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WO1992018432A1 - Procede d'impregnation de filaments orientes - Google Patents

Procede d'impregnation de filaments orientes Download PDF

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Publication number
WO1992018432A1
WO1992018432A1 PCT/US1991/002500 US9102500W WO9218432A1 WO 1992018432 A1 WO1992018432 A1 WO 1992018432A1 US 9102500 W US9102500 W US 9102500W WO 9218432 A1 WO9218432 A1 WO 9218432A1
Authority
WO
WIPO (PCT)
Prior art keywords
strand
filaments
thermoplastic
powder
impregnated
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.)
Ceased
Application number
PCT/US1991/002500
Other languages
English (en)
Inventor
Jean-Claude Pollet
Gary Lynn Williams
Gordon Patrick Armstrong
Martin Charles Flautt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Owens Corning
Original Assignee
Owens Corning Fiberglas Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Owens Corning Fiberglas Corp filed Critical Owens Corning Fiberglas Corp
Priority to JP91507777A priority Critical patent/JPH05507675A/ja
Priority to BR919106692A priority patent/BR9106692A/pt
Priority to KR1019920703168A priority patent/KR930701356A/ko
Publication of WO1992018432A1 publication Critical patent/WO1992018432A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags

Definitions

  • this invention relates to a process for producing thermoplastic or thermoset powder impregnated glass fiber strands.
  • 25 passes bundles of filaments (glass, carbon or even AramidCS) fibers) through a fluidized bed of powdered thermoplastic resin.
  • the filaments are kept separate by different means so that the resin can be picked-up by the filaments.
  • 5 powders may penetrate the filaments. Still other processes sheath the rovings with a flexible polymer sleeve after the powder has penetrated the fibers in an attempt to keep the powder on the fibers before the fibers are used in a molding process. Another alternative process fuses the powder impregnated strands into a rigid ribbon in order to keep the powder on the strands.
  • Still another process produces fiber reinforced thermoplastic material directly from the bushing by extruding filaments into a bed of dry thermoplastic powder which has a lower melting point than the filaments. The powder sticks to the filaments so that impregnation takes place when the filaments are still separate. These filaments must be cut into granules or fed directly to a heated die.
  • thermoplastic or thermoset resin powder is put between the filament bundles after the filaments have previously been gathered or glued together into a bundle.
  • the filaments in the bundles must be separated or "unglued” and often goo "wet out” or dispersion of the resin between the filaments is not achieved. Rather, the resin forms a sheath or coating around the bundle and in the final injection molded products, these glass bundles remain intact and good glass dispersion is not achieved.
  • thermoplastic or thermoset resin a method for impregnating strands with a thermoplastic or thermoset resin which would eliminate non-aqueous solvents, fluidized beds, sheaths, and time-consuming extrusion techniques or other, dangerous methods for applying thermoplastic or thermoset resins to fibers.
  • This invention is directed to that objective.
  • DISCLOSURE OF INVENTION The present invention is directed to a process for producing a highly loaded, impregnated fibrous strand where the impregnation of the strand takes place during the fiber forming process. This is accomplished by using a powdered polymer resin slurry to impregnate the strand prior to gathering the fibers together into the strand.
  • the impregnated strand can be subsequently dried to remove the water, and cured or set to attach the powder particles along the surfaces of the fibers. Heating of the impregnated strand allows for the fusing (gluing) of the melted powders to the fibers.
  • the present process may employ doctor-blade modified conventional roll applicator or positive feed, slot applicator to carry out the invention.
  • the present invention relates to an improved process for the production of a yarn or strand (bundle of filaments) pre-impregnated with a thermoplastic or thermoset polymer during the filament forming operation.
  • the process of the present invention can be practiced using conventional roll application methods or a positive feed, slot applicator. Glass, carbon, aramid polyester or polyethylene filaments, as well as other known fibers or hybrid combinations of these fibers, are suitable fibers which can be impregnated according to the process of the present invention.
  • the process involves the formulation of a size composition which contains a carrier solvent, normally water, a coupling agent, a binder or film former material, and a thickener or rheology modifier material.
  • a carrier solvent normally water, a coupling agent, a binder or film former material, and a thickener or rheology modifier material.
  • a matrix thermoplastic or thermoset resin powder is dispersed in the sizing to form a slurry.
  • any suitable coupling agent can be employed in the successful practice of this invention.
  • the coupling agent acts to produce adhesion between the matrix resin and provide strength development and retention of the matrix resin in the slurry.
  • a suitable coupling agent is a silane.
  • the silane is an organosilane including, for example, gamma- aminopropyltriethoxysilane (commercially available from Union Carbide under the trade name "A-1100").
  • the coupling agent will be contained in an amount within the range of from about 0.05 to about 5 percent, by weight, of the slurry mixture.
  • Any suitable binder material can be employed. The binder or film former material aids in the handling and processing of the filament during the process of the present invention.
