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WO1992018433A1 - Fibres de verre enrobees - Google Patents

Fibres de verre enrobees Download PDF

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Publication number
WO1992018433A1
WO1992018433A1 PCT/US1991/002501 US9102501W WO9218433A1 WO 1992018433 A1 WO1992018433 A1 WO 1992018433A1 US 9102501 W US9102501 W US 9102501W WO 9218433 A1 WO9218433 A1 WO 9218433A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass fiber
thermoplastic
polymer resin
coupling agent
thermoplastic polymer
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/US1991/002501
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 BR919106679A priority Critical patent/BR9106679A/pt
Priority to KR1019920703169A priority patent/KR930701357A/ko
Priority to JP91508810A priority patent/JPH05507677A/ja
Publication of WO1992018433A1 publication Critical patent/WO1992018433A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • 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
    • 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
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/328—Polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Definitions

  • This invention relates to a size composition useful for impregnating a highly loaded, impregnated fibrous strand where the impregnation takes place during the fiber forming operation. In one of its more specific aspects, this invention relates to a process for producing thermoplastic powder impregnated glass fiber strands.
  • Sizing compositions typically employed as coatings for glass fibers have conventionally been applied to the surface of the glass fibers after the glass fiber has been formed. Typically it is necessary to first produce the glass fibers by providing a thin layer of a size composition to the surface of the bare glass fibers.
  • the size composition must be compatible with the glass fiber and the resin which is subsequently applied to the sized fiber.
  • the size composition serves to improve the bonding relationship between the glass fibers and the polymeric or thermoplastic resins.
  • the glass fibers are then collected into a strand and the strand is wound around a take-up bobbin to form a substantially cylindrical package, conventionally termed a "yarn package".
  • the yarn package is then air dried or subjected to elevated temperatures in order to dry the size composition applied to the surface of the glass fibers.
  • the glass fibers are thereafter impregnated with the thermoplastic resin to form an impregnated yarn or cord.
  • the glass fiber could be pre-impregnated with the thermoplastic resin during the glass fiber forming process.
  • a size composition could be employed which could be directly blended with the thermoplastic resin during the glass fiber forming process.
  • a slurry composition for impregnating glass fibers which includes a thermoplastic resin, a coupling agent such as a silane, a binder or film former material and a thickening agent.
  • a rheology modifier may also be added to the composition.
  • the slurry composition is applied to the glass fiber during the fiber forming operation.
  • the composition of this invention can thus be applied as a size for glass fibers during the fiber forming operation and the resulting sized thermoplastic impregnated glass fibers can then be fabricated into glass fiber reinforced products.
  • a preferred composition of the present invention includes organos ⁇ lane, polyethylene oxide, Nylon 6 powder and water, wherein the thermoplastic content is approximately 23%, relative to the total weight of the impregnated glass strand.
  • thermoplastic impregnated glass fiber is easy to handle and to fabricate into end use items. Also, the thermoplastic impregnated glass fiber has excellent mechanical properties relative to commercially available thermoplastic impregnated glass fibers.
  • the present invention relates to a slurry composition useful for producing an improved yarn or strand (bundle of filaments) pre- impregnated with a thermoplastic polymer during the filament forming operation.
  • the present invention is compatible with any glass fiber conventionally utilized for the reinforcement of polymeric resins.
  • glass fibers as used herein shall mean filaments formed by attenuation of one or more streams of molten glass and to strands formed when such glass fiber filaments are gathered together in the forming process.
  • the term shall also mean yarns and cords formed by applying and/or twisting a multiplicity of strands together and to woven and non-woven fabrics which are formed of such glass fiber strands, yarns, or cords.
  • the size formulation of the present invention is useable with E-type fibers having a diameter in the range of from about 0.35 to about 0.75 mil.
  • the composition of this invention may contain a carrier solvent, normally water, a coupling agent, a binder or film former material, a thickener or rheology modifier material, and a matrix thermoplastic resin powder dispersed in the sizing to form a slurry.
  • a carrier solvent normally water, a coupling agent, a binder or film former material, a thickener or rheology modifier material, and a matrix thermoplastic resin powder 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 normally be contained in an amount within the range of from about 0.05 to about 5 percent, by weight, of the slurry mixture.
  • binder material can be employed.
  • the binder or film former material aids in the handling and processing of the filament during the fiber forming process.
  • 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 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 normally 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 powder particles will actually adhere to the fiber. Without the thickener material the thermoplastic 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 resins are dispersed into the sizing in the form of fine particles.
  • size of the powder particles are between about 1 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 of between about 5 to about 50 percent, by weight, of the final prepreg yarn or strand.
  • amount of the thermoplastic polymer resin in the aqueous size composition ranges either from about 20 to about 35, or from about 30 to about 50 weight percent of the aqueous size composition.
  • One particularly suitable resin is Nylon 6, poly [imino(l-oxo-l,6-hexamediyl)].
  • the sizing composition suspends the thermoplastic powder particles in the slurry.
  • the slurry compositions of this invention are best produced by blending all materials in their liquid state with agitation.
  • a uniform coating of the composition can be applied to the glass fibers in any suitable manner during the fiber forming process.
  • the compositions of the present invention are applied to the surface of the glass fiber in the manner described in the co-pending U.S. Application Serial No. 07/269,089 filed November 9, 1988 now U.S. Patent No. issued , which is a continuation of
  • the resultant slurry composition 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 and are impregnated with the slurry.
  • the highly loaded thermoplastic 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 of the fibers.
  • the resultant impregnated strands can be subsequently heated to allow the melted thermoplastic polymers to fuse.
  • organic or inorganic particulates such as metallic fillers useful in producing conductive rovings, may also be used with the thermoplastic polymer powder particles. These fillers can either be pre-combined with the polymer so that each 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 impregnated strands can be filament wound or pultruded to achieve thermoplastic 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 polyamide, 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-aminopropyltriethoxysilane available from Union Carbide.
  • Composites molded from the prepreg strands made by using the example formulation exhibit properties superior to those of competitive products.
  • thermoplastic impregnated strand having 77% glass content, of the present invention, has greatly improved mechanical properties over the commercially impregnated strands.
  • the longitudinal tensile strength and flexural strength are better than the prior art prepregs tested.
  • the thermoplastic impregnated strand has greatly improved transverse flexual strength and flexual modulus.
  • the improvement in the thermoplastic prepreg formed by the present process is most evident when compared to a prior art prepreg having a similar percentage of glass content, by weight. It will be evident from the foregoing that various modifications can be made to this invention. Such, however, are considered as being within the scope of the invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition aqueuse d'encollage pour fibres de verre. Elle comprend un agent d'accrochage, un matériau liant ou filmogène ainsi qu'une poudre de résine polymère thermoplastique, ladite composition étant appliquée aux surfaces des fibres de verre pendant le processus de formation de fibres. On peut ajouter à la composition d'encollage un matériau modifiant la rhéologie. Dans un mode de réalisation, la composition comprend un agent d'accrochage en organosilane, un matériau liant en oxyde de polyéthylène, et une résine polymère thermoplastique de polyamide.
PCT/US1991/002501 1987-03-12 1991-04-16 Fibres de verre enrobees Ceased WO1992018433A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BR919106679A BR9106679A (pt) 1991-04-16 1991-04-16 Fibras de vidro revestidas
KR1019920703169A KR930701357A (ko) 1987-03-12 1991-04-16 피복된 유리섬유
JP91508810A JPH05507677A (ja) 1991-04-16 1991-04-16 被覆ガラス繊維

