EP1124769A1 - Impregnated glass fiber strands and products including the same - Google Patents

Impregnated glass fiber strands and products including the same

Info

Publication number
EP1124769A1
EP1124769A1 EP99952920A EP99952920A EP1124769A1 EP 1124769 A1 EP1124769 A1 EP 1124769A1 EP 99952920 A EP99952920 A EP 99952920A EP 99952920 A EP99952920 A EP 99952920A EP 1124769 A1 EP1124769 A1 EP 1124769A1
Authority
EP
European Patent Office
Prior art keywords
fiber
particles
fabric
fiber strand
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.)
Withdrawn
Application number
EP99952920A
Other languages
German (de)
English (en)
French (fr)
Inventor
Ernest L. Lawton
Xiang Wu
William B. Rice
Bruce E. Novich
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.)
PPG Industries Ohio Inc
Original Assignee
PPG Industries Ohio Inc
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 PPG Industries Ohio Inc filed Critical PPG Industries Ohio Inc
Publication of EP1124769A1 publication Critical patent/EP1124769A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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
    • C03C25/465—Coatings containing composite materials
    • C03C25/47—Coatings containing composite materials containing particles, fibres or flakes, e.g. in a continuous phase
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0166—Polymeric layer used for special processing, e.g. resist for etching insulating material or photoresist used as a mask during plasma etching
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0175—Inorganic, non-metallic layer, e.g. resist or dielectric for printed capacitor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0212—Resin particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0239—Coupling agent for particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/0245—Flakes, flat particles or lamellar particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/0248—Needles or elongated particles; Elongated cluster of chemically bonded particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/0254—Microballoons or hollow filler particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0275—Fibers and reinforcement materials
    • H05K2201/029—Woven fibrous reinforcement or textile
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12—Using specific substances
    • H05K2203/127—Lubricants, e.g. during drilling of holes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0044—Mechanical working of the substrate, e.g. drilling or punching
    • H05K3/0047—Drilling of holes

Definitions

  • This invention relates generally to coated fiber strands for reinforcing composites and, more specifically, to glass fiber strands coated with particles that provide interstitial spaces between adjacent glass fibers of the strand.
  • thermosetting molding operations good "wet-through” (penetration of a polymeric matrix material through the mat or fabric) and “wet-out” (penetration of a polymeric matrix material through the individual bundles or strands of fibers in the mat or fabric) properties are desirable. In contrast, good dispersion properties are of predominant concern in typical thermoplastic molding operations.
  • Japanese Patent Application No. 9-208,268 discloses a cloth having yarn formed from glass fibers coated immediately after spinning with starch or a synthetic resin and 0.001 - 20.0 weight percent of inorganic solid particles such as colloidal silica, calcium carbonate, kaolin and talc having average particles sizes of 5 to 2000 nanometers (0.05 to 2 micrometers) to improve resin impregnation.
  • inorganic solid particles such as colloidal silica, calcium carbonate, kaolin and talc having average particles sizes of 5 to 2000 nanometers (0.05 to 2 micrometers) to improve resin impregnation.
  • inorganic solid particles such as colloidal silica, calcium carbonate, kaolin and talc having average particles sizes of 5 to 2000 nanometers (0.05 to 2 micrometers) to improve resin impregnation.
  • inorganic solid particles such as colloidal silica, calcium carbonate, kaolin and talc having average particles sizes of 5 to 2000 nanometers (0.05 to 2 micrometers) to improve resin
  • U.S. Patent No. 3,312,569 discloses adhering particles of alumina to the surfaces of the glass fibers to improve penetration of resin between glass reinforcement fibers during formation of a composite.
  • Mohs' hardness values for alumina is greater than about 9 1 , which can cause abrasion of softer glass fibers.
  • Russian Union No. 859400 discloses an impregnating composition for manufacturing laminates of glass fiber cloth, the composition containing an alcoholic solution of phenol-formaldehyde resin, graphite, molybdenum disulphide, polyvinyl butyral and surfactant. Volatile alcoholic solvents are not desirable for glass fiber production applications.
  • Hollow filler particles can be used to modify the impregnation characteristics of the reinforcing material and/or reduce the overall density of the composite material produced therefrom.
  • US Patent No. 5,412,003 discloses impregnating a glass fiber with a resin composition containing an unsaturated polyester, a polymerizable monomer, a
  • thermoplastic resin a polymerization initiator and hollow glass microspheres (col. 2, lines 6-14). Molding materials and molded products obtained from the impregnated fibers are light in weight (col. 2, lines 26-30).
  • U.S. Patent No. 4,820,575 discloses incorporating hollow body fillers, and particularly heat expandable hollow body fillers, having particle diameters ranging from about 20 to about 300 micrometers into the interspaces between fibers of reinforcing materials to permanently reduce the resin pick up and specific weight of the reinforcing materials (col. 4, lines 39-43 and col. 3, lines 15-30).
  • the fillers are applied as an aqueous, binder-free suspension to the reinforcing material (col. 3, lines 63-68 and col. 4, lines 1-3).
  • U.S. Patent No. 5,866,253 discloses incorporating heat expandable hollow particles into fiber strands.
