthalten, und deren Zusammensetzung so gewählt wird, daß die obengenannten Glastemperaturen Tg bzw. Schmelzpunkte resultieren. Besonders bevorzugt sind auch Methylmethacrylat/-Butylacrylat- und Styrol/Butylacrylat-Mischpolymerisate, welche jeweils 0.01 bis 25 Gew.-% der genannten carboxylgruppenhaltigen Monomereinheiten enthalten, und deren Zusammensetzung so gewählt wird, daß die obengenannten Glastemperaturen Tg bzw. Schmelzpunkte resultieren.Vinyl ester copolymers, styrene copolymers are preferred and acrylic acid ester copolymers. Especially preferred copolymers are vinyl acetate / ethylene copolymers, Vinyl acetate / vinyl chloride-, vinyl acetate / VeoVa5-, Vinyl acetate / VeoVa9 copolymers, each of 0.01 to 25% by weight of the above-mentioned monomer units containing carboxyl groups contain, and the composition of which is chosen so that the above-mentioned glass temperatures Tg or melting points result. Methyl methacrylate / butyl acrylate are also particularly preferred. and styrene / butyl acrylate copolymers, which each 0.01 to 25 wt .-% of the carboxyl-containing Contain monomer units, and their composition is chosen so that the above-mentioned glass temperatures Tg or melting points result.
Geeignete ethylenisch ungesättigte, carboxylgruppenhaltige Monomere sind ethylenisch ungesättigte Mono- oder Dicarbonsäuren wie Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure, Itaconsäure. Vorzugsweise beträgt der Gehalt an carboxylgruppen haltigen Comonomereinheiten 0.01 bis 10 Gew.-%, bezogen auf das Gesamtgewicht des Mischpolymerisats.Suitable ethylenically unsaturated monomers containing carboxyl groups are ethylenically unsaturated mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid. The content of carboxyl groups is preferably Comonomer units containing 0.01 to 10 wt .-%, based on the total weight of the copolymer.
Gegebenenfalls können die Mischpolymerisate 0.01 bis 10.0 Gew.-%, bezogen auf das Gesamtgewicht des Mischpolymerisats, noch Hilfsmonomere aus der Gruppe der ethylenisch ungesättigten Carbonsäureamide, vorzugsweise Acrylamid, aus der Gruppe der ethylenisch ungesättigten Sulfonsäuren bzw. deren Salze, vorzugsweise Vinylsulfonsäure, aus der Gruppe der mehrfach ethylenisch ungesättigten Comonomeren, beispielsweise Divinyladipat, Diallylmaleat, Allylmethacrylat oder Triallylcyanurat und/oder aus der Gruppe der N-Methylol(meth)acrylamide sowie deren Ether wie Isobutoxy- oder n-Butoxyether enthalten. In einer bevorzugten Ausführungsform enthalten die Mischpolymerisate jeweils 0.01 bis 2 Gew.-% Acrylsäure und/oder Acrylamid.If necessary, the copolymers 0.01 to 10.0 % By weight, based on the total weight of the copolymer, auxiliary monomers from the group of ethylenically unsaturated Carboxamides, preferably acrylamide, from the group the ethylenically unsaturated sulfonic acids or their salts, preferably vinyl sulfonic acid, from the group of multiple ethylenically unsaturated comonomers, for example divinyl adipate, Diallyl maleate, allyl methacrylate or triallyl cyanurate and / or from the group of N-methylol (meth) acrylamides and whose ethers such as isobutoxy or n-butoxy ether contain. In a preferred embodiment contain the copolymers each 0.01 to 2 wt .-% acrylic acid and / or acrylamide.