  • Suitable binder or film former materials are, for example, epoxy, polyester, polyvinyl acetate, polyvinyl alcohol, acrylics, or other chemicals which have the ability to bond the thermoplastic or thermoset powder particles to the fiber upon the evaporation of the water or which have the ability themselves to suspend the particles in the slurry and subsequently bond themselves to the fiber.
  • the binder material will be contained in an amount within the range of from about 0.5 to about 5 percent, by weight, of the slurry mixture.
  • any suitable thickener material can be employed.
  • the thickener material acts as a rheology modifier so that the thermoplastic or thermoset powder particles will transfer to the fiber. Without the thickener material the powder particles may stay behind on the rolls of the applicator while the carrier solvent goes on the fiber. The result would be a rapid build-up of powder on the applicator rolls, which in turn, rapidly causes fiber breakage.
  • thermoplastic or thermoset resins which can be produced or reduced into a powder such as, for example, polyvinyl chloride, PVC, CPVC, polyethylene, polypropylene, nylon, po!y(butylene terephthalate) PBT, or poly(ethylene terephthalate) PET, polyester, or solid epoxies.
  • high performance materials such as liquid crystal polymers, polyetheretherketone (PEEK) or poly phenylene sulfide (PPS) can be used.
  • the thermoplastic or thermoset resins are dispersed into the 5 sizing in the form of fine particles.
  • the size of the powder particles are between about 5 to 50 microns, or more preferrably between about 10-30 microns.
  • the resin powders can be applied to the filaments in an amount within the range of between about 5 to
  • the sizing mixture suspends the thermoplastic or thermoset powder particles in the slurry.
  • the resultant slurry is sufficiently liquid to be applied to the fibers during the fiber-forming operation.
  • Each fiber is coated by
  • the slurry mixture as the fibers are formed that is, at or about the place in their formation where the conventional size compositions are typically applied (e.g., between the bushing and the spindle on which the fibers are wound as a package).
  • the continuous fibers leave the bushing and are dipped into the slurry mixture and are impregnated with the slurry mixture.
  • the highly loaded thermoplastic or thermoset fibers are subsequently dried in order to evaporate or remove the water.
  • the impregnated strands are then cured in order to set the binder or film former material. The curing or setting "glues" the powder particles along the surface 5 of the fibers.
  • thermoplastic powders When thermoplastic powders are used, the resultant impregnated strands can be subsequently heated to allow the melted thermoplastic polymers to fuse.
  • Thermoset powders which are solids at room temperature, normally do not need a heatsetting step.
  • organic or inorganic particulates such as metallic fillers useful in producing conductive rovings, may also be used with the thermoplastic or thermoset polymer powder particles. These fillers can either be pre-combined with the polymer so that each
  • 35 powder particle contains polymer and filler or be added separately as a powder to the slurry.
  • the resultant impregnated strands can be chopped, either before or after drying, to be used for such operations as injection molding.
  • Continuous thermoplastic or thermoset impregnated strands can be filament wound or pultruded to achieve thermoplastic or thermoset fiber reinforced end use items.
  • thermoplastic slurry was applied to glass fibers during the forming operation to achieve a thermoplastic content of 23% relative to the total weight of the prepreg strand.
  • the polyamide thermoplastic powder has preferably an average particle size between 5 and 40 microns and no particle retained by an 80-mesh screen (more preferably 115 mesh, most preferably 200 mesh).
  • Orgasol 1002D is a nylon 6 powder available from ATOCHEM (France).
  • Polyox WSR 205 is a tradename for polyethylene oxides available from Union Carbide; other polyethylene oxides of different molecular weight, molecular weight distribution or branching may also be suitable, such as any of the Polyox series having a molecular weight between 100,000 and 4,000,000.
  • A1100 is gamma- aminopropytriethoxysilane available from Union Carbide. Once the slurry was mixed together, continuous glass fibers were coated with the slurry mixture.
  • the impregnated glass fibers were then collected into a strand, and the strand was then wound around a take-up bobbin to form a substantially cylindrical package (conventionally termed a "yarn package").
  • the yarn package was dried so as to evaporate the water from the impregnated strands and then cured or set so as to allow the binder material to "glue" the thermoplastic powder particles along the surfaces of the glass fibers.
  • Composites molded from the prepreg strands made by using the example formulation exhibit properties superior to those of competitive products.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Procédé servant à imprégner un filament orienté de particules de poudre polymère thermodurcissable ou thermoplastique pendant sa fabrication. Il consiste à former des filaments orientés, à les maintenir séparés, à les imprégner d'une boue aqueuse contenant les particules pulvérulentes, et à les sécher pour enlever l'eau et obtenir un filament imprégné de particules pulvérulentes. Ces dernières sont présentes sur le filament dans une quantité comprise entre environ 5 et 50% en poids par rapport au poids du filament imprégné. Les fibres de verre enrobées de boue selon ce procédé peuvent être imprégnées de poudres thermoplastiques.
PCT/US1991/002500 1987-03-12 1991-04-16 Procede d'impregnation de filaments orientes Ceased WO1992018432A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP91507777A JPH05507675A (ja) 1991-04-16 1991-04-16 フィラメントストランドの含浸法
BR919106692A BR9106692A (pt) 1991-04-16 1991-04-16 Um processo para impregnar cordoes de filamentos
KR1019920703168A KR930701356A (ko) 1987-03-12 1991-04-16 필라멘트사 침지방법