  • the particles are expandable into "microballoons" to create fiber strands having enlarged cross sectional dimensions to be used in composite materials.
  • the expanded particles generally have particle sizes ranging from about 40 to 50 micrometers which is greater than the diameter of the fibers of the strand (col. 3, lines 5-10).
  • Fiber strands having the expanded particles typically have about a four-fold increase in diameter as compared to fibers without the expanded particles and the density of the strand is considerably reduced (col. 4, lines 12-18). The larger strand diameter allows for fewer strands to be used in the formation of composites thereby providing lower finished product density (col. 1 , lines 39-43).
  • the coating on the surfaces of the fibers strands protect the fibers from abrasion during processing, provide for good weavability, particularly on air-jet looms and be compatible with the polymeric matrix material into which the fiber strands are incorporated.
  • Many sizing components commonly used on fiber strands to be woven into fabrics can adversely affect adhesion between the glass fibers and the laminate matrix material.
  • starch which is a commonly used sizing component for textile fibers, is generally not compatible with laminate resin matrix material.
  • the coating or sizing composition is typically removed from the woven cloth prior to lamination by thermal decomposition of the sizing components (called heat cleaning or de-oiling) or by washing the cloth with water (also called de-oiling).
  • thermal decomposition of the sizing components called heat cleaning or de-oiling
  • de-oiling thermal decomposition of the sizing components
  • a conventional heat cleaning process to thermally decompose sizing components involves heating the cloth at 380°C for 60-80 hours. The heat cleaned cloth is then re-coated with a silane coupling agent to improve adhesion between the glass fiber strands and the matrix material.
  • de-oiling processes are not always completely successful in removing the incompatible materials and can further contaminate the fabric with products of decomposition.
  • Japanese Patent Application 8-119-682 discloses a primary sizing composition containing a water-soluble epoxy resin that can be easily removed by rinsing with water (page 3, paragraph 2) to improve the removal or de-oiling characteristics of sizing compositions for use in composites.
  • the primary sizing comprises an epoxy resin having aggregated and formed particles with diameters of 0.5 to 50 micrometers and a pH between 5.5 and 7.5 (page 4, paragraph 1).
  • the epoxy resin is colloid with particles of 1 to 5 micrometers (page 6, paragraph 1). The particles are believed to be beneficial in preventing the flow or migration of the epoxy resin during drying.
  • U.S. Patent No. 4,009,317 discloses a primary sizing composition containing emulsified clad particles that produce a film on glass fibers and have good burn off characteristics (col. 1. lines 67-68 and col. 2, lines 1-3).
  • U.S. Patent No. 4,615,933 discloses saturating glass fabrics or strands with aqueous dispersions of polytetrafluoroethylene or other fluoro-polymer particles to form strands having about 50 to 70 percent by weight fiber and about 30 to 50 percent by weight polytetrafluoroethylene. The strands are subsequently pressed to form composites.
  • U.S. Patent Nos. 5,364,657 and 5,370,911 disclose incorporating polymeric particles into fiber strands by either contacting a moistened strand with a dry polymer particle-laden air stream (col.
  • One aspect of the present invention is a coated fiber strand comprising at least one fiber having a layer of a dried residue of a resin compatible coating composition on at least a portion of a surface of the at least one fiber, the resin compatible coating composition comprising: (a) a plurality of discrete, dimensionally stable particles formed from materials selected from the group consisting of organic materials, polymeric materials, composite materials and mixtures thereof that provide an interstitial space between the at least one fiber and at least one adjacent fiber, the particles having an average particle size of about 0.1 to about 5 micrometers; (b) at least one lubricious material; (c) at least one polymeric film former; and (d) at least one coupling agent, and a fabric incorporating at least one of the fiber strands.
  • the resin compatible coating composition comprising: (a) a plurality of discrete, dimensionally stable particles formed from materials selected from the group consisting of organic materials, polymeric materials, composite materials and mixtures thereof that provide an interstitial space between the at least one fiber and at least one adjacent
  • the present invention is a coated fiber strand comprising at least one glass fiber having a dried residue of an aqueous resin compatible coating composition on at least a portion of a surface of the at least one fiber, the aqueous resin compatible coating composition comprising (a) a plurality of discrete, polymeric organic particles that provide an interstitial space between the at least one glass fiber and at least one adjacent glass fiber, the particles having an average particle size of up to about 5 micrometers, (b) a lubricious material selected from the group consisting of oils, waxes, greases and mixtures thereof, (c) polymeric film-forming material selected from the group consisting of thermosetting polymeric materials, thermoplastic polymeric materials, natural polymeric materials and mixtures thereof, and (d) a coupling agent, and a fabric incorporating at least one of the fiber strands.