Die Herstellung der Mischpolymerisate erfolgt in an sich bekannter Weise nach dem Emulsionspolymerisationsverfahren in Gegenwart von Emulgator, wie beispielsweise in der WO-A 94/20661 beschrieben, deren diesbezügliche Offenbarung Teil der vorliegenden Anmeldung sein soll. Zur Herstellung der Pulver wird die dadurch erhältliche Polymerdispersion getrocknet. Die Trocknung kann mittels Sprühtrocknung, Walzentrocknung, Gefriertrocknung oder durch Koagulation der Dispersion und anschließender Wirbelschichttrocknung erfolgen. Bevorzugt werden die Sprühtrocknung und die Walzentrocknung. Bevorzugt erfolgt die Herstellung des Mischpolymerisats und dessen Trocknung ohne Zusatz von Schutzkolloid.The copolymers are prepared in a manner known per se Way after the emulsion polymerization process in Presence of emulsifier, as for example in WO-A 94/20661, the disclosure of which is part of the present application. To make the powder the resulting polymer dispersion is dried. Drying can be done by spray drying, drum drying, Freeze drying or by coagulation of the dispersion and subsequent Fluid bed drying take place. To be favoured spray drying and roller drying. Preferably done the preparation of the copolymer and its drying without Protection colloid added.
Als Vernetzer geeignet sind pulverförmige Verbindungen, welche zwei oder mehr reaktive Gruppen enthalten, die mit Carbonsäuregruppen eine kovalente Bindung eingehen, mit einem Schmelzpunkt von 40°C bis 150°C. Geeignet sind Epoxide, Isocyanate, Primide, Organohalogenverbindungen, Aziridine, Carbodiimide, Oxazoline, Alkohole, Amine, Aminosilane, Aminoformaldehyde. Bevorzugt werden Verbindungen, welche zwei oder mehr reaktive Gruppen aus der Gruppe der Epoxide, Isocyanate oder Primide enthalten.Suitable crosslinkers are powdered compounds which contain two or more reactive groups with carboxylic acid groups form a covalent bond with a melting point from 40 ° C to 150 ° C. Epoxides, isocyanates, Primides, organohalogen compounds, aziridines, carbodiimides, Oxazolines, alcohols, amines, aminosilanes, aminoformaldehydes. Compounds which are two or more reactive are preferred Groups from the group of epoxides, isocyanates or primides contain.
Beispiele für geeignete Epoxidvernetzer sind solche vom Bisphenol-A-Typ, das heißt Kondensationsprodukte von Bisphenol-A und Epichlorhydrin oder Methylepichlorhydrin. Derartige Epoxidvernetzer sind im Handel, beispielsweise unter den Handelsnamen Epicote oder Eurepox, erhältlich. Geeignete Diisocyanate sind ebenfalls gängige Handelsprodukte, beispielsweise m-Tetramethylxylen-Diisocyanat (TMXDI), Methylendiphenyl-Diisocyanat (MDI). Der Gehalt an Vernetzer beträgt im allgemeinen von 0.1 bis 25 Gew.-%, vorzugsweise von 4 bis 12 Gew.-%, bezogen auf das pulverförmige Mischpolymerisat.Examples of suitable epoxy crosslinkers are those from Bisphenol A type, that is, condensation products of bisphenol A and epichlorohydrin or methylepichlorohydrin. such Epoxy crosslinkers are commercially available, for example under the trade names Epicote or Eurepox available. Suitable diisocyanates are also common commercial products, for example m-tetramethylxylene diisocyanate (TMXDI), methylene diphenyl diisocyanate (MDI). The crosslinker content is generally from 0.1 to 25% by weight, preferably from 4 to 12% by weight, based on the powdery copolymer.
Üblicherweise werden Kombinationen aus dem Mischpolymerisat a) und dem Vernetzer b) eingesetzt. Dies gilt vor allem für Anwendungen in den hohe mechanische Festigkeit gefordert wird. In Anwendungen dagegen, wo die Styrollöslichkeit im Vordergrund steht kann auch ohne Vernetzerzusatz gearbeitet werden.Combinations of the copolymer a) are usually and the crosslinker b) used. This is especially true for applications in which high mechanical strength is required. In contrast, in applications where the styrene solubility is paramount can also be used without the addition of a crosslinker.