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US2495487A 1987-03-12 1987-03-12

Publications (1)

Publication Number Publication Date
WO1992018433A1 true WO1992018433A1 (fr) 1992-10-29

Family

ID=21823238

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/002501 Ceased WO1992018433A1 (fr) 1987-03-12 1991-04-16 Fibres de verre enrobees

Country Status (3)

Country Link
EP (1) EP0534990A1 (fr)
KR (1) KR930701357A (fr)
WO (1) WO1992018433A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5387468A (en) * 1987-03-12 1995-02-07 Owens-Corning Fiberglas Technology Inc. Size composition for impregnating filament strands
WO2010093759A1 (fr) * 2009-02-11 2010-08-19 Ppg Industries Ohio, Inc. Composites polymères renforcés avec des fibres et leurs procédés de préparation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101652174B1 (ko) * 2014-10-06 2016-08-29 주식회사 두산 프리프레그 및 이를 포함하는 금속박 적층판 및 인쇄회로기판

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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5387468A (en) * 1987-03-12 1995-02-07 Owens-Corning Fiberglas Technology Inc. Size composition for impregnating filament strands
WO2010093759A1 (fr) * 2009-02-11 2010-08-19 Ppg Industries Ohio, Inc. Composites polymères renforcés avec des fibres et leurs procédés de préparation
US9388270B2 (en) 2009-02-11 2016-07-12 Ppg Industries Ohio, Inc. Fiber reinforced polymeric composites and methods of making the same

Also Published As

Publication number Publication date
KR930701357A (ko) 1993-06-11
EP0534990A1 (fr) 1993-04-07

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