  • the aqueous resin compatible coating composition comprising (a) a plurality of discrete, polymeric organic particles that provide an interstitial space between the at least one glass fiber and at least one adjacent glass
  • Still another aspect of the present invention is a coated fiber strand comprising at least one glass fiber having a dried residue of an aqueous resin compatible coating composition on at least a portion of a surface of the at least one fiber, the aqueous resin compatible coating composition comprising: (a) a plurality of particles comprising; (i) at least one particle formed from an acrylic copolymer which is a copolymer of styrene and acrylic; and (ii) at least one particle formed from an inorganic solid lubricant material selected from the group consisting of boron nitride, graphite and metal dichalcogenides, wherein the particles have an average particle size of up to about 5 micrometers and comprise about 35 to about 55 weight percent of the resin compatible coating composition on a total solids basis; (b) a lubricious material selected from the group consisting of cetyl palmitate, cetyl laurate, octadecyl laurate, octadecyl myristate
  • Yet another aspect of the present invention is a fabric comprising a plurality of fibers strands comprising at least one fiber, at least a portion of the fabric having a residue of a resin compatible coating composition
  • a resin compatible coating composition comprising: (a) a plurality of discrete, dimensionally stable particles formed from materials selected from the group consisting of organic materials, polymeric materials, composite materials and mixtures thereof that provide an interstitial space between the at least one fiber and at least one adjacent fiber, the particles having an average particle size of about 0.1 to about 5 micrometers; (b) at least one lubricious material; (c) at least one polymeric film former; and (d) at least one coupling agent.
  • Fig. 1 is a perspective view of a coated fiber strand having a primary layer of a dried residue of a coating composition according to the present invention
  • Fig. 2 is a perspective view of a coated fiber strand having a primary layer of a dried residue of a sizing composition and thereupon a secondary layer of a secondary coating composition according to the present invention
  • Fig. 3 is a perspective view of a coated fiber strand having a primary layer of a dried residue of a sizing composition, a secondary layer of a secondary coating composition, and a tertiary layer thereupon according to the present invention
  • Fig. 4 is a top plan view of a composite according to the present invention.
  • Fig. 5 is a top plan view of a fabric according to the present invention.
  • Fig. 6 is a cross-sectional view of an electronic support according to the present invention.
  • Figs. 7 and 8 are cross-sectional views of alternate embodiments of an electronic support according to the present invention.
  • the fiber strands of the present invention have a unique coating that not only inhibits abrasion and breakage of the fibers during processing but also provides good wet-through, wet-out and dispersion properties in formation of composites.
  • Another significant advantage of the coated fiber strands of the present invention is good processability in weaving and knitting.
  • Low fuzz and halos, low broken filaments, low strand tension, high fliability and low insertion time are characteristics provided by the coated glass fiber strands of the present invention that facilitate weaving and knitting and consistently provide a fabric with few surface defects for printed circuit board applications.
  • composite materials made from the fiber strands of the present invention include good flexural strength, good interlaminar bond strength and good hydrolytic stability, i.e. resistance to migration of water along the fiber/matrix interface. Additionally, electronic supports and printed circuit boards made from the fiber strands in accordance with the present invention have good drillability and resistance to metal migration (also referred to as cathodic-anodic filament formation or CAF). In particular, printed circuit boards made from the fiber strand in accordance with the present invention have low tool wear during drilling and good locational accuracy of drilled holes.
  • a coated fiber strand 10 comprising a plurality of fibers 12, according to the present invention.
  • strand means a plurality of individual fibers.
  • fiber means an individual filament.
  • the fibers 12 typically have an average nominal fiber diameter ranging from about 3 to about 35 micrometers. Preferably the average nominal fiber diameter of the present invention is about 5 micrometers and greater. For "fine yarn” applications, the average nominal fiber diameter preferably ranges from about 5 to about 7 micrometers.
  • the fibers 12 can be formed from any type of fiberizable material known to those skilled in the art including fiberizable inorganic materials, fiberizable organic materials and mixtures and combinations thereof.
  • the inorganic and organic materials can be either man-made or naturally occurring materials.
  • the fiberizable inorganic and organic materials can also be polymeric materials.
  • polymeric material means a material formed from macromolecules composed of long chains of atoms that are linked together and that can become entangled in solution or in the solid state 2 .
  • fiberizable means a material capable of being formed into a generally continuous filament, fiber, strand or yarn.
  • the fibers 12 are formed from an inorganic, fiberizable glass material.
  • Fiberizable glass materials useful in the present invention include but are not limited to those prepared from fiberizable glass compositions such as "E-glass”, “A-glass”, “C-glass”, “D-glass”, “R-glass”, “S-glass”, and E-glass derivatives.
  • E-glass derivatives means glass compositions that include minor amounts of fluorine and/or boron and preferably are fluorine-free and/or boron-free.
  • minor means less than about 1 weight percent fluorine and less than about 5 weight percent boron.
  • Basalt and mineral wool are examples of other fiberizable glass materials useful in the present invention.
  • Preferred glass fibers are formed from E-glass or E-glass derivatives. Such compositions are well known to those skilled in the art and further discussion thereof is not believed to be necessary in view of the present disclosure.
  • the glass fibers of the present invention can be formed in any suitable method known in the art, for forming glass fibers.
  • glass fibers can be formed in a direct-melt fiber forming operation or in an indirect, or marble- melt, fiber forming operation. In a direct-melt fiber forming operation, raw materials are combined, melted and homogenized in a glass melting furnace. The molten glass moves from the furnace to a forehearth and into fiber
  • the glass fibers are preferably formed by the direct-melt fiber forming operation.