In einer bevorzugten Ausführungsform enthält die pulverförmige Bindemittel-Zusammensetzung noch einen Vernetzungskatalysator auf der Basis von organischen Verbindungen, welche quarternäre Gruppen von Elementen der 5. Hauptgruppe des PSE enthalten. Bevorzugt sind pulverförmige Katalysatoren, welche sich von Triphenylphosphonium-Halogeniden oder quarternären Ammoniumverbindungen ableiten. Beispiele hierfür sind Methyl-, Ethyl-, Propyl-, Butyl-Triphenylphosphonium-Bromid bzw. die entsprechenden Iodide und Chloride. Geeignet sind auch Triphenylphosphonium-Halogenide mit substituiertem Alkylrest wie 2-Carboxyethyl-, 3-Bromopropyl- oder Formylmethyl-Triphenylphosphoniumbromid. Geeignete quarternäre Ammoniumverbindungen sind Tetrabutylammonium-, Benzyltrimethylammonium-, Methyltributylammonium-Salze. Die genannten Verbindungen sind im Handel erhältlich und werden vorzugsweise in Mengen von 0.1 bis 5 Gew%, bezogen auf das pulverförmige Mischpolymerisat, eingesetzt.In a preferred embodiment, the powdered Binder composition still a crosslinking catalyst based on organic compounds, which are quaternary Groups of elements of the 5th main group of the PSE included. Powdered catalysts are preferred, which differ from Triphenylphosphonium halides or quaternary ammonium compounds derived. Examples include methyl, ethyl, Propyl, butyl triphenylphosphonium bromide or the corresponding Iodides and chlorides. Triphenylphosphonium halides are also suitable with substituted alkyl radical such as 2-carboxyethyl, 3-bromopropyl or formylmethyl triphenylphosphonium bromide. Suitable quaternary ammonium compounds are tetrabutylammonium, Benzyltrimethylammonium, methyltributylammonium salts. The compounds mentioned are commercially available and are preferably obtained in amounts of 0.1 to 5% by weight on the powdery copolymer, used.
In Anwendungen, in denen es auf die Schmelzflußcharakteristik ankommt, haben sich als Polymerisate a) solche bewährt, welche ein Molekulargwicht Mw von 60000 bis 300000 aufweisen. Das Molekulargewicht kann dabei in dem Fachmann bekannter Art und Weise mittels Reglern, wie Dodecylmercaptan, während der Polymerisation eingestellt werden.In applications where it depends on the melt flow characteristics arrives, have proven as polymers a) those which have a molecular weight Mw of 60,000 to 300,000. The molecular weight can be known in the art and Way by means of regulators, such as dodecyl mercaptan, during the polymerization can be set.
Die Herstellung der pulverförmigen Bindemittel-Zusammensetzung erfolgt durch Vermischen der pulverförmigen Komponenten in den angegebenen Mischungsverhältnissen. Hierzu können die bekannten Vorrichtungen zur Mischung von Pulvern eingesetzt werden.The preparation of the powdered binder composition is done by mixing the powdered components in the specified mixing ratios. For this, the known Devices for mixing powders are used.
Als Fasermaterial sind alle Fasern geeignet, die üblicherweise zur Verstärkung von faserverstärkten Kunststoffen herangezogen werden. Dazu zählen insbesondere Glasfasern, Polyamidfasern und Kohlenstoff-Fasern. Bei den Polyamidfasern werden Aramidfasern bevorzugt. Die Fasermaterialien können als Einzelfilamente oder als Garne, sogenannte Rovings, oder als Vliese, Gewirre oder Gelege eingesetzt werden. Die Fasern können sowohl jeweils für sich als auch in Form von Kombinationen untereinander eingesetzt werden, beispielsweise in Form von Mischgarnen oder Mischgeweben.All fibers, which are usually suitable, are suitable as fiber material used to reinforce fiber-reinforced plastics become. These include in particular glass fibers, polyamide fibers and carbon fibers. The polyamide fibers are aramid fibers prefers. The fiber materials can be used as single filaments or as yarns, so-called rovings, or as fleeces, tangles or scrim can be used. The fibers can both both individually and in the form of combinations with each other are used, for example in the form of blended yarns or blended fabrics.
