WO1992018433A1 - Coated glass fibers - Google Patents
Coated glass fibers Download PDFInfo
- 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
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.
Abstract
An aqueous size composition for glass fibers is disclosed which includes a coupling agent, a binder or film former material and a thermoplastic polymer resin powder, wherein said composition is applied to the glass fiber surfaces during the fiber forming process. A rheology modifier material may be added to the size composition. One embodiment of the composition includes an organosilane coupling agent, a polyethylene oxide binder material and a polyamide thermoplastic polymer resin.
Description
DESCRIPTION
COATED GLASS FIBERS
TECHNICAL FIELD 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.
BACKGROUND ART
The production of impregnated fibers and the application of thermoplastic resins to the fibers is well-known.
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.
Considerable time and expense would be saved if a size composition useful for impregnating strands with a thermoplastic resin were available which could be applied during the fiber forming process without the need for non-aqueous solvents, fluϊdϊzed beds, sheaths or time-consuming manufacturing processes.
Further, considerable processing time would be saved if the glass fiber could be pre-impregnated with the thermoplastic resin during the glass fiber forming process. Moreover, it would be beneficial if a size composition could be employed which could be directly blended with the thermoplastic resin during the glass fiber forming process.
DISCLOSURE OF INVENTION
According to the present invention, there is provided 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.
According to the present invention, there is no need to first apply a sizing composition to the glass fibers and thereafter impregnate the resulting sized glass fibers with a compatible polymeric resin matrix in order to provide a glass fiber reinforced product. A preferred composition of the present invention includes organosϊlane, polyethylene oxide, Nylon 6 powder and water, wherein
the thermoplastic content is approximately 23%, relative to the total weight of the impregnated glass strand.
Also, according to this invention there is provided a glass fiber impregnated with the above-identified thermoplastic composition. The 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.
These and other aspects and advantages of the present invention will become clear after consideration is given to the detailed description of the invention which follows.
BEST MODE OF CARRYING OUT INVENTION 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. The term "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. Preferably, 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 individual components utilized in the practice of this invention are commercially available and can thus be simply blended with one another in the preparation of the formulation embodying the features of the present invention.
Generally, 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.
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. One example of a suitable coupling agent is a silane. Preferrably, 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.
Any suitable 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.
Any suitable resin can be employed. The thermoplastic resins are dispersed into the sizing in the form of fine particles. In a preferred embodiment the size of the powder particles are between about 1 to 50 microns, or more preferrably between about 10-30 microns. According to the present invention 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. In preferred embodiments the 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)].
According to the present invention 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. Preferably, 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
Serial No. 07/024,953 filed March 12, 1984, now abandoned, (the entire disclosure thereof being expressly incorporated herein to by reference). 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). In one fiber
forming process, 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.
It is also within the contemplated scope of this invention that 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.
INDUSTRIAL APPLICABILITY While the above describes the present invention with sufficient particularity, the following is intended to further exemplify the present invention. The following 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.
Composition and Range Example
Polyamide powder 30 to 50% Orgasol 1002D 40%
Polyoxyethylene .5 to 5% Polyox WSR 205 1.2%
Coupling Agent .05 to 5% All 00 .2%
Water balance to 100% Water 58-60%
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.
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. The yarn package was dried so as to evaporate the water from the impregnated strands and then 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.
As can be readily seen from Table I, the thermoplastic impregnated strand, having 77% glass content, of the present invention, has greatly improved mechanical properties over the commercially impregnated strands. In particular, the longitudinal tensile strength and flexural strength are better than the prior art prepregs tested. Also, 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.
COMPARATIVE PROPERTIES OF COMPRESSION MOLDED UNIDIRECTIONAL GLASS/POLYAMIDE 6 COMPOSITES
Modulus Strength Modulus Content
Prepreg (106 kg/ (103 kg/ (106 kg/ (Percent) Type sq.cm) sq.cm) sq.cm)
(M) measured (P) published * PCI NG GL 50 ** ATO 1200 TEX
Claims
1. A glass fiber having a coating thereon, consisting essentially of a coupling agent, a film former material and a thermoplastic polymer resin powder wherein the coating is the dried residue formed by evaporation of water from an aqueous composition, , m comprising, in weight percent, based on the weight of the aqueous composition, about 0.05 to about 5.0 wt. % coupling agent, about 0.5 to about 5.0 wt. % film former material and about 30 to about 50 wt. % thermoplastic polymer resin powder.
mm 2. The glass fiber of claim 1, wherein the coupling agent is gamma-aminopropyltrϊethoxysilane.
