EP1106724A1 - Verfahren zur Vorbindung von Fasermaterialien - Google Patents
Verfahren zur Vorbindung von Fasermaterialien Download PDFInfo
- Publication number
- EP1106724A1 EP1106724A1 EP00124328A EP00124328A EP1106724A1 EP 1106724 A1 EP1106724 A1 EP 1106724A1 EP 00124328 A EP00124328 A EP 00124328A EP 00124328 A EP00124328 A EP 00124328A EP 1106724 A1 EP1106724 A1 EP 1106724A1
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- EP
- European Patent Office
- Prior art keywords
- fiber
- fiber material
- bound
- vinyl
- fiber materials
- 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.)
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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
-
- 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
-
- 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 prebinding fiber materials by means of a powdered binder composition.
- the invention further relates to the use of the prebound Fiber material for the production 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 rigidity 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 melted 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 Solves as quickly as possible, but also for pre-binding in processes is suitable, especially for the compatibility of the previous binder with the polyester resin in the foreground.
- Another object of the invention is the use of pre-bonded fiber materials for the production of plastic molded parts made of fiber-reinforced, unsaturated polyester resins by laying out the pre-bound fiber material, Soak the fiber material with the unsaturated polyester resin and molding the molded part.
- Another object of the invention is the use of pre-bonded fiber material for the production of preformed Preforming and the use of these preformed Fiber materials for the production of fiber reinforced Plastic molded parts made of reactive resins such as Epoxy 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 is 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, carboxyl group-containing monomers 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 according to 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, i.e. 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).
- TXDI m-tetramethylxylene diisocyanate
- MDI methylene diphenyl diisocyanate
- the crosslinker content is in general 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 styrene solubility is paramount can also be used without the addition of a crosslinker.
- the powder contains 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.
- 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 are customary as fiber material, usually 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 one another 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 to 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.
- the powder mixture into the laid fiber material interspersed; powder spreaders, roller application systems and electrostatic spraying methods are preferred.
- 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 itself as a semi-finished product for the production of 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
- Monomer dosage 2 with 67.3 g water, 44.9 g acrylamide (30%).
- Initiator dosage with 217.6 g water and 6.7 g potassium peroxodisulfate. After the metered additions, the polymerization was continued at 80 ° C. for about 2 hours. After cooling and adjusting the pH to 8 using ammonia, the dispersion was spray-dried. The glass temperature of this product was 59 ° C.
- Monomer dosage 2 with 67.3 g water and 28.0 g N-methylolacrylamide (48%).
- Initiator dosage with 217.4 g water and 6.6 g potassium peroxodisulfate. After the metering, the polymerization was continued at 80 ° C. for about 2 hours. After cooling and adjusting the pH to 8 using ammonia, the dispersion was spray-dried. The glass temperature of this product was 59 ° C.
- a commercial polyester powder based on an unsaturated Esters A commercial polyester powder based on an unsaturated Esters.
- 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 used to produce a glass fiber mat 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 so obtained Fiber mats showed no discoloration.
- the table shows that the procedure according to the invention is clear better styrene solubility is obtained than with conventional Preliminary ties.
- 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)
Abstract
Description
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:
Monomerdosierung 1 mit 67.3 g Methacrylsäure, 403.7 g Butylacrylat, 861.3 g Styrol und 6.7 g Dodecylmercaptan. Monomerdosierung 2 mit 67.3 g Wasser, 44.9 g Acrylamid (30 %). Initiatordosierung mit 217.6 g Wasser und 6.7 g Kaliumperoxodisulfat.
Nach den Dosierungen wurde ca. 2 Stunden bei 80°C nachpolymerisiert. Nach dem Abkühlen und dem Einstellen des pH-Wertes auf 8 mittels Ammoniak wurde die Dispersion sprühgetrocknet. Die Glastemperatur dieses Produktes lag bei 59°C.
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 Temperatur 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:
Monomerdosierung 1 mit 67.2 g Methacrylsäure, 403.4 g Butylacrylat, 860.5 g Styrol, 6.7 g Dodecylmercaptan. Monomerdosierung 2 mit 67.3 g Wasser und 28.0 g N-Methylolacrylamid (48 %).
Initiatordosierung mit 217.4 g Wasser und 6.6 g Kaliumperoxodisulfat.
Nach den Dosierungen wurde ca. 2 Stunden bei 80°C nachpolymerisiert. Nach dem Abkühlen und dem Einstellen des pH-Wertes auf 8 mittels Ammoniak wurde die Dispersion sprühgetrocknet. Die Glastemperatur dieses Produktes lag bei 59°C.
98 g des carbonsäuregruppenhaltigen Polymerpulvers aus Beispiel 1 wurde in einem Pulvermischer mit 2 g einer pulverförmigen, multifunktionellen Epoxidverbindung vermischt.
98 g des carbonsäuregruppenhaltigen Polymerpulvers aus Beispiel 2 wurde in einem Pulvermischer mit 2 g einer pulverförmigen, multifunktionellen Epoxidverbindung vermischt.