Zur Faserbindung wird die Pulverzusammensetzung im allgemeinen in einer Menge von 1 bis 50 Gew.-%, bevorzugt 4 bis 15 Gew.-%, besonders bevorzugt 3 bis 8 Gew.-%, jeweils bezogen auf das Fasergewicht eingesetzt. The powder composition is generally used for fiber binding in an amount of 1 to 50% by weight, preferably 4 to 15% by weight, particularly preferably 3 to 8 wt .-%, each based on the Fiber weight used.
Zur Herstellung der Formteile oder Flächengebilde kann dabei so vorgegangen werden, daß die Fasermaterialien mit der Pulverzusammensetzung vermischt werden und das Gemisch aus Faser und Pulver vor der Verfestigung mittels der üblichen Verfahren der Nonwoven-Technologie, beispielsweise mittels einer Luftlege-, Naßlege-, Direktspinn- oder Krempelvorrichtung, ausgelegt wird. Gegebenenfalls kann die Faser/Pulver-Mischung kardiert werden. Anschließend wird mittels Temperaturerhöhung, vorzugsweise auf 130°C bis 250°C, gegebenenfalls unter Anwendung von Druck und/oder Heißdampf das Fasermaterial gebunden.It can be used to manufacture the molded parts or fabrics be proceeded so that the fiber materials with the powder composition be mixed and the mixture of fiber and powder before solidification by the usual methods nonwoven technology, for example by means of an air laying, Wet laying, direct spinning or carding device becomes. The fiber / powder mixture can optionally be carded become. Then by means of temperature increase, preferably to 130 ° C to 250 ° C, if necessary using Pressure and / or superheated steam bound the fiber material.
Es kann auch so vorgegangen werden, daß vor der Verfestigung die Fasern flächenhaft ausgebreitet werden, wobei die Faser-Pulver-Mischung gegebenenfalls noch kardiert werden kann, oder ein Faser-Gelege, -Gewebe oder -Vlies ausgelegt wird. Anschließend wird die Pulvermischung in das ausgelegte Fasermaterial eingestreut; dabei werden Pulverstreuer, Walzenauftragssysteme und elektrostatische Sprühverfahren bevorzugt. Anschließend wird mittels Temperaturerhöhung, gegebenenfalls mittels Infrarotstrahlungsquelle oder Mikrowelle, vorzugsweise auf 130°C bis 250°C, gegebenenfalls unter Anwendung von Druck und/oder Heißdampf, das Fasermaterial gebunden.It can also be done so that before solidification the fibers are spread out area-wide, the fiber-powder mixture can still be carded if necessary, or a fiber scrim, fabric or fleece is laid out. Subsequently is the powder mixture in the laid fiber material interspersed; powder spreaders, roller application systems and electrostatic spraying methods are preferred. Then, if necessary, by increasing the temperature by means of infrared radiation source or microwave, preferably to 130 ° C to 250 ° C, if necessary using pressure and / or superheated steam, the fiber material bound.