  • Non-limiting examples of suitable non-glass fiberizable inorganic materials include ceramic materials formed from silicon carbide, carbon, graphite, mullite, aluminum oxide and piezoelectric ceramic materials.
  • suitable fiberizable organic materials include cotton, cellulose, natural rubber, flax, ramie, hemp, sisal and wool.
  • suitable fiberizable organic polymeric materials include those formed from polyamides (such as nylon and aramids), thermoplastic polyesters (such as polyethylene terephthalate and polybutylene terephthalate), acrylics (such as polyacrylonitriles), polyolefins, polyurethanes and vinyl polymers (such as polyvinyl alcohol).
  • Non-glass fiberizable material useful in the present invention and methods for preparing and processing such fibers are discussed at length in the Encyclopedia of Polymer Science and Technology. Vol. 6 (1967) at pages 505-712, which is hereby incorporated by reference. It is understood that blends or copolymers of any of the above materials and combinations of fibers formed from any of the above materials can be used in the present invention, if desired.
  • the present invention will now be discussed generally in the context of glass fiber strands, although one skilled in the art would understand that the strand 10 can comprise fibers 12 formed from any fiberizable material known in the art as discussed above.
  • At least one and preferably all of the fibers 12 of fiber strand 10 of the present invention have a layer 14 of a residue of a coating composition on at least a portion 17 of the surfaces 16 of the fibers 12 to protect the fiber surfaces 16 from abrasion during processing and inhibit fiber breakage.
  • the layer 14 is present on the entire outer surface 16 or periphery of the fibers 12.
  • the coating compositions of the present invention are preferably aqueous coating compositions and more preferably aqueous, resin compatible coating compositions.
  • the coating compositions can contain volatile organic solvents such as alcohol or acetone as needed, but preferably are free of such solvents.
  • the coating compositions of the present invention can be used as primary sizing compositions and/or secondary sizing or coating compositions. As used herein, in a preferred embodiment the terms "size", "sized" or
  • sizing refer to a coating composition applied to the fibers.
  • primary size or “primary sizing” refer to the coating composition applied to the fibers immediately after formation of the fibers.
  • secondary size means coating compositions applied to the fibers after the application of a primary size. This coating can be applied to the fiber before the fiber is incorporated into a fabric or it can be applied to the fiber after the fiber is incorporated into a fabric , e.g. by coating the fabric.
  • the terms "size”, “sized” or “sizing” additionally refer to a coating composition (also known as a “finishing size”) applied to the fibers after at least a portion, and typically all of a conventional, non-resin compatible sizing composition has been removed by heat or chemical treatment, i.e., the finishing size is applied to bare glass fibers incorporated into a fabric form.
  • a coating composition also known as a “finishing size”
  • the term "resin compatible” means the coating composition applied to the glass fibers is compatible with the polymeric matrix material into which the glass fibers will be incorporated such that the coating composition (or selected coating components) does not require removal prior to incorporation into the matrix material (such as by heat cleaning), facilitates good wet-out and wet-through of the matrix material during processing and results in composite materials having desired physical properties and hydrolytic stability.
  • the coating composition of the present invention comprises one or more, and preferably a plurality of particles 18 that when applied to at least one fiber 23 of the plurality of fibers 12 adheres to the outer surface 16 of the at least one fiber 23 and provides one or more interstitial spaces 21 between adjacent glass fibers 23, 25 of the strand 10. These interstitial spaces 21 correspond generally to the average size 19 of the particles 18 positioned between the adjacent fibers.
  • the particles 18 of the present invention are preferably discrete particles. As used herein the term "discrete" means that the particles do not tend to coalesce or combine to form films under processing conditions, but instead generally retained their individual shape or form. In addition, the particles are preferably dimensionally stable.
  • the term "dimensionally stable particles” means that the particles will generally maintain their average particle size and shape under processing conditions, such as the forces generated between adjacent fibers during weaving, roving and other processing operations, so as to maintain the desired interstitial spaces between adjacent fibers 23, 25.
  • the particles preferably will not crumble, dissolve or substantially deform in the coating composition to form a particle having a maximum dimension less than its selected average particle size under typical glass fiber processing conditions, such as exposure to temperatures of up to about 25°C and preferably up to about 100°C, and more preferably up to about 140°C.
  • the particles 18 should not substantially enlarge or expand in size under glass fiber processing conditions and, more particularly, under composite processing conditions where the processing temperatures can exceed 150°C.
  • the phrase “should not substantially enlarge in size” in reference to the particles means that the particles should not expand or increase in size to more than approximately 3 times their initial size during processing.
  • the coating compositions of the present invention are essentially free of heat expandable hollow particles.
  • heat expandable hollow particles means hollow particles filled with or containing a blowing agent, which when exposed to temperatures sufficient to volatilize the blowing agent expand or substantially enlarge in size.
  • essentially free of means the sizing composition comprises less than about 20 weight percent of heat expandable hollow particles on a total solids basis, more preferably less than about 5 weight percent, and most preferably less than 0.001 weight percent.
  • the term “dimensionally stable” includes both crystalline and non-crystalline materials.
  • the particles 18 are non-waxy.
  • non-waxy means the materials from which the particles are formed are not wax-like.