Die Ergebnisse der anwendungstechnischen Prüfung sind in Tabelle 1 zusammengefaßt.
Vorbinder | Styrollöslichkeit [s] |
Beispiel 1 | 8 |
Beispiel 2 | 12 |
Beispiel 3 | 13 |
Beispiel 4 | 14 |
Vergleichsbeispiel 5 | 130 |
Vergleichsbeispiel 6 | 31 |
Vergleichsbeispiel 7 | 34 |
Claims (12)
- Verfahren zur Vorbindung von Fasermaterialien wobei eine pulverförmigen Bindemittel-Zusammensetzung enthaltenda) ein pulverförmiges Mischpolymerisat, erhältlich durch Emulsionspolymerisation und anschließende Trocknung, von einem oder mehreren Monomeren aus der Gruppe umfassend Vinylester, Acrylsäureester, Methacrylsäureester, Vinylaromaten und Vinylchlorid und von 0.01 bis 25 Gew.-%, bezogen auf das Gesamtgewicht des Mischpolymerisats, von einem oder mehreren ethylenisch ungesättigten, carboxylgruppenhaltigen Monomeren, wobei das Mischpolymerisat eine Glastemperatur Tg oder einen Schmelzpunkt von größer 35°C und gegebenenfallsb) mindestens eine pulverförmige Verbindung, welche mindestens zwei reaktive Gruppen aufweist, die mit den unter a) genannten Carboxylgruppen reagieren können, und einen Schmelzpunkt von 35°C bis 150°C aufweist, mit dem Fasermaterial vermischt und ausgebreitet wird, oder das pulverförmige Bindemittel auf das ausgebreitete Fasermaterial aufgestreut wird, und anschließend das Fasermaterial mittels Temperaturerhöhung auf 50°C bis 250°C gebunden wird.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Mischpolymerisat Vinylacetat-Ethylen, Vinylacetat-Vinylchlorid-, Vinylacetat-VeoVa5-,Vinylacetat-VeoVa9-, Methylmethacrylat-Butylacrylat-, Styrol/Butylacrylat-Mischpolymerisate, welche jeweils 0.01 bis 25 Gew.-% carboxylgruppenhaltige Monomereinheiten enthalten, eingesetzt werden.
- Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß als ethylenisch ungesättigte, carboxylgruppenhaltige Monomere ein oder mehrere Monomere aus der Gruppe Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure, Itaconsäure copolymerisiert werden.
- Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß als pulverförmige Verbindung, welche zwei oder mehr reaktive Gruppen enthalten, ein oder mehrere aus der Gruppe umfassend Epoxide, Isocyanate, Primide, Organohalogenverbindungen, Aziridine, Carbodiimide, Oxazoline, Alkohole, Amine, Aminosilane, Aminoformaldehyde, eingesetzt werden.
- Verfahren nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß als Fasermaterial Glasfasern, Polyamidfasern oder Kohlenstoff-Fasern eingesetzt werden.
- Vorgebundene Fasermaterialien erhältlich mit einem Verfahren gemäß einem der Ansprüche 1 bis 5.
- Verwendung der vorgebundenen Fasermaterialien gemäß Anspruch 6 zur Herstellung von Kunststoff-Formteilen aus faserverstärkten, ungesättigten Polyesterharzen mittels Auslegen des vorgebundenen Fasermaterials, Tränken des Fasermaterials mit dem ungesättigten Polyesterharz und Ausformen des Formteils.
- Verwendung der vorgebundenen Fasermaterialien gemäß Anspruch 6 zur Herstellung von Kunststoff-Formteilen aus faserverstärkten, Epoxidharzen mittels Auslegen des vorgebundenen und gegebenenfalls auch vorgeformten Fasermaterials, Tränken des Fasermaterials mit dem Epoxidharz und Ausformen des Formteils.
- Verwendung der vorgebundenen Fasermaterialien gemäß Anspruch 6, wobei das vorgebundene Fasermaterial in einem geeigneten Formwerkzeug, gegebenenfalls unter Anwendung von Temperatur und Druck geformt wird und nach Tränken mit einem Epoxidharz zu einem Kunststoff-Formteil verarbeitet wird.
- Verwendung der vorgebundenen Fasermaterialien gemäß Anspruch 6 zur Herstellung von RTM-Formteilen.
- Verwendung der vorgebundenen Fasermaterialien gemäß Anspruch 6 zur Herstellung von SMC-Formteilen.
- Formteile erhältlich gemäß der Verwendung nach Anspruch 6 bis 11.