Die dadurch erhältlichen, vorgebundenen Fasermaterialien eignen sich zur Herstellung von faserverstärkten Kunststoffen, welches sich insbesondere durch eine gute und rasche Löslichkeit in Styrol auszeichnet. Bei dieser Anwendung wird zur Herstellung von Kunststoff-Formteilen aus faserverstärkten, ungesättigten Polyesterharzen das vorgebundene Fasermaterial ausgelegt, anschließend mit dem ungesättigten Polyesterharz getränkt und schließlich das Formteil ausgeformt,The pre-bonded fiber materials available in this way are suitable to manufacture fiber reinforced Plastics, which is particularly characterized by a good and characterized by rapid solubility in styrene. In this application is used to manufacture plastic molded parts from fiber-reinforced, unsaturated polyester resins the pre-bonded fiber material designed, then with the unsaturated polyester resin soaked and finally molded the molded part,
Ein weiterer bevorzugter Anwendungsbereich ist die Verfestigung von Glas-, Aramid- oder Kohlenstoff-Fasermatten in Form von Gelegen oder Geweben, Mischgelegen oder Mischgeweben mittels der Pulverzusammensetzung, wobei analog der obigen Verfahrensbeschreibung gearbeitet werden kann. Die damit erhältlichen, vorgebundenen Fasermaterialien werden beispielsweise zur Herstellung von faserverstärkten, epoxidgebundenen RTM-Formteilen (RTM = Resin Transfer Molding) oder SMC-Formteilen (SMC = Sheet Molding Composites) eingesetzt. Zur Herstellung von vorgeformten Flächengebilden ("preforming") kann das vorgebundene Fasermaterial in einem geeigneten Formwerkzeug, gegebenenfalls unter Anwendung von erhöhter Temperatur und Druck geformt werden.Another preferred area of application is solidification of glass, aramid or carbon fiber mats in the form of laid or woven fabrics, mixed beds or mixed fabrics by means of the powder composition, analogous to the process description above can be worked. The available pre-bonded fiber materials are, for example for the production of fiber-reinforced, epoxy-bonded RTM molded parts (RTM = Resin Transfer Molding) or SMC molded parts (SMC = Sheet Molding Composites). For the production of preformed fabrics ("preforming") can the pre-bound Fiber material in a suitable mold, if necessary using elevated temperature and pressure be shaped.
Die nachfolgenden Beispiele dienen der weiteren Erläuterung der Erfindung.The following examples serve for further explanation the invention.
Herstellung eines carbonsäuregruppenhaltigen Polymerpulvers:
In einem Reaktor mit 3 Liter Volumen wurden 838.8 g deionisiertes
Wasser und 6.7 g Natriumlaurylsulfat vorgelegt und unter
Stickstoff und Rühren auf 80°C aufgeheizt. Bei dieser Temperatur
wurde die Initiatorlösung (6.7 g Kaliumperoxodisulfat
und 218.4 g Wasser) in den Reaktor gegeben und aus separaten
Behältern wurden innerhalb von 4 Stunden folgende Zusammensetzungen
in den Reaktor zudosiert:
838.8 g of deionized water and 6.7 g of sodium lauryl sulfate were placed in a reactor with a volume of 3 liters and heated to 80 ° C. with nitrogen and stirring. At this temperature, the initiator solution (6.7 g of potassium peroxodisulfate and 218.4 g of water) was added to the reactor and the following compositions were metered into the reactor over the course of 4 hours from separate containers:
Herstellung eines carbonsäuregruppenhaltigen Polymerpulvers:
In einem Reaktor mit 3 Liter Volumen wurden 855 g deionisiertes
Wasser und 6.7 g Natriumlaurylsulfat vorgelegt und unter
Stickstoff und Rühren auf 80°C aufgeheizt. Bei dieser Températur
wurde die Initiatorlösung (6.7 g Kaliumperoxodisulfat und
217.4 g Wasser) in den Reaktor gegeben und aus separaten Behältern
wurden innerhalb von 4 Stunden folgende Zusammensetzungen
in den Reaktor zudosiert:
855 g of deionized water and 6.7 g of sodium lauryl sulfate were placed in a reactor with a volume of 3 liters and heated to 80 ° C. with nitrogen and stirring. At this temperature, the initiator solution (6.7 g of potassium peroxodisulfate and 217.4 g of water) was added to the reactor and the following compositions were metered into the reactor from separate containers within 4 hours:
Herstellung der Pulvermischung: 98 g des carbonsäuregruppenhaltigen Polymerpulvers aus Beispiel 1 wurde in einem Pulvermischer mit 2 g einer pulverförmigen, multifunktionellen Epoxidverbindung vermischt.Production of the powder mixture: 98 g of the polymer powder containing carboxylic acid groups from Example 1 was in a powder mixer with 2 g of a powder, multifunctional epoxy compound mixed.