  • wax-like means materials composed primarily of unentangled hydrocarbons chains having an average carbon chain length ranging from about 25 to about 100 carbon atoms 3,4 .
  • the particles 18 in the present invention are discrete, dimensionally stable, non-waxy particles.
  • the particles 18 can have any shape or configuration desired.
  • suitable particle shapes include spherical (such as beads, microbeads or hollow spheres), cubic, platy or acicular (elongated or fibrous).
  • the particles 18 can have an internal structure that is hollow, porous or void free, or a combination thereof.
  • the particles 18 can have a combination of these structures, e.g. a hollow center with porous or solid walls.
  • the particles 18 can be formed from materials selected from the group consisting of polymeric and non-polymeric inorganic materials, polymeric and non-polymeric organic materials, composite materials and mixtures thereof.
  • polymeric inorganic material means a polymeric material having a backbone repeat unit based on an element or elements other than carbon.
  • Polymeric organic materials include synthetic polymeric materials, semisynthetic polymeric materials and natural polymeric materials.
  • An "organic material”, as used herein, means all compounds of carbon except such binary compounds as the carbon oxides, the carbides, carbon disulfide, etc.; such ternary compounds as the metallic cyanides, metallic carbonyls, phosgene, carbonyl sulfide, etc.; and metallic
  • organic materials include carbon containing compounds wherein the carbon is typically bonded to itself and to hydrogen, and often to other elements as well and excludes carbon-containing ionic compounds. See M. Silberberg, Chemistry The Molecular Nature of Matter and Change, (1996) at page 586, which is hereby incorporated by reference.
  • inorganic material generally means all materials that are not compounds of carbon with the exception of carbon oxides and carbon disulfide. See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) at page 636 which are hereby incorporated by reference.
  • inorganic materials means any material that is not an organic material.
  • composite material means a combination of two or more different materials. For more information on particles useful in the present invention, see G. Wypych, Handbook of Fillers, 2nd Ed. (1999) at pages 15-202, which are hereby incorporated by reference.
  • Non-polymeric, inorganic materials useful in forming the particles 18 of the present invention include inorganic materials selected from the group consisting of metals, oxides, carbides, nitrides, borides, sulfides, silicates, carbonates, sulfates and hydroxides.
  • a non-limiting example of a suitable inorganic nitride from which the particles 18 are formed is boron nitride, which is the preferred inorganic material from which particles 18 useful in the present invention are formed.
  • a non-limiting example of a useful inorganic oxide is zinc oxide.
  • Suitable inorganic sulfides include molybdenum disulfide, tantalum disulfide, tungsten disulfide and zinc sulfide.
  • Useful inorganic silicates include aluminum silicates and magnesium silicates, such as
  • Suitable metals include molybdenum, platinum, palladium, nickel, aluminum, copper, gold, iron, silver and alloys and mixtures thereof.
  • the particles 18 are formed from solid lubricant materials.
  • solid lubricant means any solid used between two surfaces to provide protection from damage during relative movement and/or to reduce friction and wear.
  • the solid lubricants are inorganic solid lubricants.
  • inorganic solid lubricant means that the solid lubricants have a characteristic crystalline habit which causes them to shear into thin, flat plates which readily slide over one another and thus produce an antifriction lubricating effect between the glass fiber surface and an adjacent solid surface, at least one of which is in motion. See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary. (12th Ed.
  • Friction is the resistance to sliding one solid over another.
  • F. Clauss, Solid Lubricants and Self-Lubricating Solids, (1972) at page 1 which is hereby incorporated by reference.
  • the solid lubricant materials have a lamellar structure.
  • Solid lubricants having a lamellar structure are composed of sheets or plates of atoms in hexagonal array, with strong bonding within the sheet and weak van der Waals bonding between sheets, providing low shear strength between sheets.
  • a non-limiting example of a lamellar structure is a hexagonal crystal structure.
  • particles having a lamellar fullerene structure are also useful in the present invention.
  • Non-limiting examples of suitable inorganic solid lubricant materials having a lamellar structure that are useful in forming the particles 18 of the present invention include boron nitride, graphite, metal dichalcogenides, mica, talc, gypsum, kaolinite, calcite, cadmium iodide, silver sulfide and mixtures thereof.
  • Preferred inorganic solid lubricant materials include boron nitride, graphite, metal dichalcogenides and mixtures thereof.
  • Suitable metal dichalcogenides include molybdenum disulfide, molybdenum diselenide, tantalum disulfide, tantalum diselenide, tungsten disulfide, tungsten diselenide and mixtures thereof.
  • a non-limiting example of an inorganic solid lubricant material for use in the coating composition of the present invention having a hexagonal crystal structure is boron nitride. Particles formed from boron nitride, zinc sulfide and montmorillonite also provide good whiteness in composites with polymeric matrix materials such as nylon 6,6.
  • Non-limiting examples of particles formed from boron nitride that are suitable for use in the present invention are PolarTherm® 100 Series (PT 120, PT 140, PT 160 and PT 180), 300 Series (PT 350) and 600 Series (PT 620, PT 630, PT 640 and PT 670) boron nitride powder particles which are commercially available from Advanced Ceramics Corporation of Lakewood, Ohio. "PolarTherm® Thermally Conductive Fillers for Polymeric Materials” a technical bulletin of Advanced Ceramics Corporation of Lakewood, Ohio (1996), which is hereby incorporated by reference.