3. The glass fiber of claim 1, wherein the thermoplastic resin is a polyamide resin.
25
4. The glass fiber of claim 1, wherein the thermoplastic polymer resin is a Nylon 6 resin.
5. The glass fiber of claim 1, wherein the thermoplastic mrs polymer resin is poly[imino(l-oxo-l,6-hexanediyl)].
6. The glass fiber of elaim 1, wherein the binder material is polyethylene oxide.
,c 7. The glass fiber of claim 1, wherein the thermoplastic polymer resin is present in average particle size between about 1 to about 40 microns.
8. The glass fiber of claim 1, wherein the aqueous composition contains metallic powders.
9. The glass fiber of claim 1, wherein the aqueous composition further comprises a rheology modifier material.
10. The glass fiber of claim 1, wherein the aqueous size composition comprises, in weight percent about 30 to 50 thermoplastic polymer resin powder, about .5 to about 5.0 film former material, and about 0.05 to about 5.0 coupling agent and the balance being water.
11. The glass fiber of claim 1, wherein the aqueous composition comprises, in weight percent of the following: the thermoplastic polymer resin powder comprising Nylon 6 powder in an amount of about 40.0 wt. percent; the film former material comprising polyethylene oxide in an amount of about 1.2 wt. percent; the coupling agent comprising gamma-aminopropyltriethoxysilane in an amount of about 0.2 wt. percent; and water in an amount of about 58-60 wt. percent.
12. A plurality of glass fibers, at least a portion of the fibers' surfaces having a coating thereon consisting essentially of a coupling agent, a film former material and a thermoplastic polymer resin powder wherein the coating is the dried residue formed by evaporation of water from an aqueous composition comprising, in weight percent, based on the weight of the aqueous composition, about 0.05 to about 5.0 wt. % coupling agent, about 0.5 to about 5.0 wt. % film former material and about 30 to about 50 wt. % thermoplastic polymer resin powder.
13. The glass fiber of claim 12, wherein said organosilane is gamma-aminopropyltriethoxysilane.
14. The glass fiber of claim 12, wherein said polyamide thermoplastic resin is poly[imino(l-oxo-,6-hexanediyI)].
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR919106679A BR9106679A (en) | 1991-04-16 | 1991-04-16 | COATED GLASS FIBERS |
KR1019920703169A KR930701357A (en) | 1987-03-12 | 1991-04-16 | Coated fiberglass |
JP91508810A JPH05507677A (en) | 1991-04-16 | 1991-04-16 | coated fiberglass |
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 (en) | 1992-10-29 |
Family
ID=21823238
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1991/002501 WO1992018433A1 (en) | 1987-03-12 | 1991-04-16 | Coated glass fibers |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0534990A1 (en) |
KR (1) | KR930701357A (en) |
WO (1) | WO1992018433A1 (en) |
Cited By (2)
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 (en) * | 2009-02-11 | 2010-08-19 | Ppg Industries Ohio, Inc. | Fiber reinforced polymeric composites and methods of making the same |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101652174B1 (en) * | 2014-10-06 | 2016-08-29 | 주식회사 두산 | Prepreg, and metal-clad laminate and printed circuit board comprising the same |
Citations (5)
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 (en) * | 1969-04-28 | 1972-02-23 | ||
FR2319660A1 (en) * | 1975-07-31 | 1977-02-25 | Basf Ag | MOLDED PARTS WITH SMOOTH SURFACE IN PLASTIC MATERIAL REINFORCED WITH FIBERGLASS |
EP0058141A1 (en) * | 1981-02-05 | 1982-08-18 | KemaNord AB | Resin-impregnated fibre composite materials and a method for their manufacture |
-
1991
- 1991-04-16 EP EP91909151A patent/EP0534990A1/en not_active Withdrawn
- 1991-04-16 KR KR1019920703169A patent/KR930701357A/en not_active Application Discontinuation
- 1991-04-16 WO PCT/US1991/002501 patent/WO1992018433A1/en not_active Application Discontinuation
Patent Citations (5)
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 (en) * | 1969-04-28 | 1972-02-23 | ||
FR2319660A1 (en) * | 1975-07-31 | 1977-02-25 | Basf Ag | MOLDED PARTS WITH SMOOTH SURFACE IN PLASTIC MATERIAL REINFORCED WITH FIBERGLASS |
EP0058141A1 (en) * | 1981-02-05 | 1982-08-18 | KemaNord AB | Resin-impregnated fibre composite materials and a method for their manufacture |
Cited By (3)
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 (en) * | 2009-02-11 | 2010-08-19 | Ppg Industries Ohio, Inc. | Fiber reinforced polymeric composites and methods of making the same |
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 (en) | 1993-06-11 |
EP0534990A1 (en) | 1993-04-07 |
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