Herstellung der Pulvermischung: 98 g des carbonsäuregruppenhaltigen Polymerpulvers aus Beispiel 2 wurde in einem Pulvermischer mit 2 g einer pulverförmigen, multifunktionellen Epoxidverbindung vermischt.Production of the powder mixture: 98 g of the polymer powder containing carboxylic acid groups from Example 2 was in a powder mixer with 2 g of a powdery, multifunctional epoxy compound mixed.
Ein kommerzielles Polyesterpulver auf Basis eines ungesättigten Esters.A commercial polyester powder based on an unsaturated Ester.
Ein kommerzielles Polyesterpulver auf Basis eines Bisphenol-A-Fumarats.A commercial polyester powder based on a bisphenol A fumarate.
Ein kommerzielles Polyesterpulver auf Basis eines ungesättigten Bisphenol-Polyesters.A commercial polyester powder based on an unsaturated Bisphenol polyester.
Zur Herstellung einer Glasfasermatte wurden Glasrovings statistisch auf einer Trägerplatte ausgebreitet und jeweils gleichmäßig mit einem Pulver aus den Beispielen bzw. Vergleichsbeispielen bestreut. Der Pulverauftrag betrug jeweils 5 Gew.-%, bezogen auf das Fasergewicht. Zur Verfestigung wurde die Trägerplatte mit dem Faser/Pulver-Gemisch für 3 Minuten auf 210°C erhitzt, wobei das Pulver schmolz, die Fasern durchtränkte und an den Kreuzungspunkten miteinander verband. Die damit erhaltenen Fasermatten zeigten keine Verfärbung.To produce a glass fiber mat, glass rovings were statistical spread out on a carrier plate and evenly with a powder from the examples or comparative examples sprinkled. The powder application was 5% by weight in each case, based on the fiber weight. The carrier plate was used for solidification with the fiber / powder mixture for 3 minutes at 210 ° C heated, melting the powder, soaking the fibers and joined together at the crossing points. The received with it Fiber mats showed no discoloration.
Zur Prüfung der Styrollöslichkeit wurden die Fasermatten auf einen Prüfkörper der Größe 10 x 15 cm zurechtgeschnitten, mit einem 100 g Gewicht behängt und vertikal in monomeres Styrol getaucht. Die Styrollöslichkeit wurde charakterisiert durch die Zeitspanne (in Sekunden) vom Zeitpunkt des Eintauchens bis zum Abreißen der Fasermatte.The fiber mats were used to test the styrene solubility cut a test specimen of size 10 x 15 cm, with 100 g weight and hung vertically in monomeric styrene dipped. The styrene solubility was characterized by the time span (in seconds) from the time of immersion to to tear off the fiber mat.
Die Ergebnisse der anwendungstechnischen Prüfung sind in Tabelle
1 zusammengefaßt.
Die Tabelle zeigt, daß bei erfindungsgemäßem Vorgehen deutlich bessere Styrollöslichkeit erhalten wird als mit herkömmlichen Vorbindern.The table shows that the procedure according to the invention is clear better styrene solubility is obtained than with conventional Vorbindern.