  • These particles have a thermal conductivity of about 250-300 Watts per meter °K at 25°C, a dielectric constant of about 3.9 and a volume resistivity of about 10 15 ohm-centimeters.
  • the 100 Series powder particles have an average particle size ranging from about 5 to about 14 micrometers
  • the 300 Series powder particles have an average particle size ranging from about 100 to about 150 micrometers
  • the 600 Series powder particles have an average particle size ranging from about 16 to greater than about 200 micrometers.
  • the particles 18 are formed from inorganic solid lubricant materials that are non-hydratable.
  • non-hydratable means that the solid inorganic lubricant particles do not react with molecules of water to form hydrates and contain water of hydration or water of crystallization.
  • a "hydrate” is produced by the reaction of molecules of water with a substance in which the H-OH bond is not split. See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) at pages 609-610 and T. Perros, Chemistry. (1967) at pages 186- 187, which are hereby incorporated by reference.
  • the coating composition is essentially free of hydratable inorganic solid lubricants.
  • the term "essentially free of means the coating composition comprises less than about 20 weight percent of hydratable inorganic lubricant particles on a total solids basis, more preferably less than about 5 weight percent, and most preferably less than 0.001 weight percent.
  • the coating compositions according to the present invention can contain particles formed from hydratable or hydrated inorganic solid lubricant materials in addition to the non-hydratable inorganic solid lubricant materials discussed above.
  • hydratable inorganic solid lubricant materials are clay mineral phyllosilicates, including micas (such as muscovite), talc, montmorillonite, kaolinite and gypsum.
  • the particles 18 can be formed from non-polymeric, organic materials. Examples of non-polymeric, organic materials useful in the present invention include but are not limited to stearates (such as zinc stearate and aluminum stearate), carbon black and stearamide.
  • the particles 18 can be formed from inorganic polymeric materials.
  • Non-limiting examples of useful inorganic polymeric materials include polyphosphazenes, polysilanes, polysiloxane, polygeremanes, polymeric sulfur, polymeric selenium, silicones and mixtures thereof.
  • a specific, non- limiting example of a particle formed from an inorganic polymeric material suitable for use in the present invention is Tospearl 5 , which is a particle formed from cross-linked siloxanes and is commercially available from Toshiba Silicones Company, Ltd. of Japan.
  • Suitable synthetic, organic polymeric materials from which the particles can be formed include, but are not limited to, thermosetting materials and thermoplastic materials.
  • Suitable thermosetting materials include thermosetting polyesters, vinyl esters, epoxy materials, phenolics, aminoplasts, thermosetting polyurethanes and mixtures thereof.
  • a specific, non-limiting example of a preferred synthetic polymeric particle formed from an epoxy material is an epoxy microgel particle.
  • Suitable thermoplastic materials include thermoplastic polyesters, polycarbonates, polyolefins, acrylic polymers, polyamides, thermoplastic polyurethanes, vinyl polymers and mixtures thereof.
  • Preferred thermoplastic polyesters include but are not limited to polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate.
  • Preferred polyolefins include but are not limited to polyethylene, polypropylene and polyisobutene.
  • Preferred acrylic polymers include copolymers of styrene and acrylic and polymers containing methacrylate.
  • ROPAQUE® HP-1055 6 which is an opaque, non-film-forming, styrene acrylic polymeric synthetic pigment having a 1.0 micrometer particle size, a solids content of 26.5 percent by weight and a 55 percent void volume
  • ROPAQUE® OP-96 7 which is an opaque, non-film-forming, styrene acrylic polymeric synthetic pigment dispersion having a particle size of 0.55 micrometers and a solids content of 30.5 percent by weight
  • ROPAQUE® OP-62 LO 8 which is also an opaque, non-film-forming, styrene acrylic polymeric synthetic pigment dispersion having a particles size of 0.40 micrometers and a solids content of about 36.5 percent by weight, each of which are commercially available from Rohm and Haas Company of Philadelphia, PA.
  • Suitable semisynthetic, organic polymeric materials from which the particles 18 can be formed include but are not limited to cellulosics, such as methylcellulose and cellulose acetate; and modified starches, such as starch acetate and starch hydroxyethyl ethers.
  • Suitable natural polymeric materials from which the particles 18 can be formed include but are not limited to polysaccharides, such as starch; polypeptides, such as casein; and natural hydrocarbons, such as natural rubber and gutta percha.
  • the polymeric particles 18 are formed from hydrophobic polymeric materials to reduce or limit moisture absorption by the coated strand.
  • hydrophobic polymeric materials believed to be useful in the present invention include but are not limited to polyethylene, polypropylene, polystyrene and
  • Non-limiting examples of polystyrene copolymers include ROPAQUE® HP-1055, ROPAQUE® OP-96, and ROPAQUE® OP-62 LO pigments (each discussed above).
  • polymeric particles 18 are formed from polymeric materials having a glass transition temperature (T g ) and/or melting point greater than about 25°C and preferably greater than about 50°C.