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US2495387A 1987-03-12 1987-03-12

Publications (1)

Publication Number Publication Date
WO1992018432A1 true WO1992018432A1 (fr) 1992-10-29

Family

ID=21823230

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/002500 Ceased WO1992018432A1 (fr) 1987-03-12 1991-04-16 Procede d'impregnation de filaments orientes

Country Status (3)

Country Link
EP (1) EP0534979A1 (fr)
KR (1) KR930701356A (fr)
WO (1) WO1992018432A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005238596A (ja) * 2004-02-25 2005-09-08 Toho Tenax Co Ltd 均一性に優れたプリプレグ及びその製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2778764A (en) * 1951-09-13 1957-01-22 Owens Corning Fiberglass Corp Method of sizing glass fibers to form strands
US3498826A (en) * 1966-03-30 1970-03-03 Owens Corning Fiberglass Corp Treated glass fibers and fabrics formed thereof
GB1264432A (fr) * 1969-04-28 1972-02-23
FR2319660A1 (fr) * 1975-07-31 1977-02-25 Basf Ag Pieces moulees a surface lisse en matiere plastique armee de fibres de verre
EP0058141A1 (fr) * 1981-02-05 1982-08-18 KemaNord AB Des matériaux composites fibreux impregnés de résine et un procédé pour les préparer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2778764A (en) * 1951-09-13 1957-01-22 Owens Corning Fiberglass Corp Method of sizing glass fibers to form strands
US3498826A (en) * 1966-03-30 1970-03-03 Owens Corning Fiberglass Corp Treated glass fibers and fabrics formed thereof
GB1264432A (fr) * 1969-04-28 1972-02-23
FR2319660A1 (fr) * 1975-07-31 1977-02-25 Basf Ag Pieces moulees a surface lisse en matiere plastique armee de fibres de verre
EP0058141A1 (fr) * 1981-02-05 1982-08-18 KemaNord AB Des matériaux composites fibreux impregnés de résine et un procédé pour les préparer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005238596A (ja) * 2004-02-25 2005-09-08 Toho Tenax Co Ltd 均一性に優れたプリプレグ及びその製造方法

Also Published As

Publication number Publication date
KR930701356A (ko) 1993-06-11
EP0534979A1 (fr) 1993-04-07

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