Es wurde ein Kohlefasergelege ausgelegt, geerdet und das Pulver aus Beispiel 1 mittels elektrostatischem Sprühauftrag in einer Menge von 5 Gew.-%, bezogen auf Fasergewicht, aufgebracht. In einer anschließenden Ofenfahrt bei 150°C/20 sec wurde die Matte vorverfestigt. Anschließend wurde die vorverfestigte Matte in einem Preßwerkzeug in eine halbkugelförmige Form gebracht.A carbon fiber fabric was laid out, grounded and the powder from example 1 by means of electrostatic spray application in an amount of 5 wt .-%, based on fiber weight, applied. In a subsequent oven run at 150 ° C / 20 sec the mat was pre-consolidated. Then the pre-consolidated Mat in a crimping tool into a hemispherical Formed.
Dieser Versuch wurde mit dem Pulver aus Beispiel 3 wiederholt, wobei anstelle von einem Kohlefasergelege ein Glasfasergewebe eingesetzt worden ist.This experiment was repeated with the powder from Example 3, with a glass fiber fabric instead of a carbon fiber fabric has been used.
Die vorgebundenen und vorgeformten Gelege bzw. Gewebe waren formstabil und ließen sich problemlos ohne Formverlust in ein entsprechend geformtes Injektionswerkzeug überführen.The pre-bound and pre-formed scrims or fabrics were dimensionally stable and can be easily integrated without loss of shape Transfer the appropriately shaped injection tool.
Claims (7)
- Process for producing plastics mouldings, which comprises a first step of mixing a pulverulent binder composition comprisinga) a pulverulent interpolymer, obtainable by emulsion polymerization and subsequent drying, of one or more monomers from the group consisting of vinyl esters, acrylic esters, methacrylic esters, vinylaromatics and vinyl chloride and 0.01 to 25% by weight, based on the total weight of the interpolymer, of one or more ethylenically unsaturated carboxyl-containing monomers, the interpolymer having a glass transition temperature Tg or a melting point of above 35°C, and optionallyb) at least one pulverulent compound containing at least two reactive groups capable of reaction with the carboxyl groups mentioned under a), and having a melting point of 35°C to 150°C,
or sprinkling the pulverulent binder on the spread-out fibre material and then binding the fibre material by raising the temperature to 50°C to 250°C,
and a second step of laying up the prebound fibre material, saturating said fibre material with unsaturated styrene-containing polyester resin or with epoxy resin, and forming the plastics moulding. - Process according to Claim 1, characterized in that the interpolymer used is selected from vinyl acetate-ethylene, vinyl acetate-vinyl chloride, vinyl acetate-VeoVa5, vinyl acetate-VeoVa9, methyl methacrylate-butyl acrylate and styrene/butyl acrylate interpolymers which each contain 0.01 to 25% by weight of carboxyl-containing monomer units.
- Process according to Claim 1 or 2, characterized in that said one or more ethylenically unsaturated carboxyl-containing monomers are selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid.
- Process according to any of Claims 1 to 3, characterized in that the one or more pulverulent compounds containing two or more reactive groups are selected from the group consisting of epoxides, isocyanates, Primids, organohalogens, aziridines, carbodiimides, oxazolines, alcohols, amines, aminosilanes and aminoformaldehydes.
- Process according to any of Claims 1 to 4, characterized in that the fibre material used is glass fibre, polyamide fibre or carbon fibre.
- Process according to any of Claims 1 to 5, which comprises the prebound fibre material also being preformed.