  • T g glass transition temperature
  • Composite particles 18 useful in the present invention include particles formed by cladding, encapsulating or coating particles formed from a primary material with one or more secondary materials.
  • an inorganic particle formed from an inorganic material such as silicon carbide or aluminum nitride can be provided with a silica, carbonate or nanoclay coating to form a useful composite particle.
  • a silane coupling agent with alkyl side chains can be reacted with the surface of an inorganic particle formed from an inorganic oxide to provide a useful composite particle having a "softer" surface.
  • Other examples include cladding, encapsulating or coating particles formed from organic or polymeric materials with inorganic materials or different organic or polymeric materials.
  • DUALITE is a synthetic polymeric particle coated with calcium carbonate that is commercially available from Pierce and Sevens Corporation of Buffalo, NY.
  • the particles 18 can be hollow particles formed from materials selected from the group consisting of inorganic materials, organic materials, polymeric materials, composite materials and mixtures thereof.
  • suitable materials from which the hollow particles can be formed are described above.
  • Non-limiting examples of a hollow polymeric particle useful in present invention are ROPAQUE® HP-1055, ROPAQUE® OP-96 and ROPAQUE® OP-62 LO pigments (each discussed above).
  • For other non-limiting examples of hollow particles that can be useful in the present invention see H. Katz et al. (Ed.) (1987) at pages 437-452 which are hereby incorporated by reference.
  • the particles 18 can be present in a dispersion, suspension or emulsion in water.
  • Other solvents such as mineral oil or alcohol (preferably less than about 5 weight percent), can be included in the dispersion, suspension or emulsion, if desired.
  • a non-limiting example of a preferred dispersion of particles formed from an inorganic material is ORPAC BORON NITRIDE RELEASECOAT-CONC, which is a dispersion of about 25 weight percent boron nitride particles in water and is commercially available from ZYP Coatings, Inc. of Oak Ridge, Tennessee. "ORPAC BORON NITRIDE RELEASECOAT-CONC", a technical bulletin of ZYP Coatings, Inc., is hereby incorporated by reference.
  • the boron nitride particles in this product have an average particle size of less than about 3 micrometers and include about 1 percent of magnesium-aluminum silicate to bind the boron nitride particles to the substrate to which the dispersion is applied.
  • Other useful products which are commercially available from ZYP Coatings include BORON NITRIDE LUBRICOAT® paint, and BRAZE STOP and WELD RELEASE products.
  • emulsions and dispersions of synthetic polymeric particles formed from acrylic polymers and copolymers include: Rhoplex® GL-623 9 which is an all acrylic firm polymer emulsion having a solids content of 45 percent by weight and a glass transition temperature of about 98°C; EMULSION E-2321 10 which is a hard, methacrylate polymer emulsion having a solids content of 45 percent by weight and a glass transition temperature of about 105°C; ROPAQUE® OP-96 (discussed
  • the particles 18 are selected to have a average particle size 19 sufficient to effect the desired spacing between adjacent fibers.
  • the average size 19 of the particles 18 incorporated into a sizing composition applied to fibers 12 to be processed on air-jet looms is preferably selected to provide sufficient spacing between adjacent fibers to permit air-jet transport of the fiber strand 10 across the loom.
  • air-jet loom means a type of loom in which the fill yarn (weft) is inserted into the warp shed by a blast of compressed air from one or more air jet nozzles.
  • the average size 19 of the particles 18 incorporated into a sizing composition applied to fibers 12 to be impregnated with a polymeric matrix material is selected to provide sufficient spacing between adjacent fibers to permit good wet-out and wet-through of the fiber strand 10.
  • the average particle size 19 of the particles 18 is at least about 0.1 micrometers, preferably at least about 0.5 micrometers, and ranges from about 0.1 micrometers to about 5 micrometers and preferably from about 0.5 micrometers to about 2.0 micrometers.
  • the particles 18 have an average particle sizes 19 that is generally smaller than the average diameter of the fibers 12 to which the coating composition is applied. It has been observed that twisted yarns made from fiber strands 10 having a layer 14 of a residue of a primary sizing composition comprising particles 18 having average particles sizes 19 discussed above can provide sufficient spacing between adjacent fibers 23, 25 to permit air-jet weavability (i.e. air-jet transport across the loom) while maintaining the integrity of the fiber strand 10 and providing acceptable "wet-through” and "wet-out” characteristics when impregnated with a polymeric matrix material.
  • the average particles size 19 of particles 18 is at least 3 micrometers, preferably at least about 5 micrometers, and ranges from 3 to about 1000 micrometers, preferably about 5 to about 1000 micrometers, and more preferably about 10 to about 25 micrometers.
  • each of the particles 18 has a minimum particle size of at least 3 micrometers, and preferably of at least about 5 micrometers.
  • the average particle size 19 of the particles 18 corresponds generally to the average nominal diameter of the glass fibers. It has been observed that fabrics made with strands coated with the particles of the sizes as discussed above exhibit good "wet-through” and "wet-out” characteristics when impregnated with a polymeric matrix material.