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DE19959415 | 1999-12-09 | ||
DE19959415A DE19959415C2 (de) | 1999-12-09 | 1999-12-09 | Verfahren zur Vorbindung von Fasermaterialien |
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EP1106724A1 true EP1106724A1 (de) | 2001-06-13 |
EP1106724B1 EP1106724B1 (de) | 2003-07-30 |
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EP20000124328 Expired - Lifetime EP1106724B1 (de) | 1999-12-09 | 2000-11-16 | Verfahren zur Vorbindung von Fasermaterialien |
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US (1) | US6472462B1 (de) |
EP (1) | EP1106724B1 (de) |
DE (2) | DE19959415C2 (de) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1348791A1 (de) * | 2002-03-07 | 2003-10-01 | Chomarat Composites | Verstärkungsstruktur |
EP1413669A1 (de) * | 2002-10-21 | 2004-04-28 | Bamberger Kaliko GmbH | Witterungsbeständige, PVC-freie Flächenmaterialien auf Textilbasis |
EP1413668A1 (de) * | 2002-10-21 | 2004-04-28 | Bamberger Kaliko GmbH | Witterungsbeständige, PVC-freie Flächenmaterialien auf Textilbasis |
EP1775371A1 (de) * | 2005-10-12 | 2007-04-18 | Rohm and Haas Company | Verbundmaterialien und deren Herstellung |
WO2008088545A1 (en) * | 2007-01-19 | 2008-07-24 | Celanese International Corporation | Emulsion polymer binder with aziridine crosslinking agent for mineral fiber webs |
WO2010097192A3 (de) * | 2009-02-27 | 2010-11-18 | Celanese Emulsions Gmbh | Mineralwollfasermatten, verfahren zu deren herstellung und verwendung |
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DE10161773A1 (de) * | 2001-12-15 | 2003-06-26 | Bayerische Motoren Werke Ag | Verfahren zur Herstellung eines dreidimensional geformten Faserverbundkunststoffbauteils |
DE10258441A1 (de) * | 2002-12-13 | 2004-06-24 | Basf Ag | Pulverförmige, formaldehydfreie Bindemittelzusammensetzung und deren Anwendung zum thermischen Härten von Substraten |
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 |
GB0818186D0 (en) * | 2008-10-06 | 2008-11-12 | 3M Innovative Properties Co | Scouring material comprising natural fibres |
DE102011012654A1 (de) | 2011-02-28 | 2012-08-30 | Benteler Sgl Gmbh & Co. Kg | Verfahren zur Herstellung einer Blattfeder als Faserverbundbauteil sowie Blattfeder |
AU2013402859C1 (en) * | 2013-10-10 | 2019-01-24 | Rohm And Haas Company | Coating composition with improved liquid stain repellency |
EP3055368B1 (de) | 2013-10-10 | 2019-08-14 | Rohm and Haas Company | Beschichtungszusammensetzung mit verbessertem flüssigkeitsfleckenabweisung und verfahren zur herstellung davon |
CA2926150C (en) | 2013-10-10 | 2021-02-16 | Rohm And Haas Company | Binder composition and coating composition made thereof |
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- 2000-11-06 US US09/707,649 patent/US6472462B1/en not_active Expired - Fee Related
- 2000-11-16 DE DE50003093T patent/DE50003093D1/de not_active Expired - Lifetime
- 2000-11-16 EP EP20000124328 patent/EP1106724B1/de not_active Expired - Lifetime
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US4054713A (en) * | 1973-12-28 | 1977-10-18 | Kao Soap Co., Ltd. | Process for preparing glass fiber mats |
DE2604544A1 (de) * | 1976-02-06 | 1977-08-11 | Basf Ag | Bindemittel zum verfestigen von glasfasermatten |
WO1994020661A1 (de) * | 1993-03-04 | 1994-09-15 | Wacker-Chemie Gmbh | Vernetzbare dispersionspulver als bindemittel für fasern |
EP0894888A1 (de) * | 1997-07-31 | 1999-02-03 | Wacker-Chemie GmbH | Pulverförmige, vernetzbare Textilbinder-Zusammenseztung |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1348791A1 (de) * | 2002-03-07 | 2003-10-01 | Chomarat Composites | Verstärkungsstruktur |
EP1413669A1 (de) * | 2002-10-21 | 2004-04-28 | Bamberger Kaliko GmbH | Witterungsbeständige, PVC-freie Flächenmaterialien auf Textilbasis |
EP1413668A1 (de) * | 2002-10-21 | 2004-04-28 | Bamberger Kaliko GmbH | Witterungsbeständige, PVC-freie Flächenmaterialien auf Textilbasis |
EP1775371A1 (de) * | 2005-10-12 | 2007-04-18 | Rohm and Haas Company | Verbundmaterialien und deren Herstellung |
US7405169B2 (en) | 2005-10-12 | 2008-07-29 | Rohm And Hass Company | Composite materials and methods of making the same |
WO2008088545A1 (en) * | 2007-01-19 | 2008-07-24 | Celanese International Corporation | Emulsion polymer binder with aziridine crosslinking agent for mineral fiber webs |
WO2010097192A3 (de) * | 2009-02-27 | 2010-11-18 | Celanese Emulsions Gmbh | Mineralwollfasermatten, verfahren zu deren herstellung und verwendung |
Also Published As
Publication number | Publication date |
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DE50003093D1 (de) | 2003-09-04 |
DE19959415C2 (de) | 2002-03-07 |
EP1106724B1 (de) | 2003-07-30 |
DE19959415A1 (de) | 2001-06-21 |
US6472462B1 (en) | 2002-10-29 |
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