- Process according to Claim 6, which comprises the prebound fibre material being formed in a suitable mould, if necessary by the application of heat and pressure.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19959415 | 1999-12-09 | ||
DE19959415A DE19959415C2 (en) | 1999-12-09 | 1999-12-09 | Process for pre-bonding fiber materials |
Publications (2)
Publication Number | Publication Date |
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EP1106724A1 EP1106724A1 (en) | 2001-06-13 |
EP1106724B1 true EP1106724B1 (en) | 2003-07-30 |
Family
ID=7932026
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP20000124328 Expired - Lifetime EP1106724B1 (en) | 1999-12-09 | 2000-11-16 | Process for pre-binding fibrous materials |
Country Status (3)
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US (1) | US6472462B1 (en) |
EP (1) | EP1106724B1 (en) |
DE (2) | DE19959415C2 (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10161773A1 (en) * | 2001-12-15 | 2003-06-26 | Bayerische Motoren Werke Ag | Method for producing a three-dimensionally shaped fiber composite plastic component |
FR2836935B1 (en) * | 2002-03-07 | 2012-06-08 | Chomarat Composites | NEW REINFORCEMENT COMPLEX |
EP1413669B1 (en) * | 2002-10-21 | 2008-02-13 | Bamberger Kaliko GmbH | Water resistant, PVC-free flat textile material |
EP1413668A1 (en) * | 2002-10-21 | 2004-04-28 | Bamberger Kaliko GmbH | Weather resistant, PVC-free flat textile material |
DE10258441A1 (en) * | 2002-12-13 | 2004-06-24 | Basf Ag | Powdery, formaldehyde-free binder composition and its use for the thermal curing of substrates |
US20070026754A1 (en) * | 2003-04-25 | 2007-02-01 | Carmen Martin Rivera | Scouring material |
US20050239362A1 (en) * | 2004-04-23 | 2005-10-27 | Goldstein Joel E | Nonwoven binders with high wet/dry tensile strength ratio |
CA2561248A1 (en) | 2005-10-12 | 2007-04-12 | Rohm And Haas Company | Composite materials and methods of making the same |
US20080175997A1 (en) * | 2007-01-19 | 2008-07-24 | Goldstein Joel E | Emulsion polymer binder with azirdine crosslinking agent for glass fiber webs |
GB0818186D0 (en) * | 2008-10-06 | 2008-11-12 | 3M Innovative Properties Co | Scouring material comprising natural fibres |
DE102009010938A1 (en) * | 2009-02-27 | 2010-09-09 | Celanese Emulsions Gmbh | Mineral wool fiber mats, process for their preparation and use |
DE102011012654A1 (en) | 2011-02-28 | 2012-08-30 | Benteler Sgl Gmbh & Co. Kg | Process for producing a leaf spring as a fiber composite component and leaf spring |
WO2015051514A1 (en) * | 2013-10-10 | 2015-04-16 | Rohm And Haas Company | Coating composition with improved liquid stain repellency |
CN105579534B (en) | 2013-10-10 | 2019-04-02 | 罗门哈斯公司 | Coating composition with improved liquid stain fastness with and preparation method thereof |
BR112016005851B1 (en) * | 2013-10-10 | 2021-11-23 | Rohm And Haas Company | BINDER COMPOSITION AND PREPARED COATING COMPOSITION |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US4054713A (en) | 1973-12-28 | 1977-10-18 | Kao Soap Co., Ltd. | Process for preparing glass fiber mats |
DE2604544A1 (en) | 1976-02-06 | 1977-08-11 | Basf Ag | BINDING AGENT FOR STRENGTHENING GLASS FIBER MATS |
DE4306808A1 (en) | 1993-03-04 | 1994-09-08 | Wacker Chemie Gmbh | Crosslinkable dispersion powder as a binder for fibers |
DE19733133A1 (en) * | 1997-07-31 | 1999-02-04 | Wacker Chemie Gmbh | Powdery, crosslinkable textile binder composition |
-
1999
- 1999-12-09 DE DE19959415A patent/DE19959415C2/en not_active Expired - Fee Related
-
2000
- 2000-11-06 US US09/707,649 patent/US6472462B1/en not_active Expired - Fee Related
- 2000-11-16 DE DE50003093T patent/DE50003093D1/en not_active Expired - Lifetime
- 2000-11-16 EP EP20000124328 patent/EP1106724B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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DE19959415A1 (en) | 2001-06-21 |
US6472462B1 (en) | 2002-10-29 |
DE19959415C2 (en) | 2002-03-07 |
EP1106724A1 (en) | 2001-06-13 |
DE50003093D1 (en) | 2003-09-04 |
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