  • mixtures of one or more particles 18 having different average particle sizes 19 can be incorporated into the sizing composition in accordance with the present invention to impart the desired properties and processing characteristics to the fiber strands 10 and to the products subsequently made therefrom. More specifically, different sized particles can be combined in required amounts so as provide fibers having good air-jet transport properties as well a fabric exhibiting good wet-out and wet-through characteristics.
  • Glass fibers are subject to abrasive wear by contact with asperities of adjacent glass fibers and/or other solid objects or materials which the glass fibers contact during forming and subsequent processing, such as weaving or roving.
  • “Abrasive wear” means scraping or cutting off of bits of the glass fiber surface or breakage of glass fibers by frictional contact with particles, edges or entities of materials which are hard enough to produce damage to the glass fibers. See K. Ludema at page 129, which is hereby incorporated by reference. Abrasive wear of glass fiber strands causes strand breakage during processing and surface defects in products such as woven cloth and composites, which increases waste and manufacturing cost.
  • the particles 18 have a hardness value which does not exceed, i.e., is less than or equal to, a hardness value of the glass fiber(s).
  • the hardness values of the particles and glass fibers can be determined by any conventional hardness measurement method, such as Vickers or Brinell hardness, but is preferably determined according to the original Mohs' hardness scale which indicates the relative scratch resistance of the surface of a material.
  • the Mohs' hardness value of glass fibers generally ranges from about 4.5 to about 6.5, and is preferably about 6. R. Weast (Ed.), Handbook of Chemistry and Physics. CRC Press (1975) at page F-22, which is hereby incorporated by reference.
  • the Mohs' hardness value of the particles 18 preferably ranges from about 0.5 to about 6.
  • the Mohs' hardness values of several non-limiting examples of particles formed from inorganic materials suitable for use in the present invention are given in Table A below.
  • the particles 18 are thermally conductive, i.e., have a thermal conductivity greater than about 30 Watts per meter K, such as for example boron nitride, graphite, and the metallic inorganic solid lubricants discussed above.
  • the thermal conductivity of a solid material can be determined by any method known to one skilled in the art, such as the guarded hot plate method according to ASTM C-177-85 (which is hereby incorporated by reference) at a temperature of about 300K.
  • the particles 18 are electrically insulative or have high electrical resistivity, i.e., have an electrical resistivity greater than about 1000 microohm-cm, such as for example boron nitride.
  • the particles 18 can comprise about 1 to about 80 weight percent of the coating composition on a total solids basis, preferably about 1 to about 60 weight percent. In one embodiment, the coating composition contains about 20 to about 60 weight percent of particles 18 on total solids basis, and preferably about 35 to about 55 weight percent, and more preferably about 30 to about 50 weight percent.
  • discrete particles 18 of the coating composition can include any combination or mixture of particles 18 discussed above. More specifically, the particles 18 can include additional discrete particles made from any of the materials described above for forming the particles 18 in an amount less than the particles 18. These additional particles are different from the other particles 18 in the resin compatible coating composition, i.e. the addition particles (1) are chemically different from the other particles; or (2) are chemically the same but different in configuration or properties. The additional particles can comprise up to half of the particles 18, preferably up to about 1 5 percent of the particles 1 8.
  • the coating composition preferably comprises one or more polymeric film-forming materials, such as organic, inorganic and natural polymeric materials.
  • polymeric film-forming materials include but are not limited to synthetic polymeric materials, semisynthetic polymeric materials, natural polymeric materials and mixtures thereof.
  • Synthetic polymeric materials include but are not limited to thermoplastic materials and thermosetting materials.
  • the polymeric film-forming materials form a generally continuous film when applied to the surface 16 of the glass fibers.
  • the amount of polymeric film-forming materials can range from about 1 to about 60 weight percent of the coating composition on a total solids basis, preferably about 5 to about 50 weight percent, and more preferably about 10 to about 30 weight percent.
  • thermosetting polymeric film-forming materials are the preferred polymeric film-forming materials for use in the coating composition for coating glass fiber strands. Such materials are compatible with thermosetting matrix materials used as laminates for printed circuit boards, such as FR-4 epoxy resins, which are polyfunctional epoxy resins and in one particular embodiment of the invention is a difunctional brominated epoxy resins. See Electronic Materials HandbookTM. ASM International (1989) at pages 534-537, which are hereby incorporated by reference.
  • Useful thermosetting materials include thermosetting polyesters, epoxy materials, vinyl esters, phenolics, aminoplasts, thermosetting polyurethanes and mixtures thereof. Suitable thermosetting polyesters include STYPOL polyesters that are commercially available from Cook Composites and Polymers of Port Washington, Wisconsin and NEOXIL polyesters that are commercially available from DSM B.V. of Como, Italy.
  • thermosetting polymeric material is an epoxy material.
  • Useful epoxy materials contain at least one epoxy or oxirane group in the molecule, such as polyglycidyl ethers of polyhydric alcohols or thiols.
  • suitable epoxy film-forming polymers include EPON® 826 and EPON® 880 epoxy resins, which are commercially available from Shell Chemical Company of Houston, Texas.
  • thermoplastic polymeric materials include vinyl polymers, thermoplastic polyesters, polyolefins, polyamides (e.g. aliphatic polyamides or aromatic polyamides such as aramid), thermoplastic polyurethanes, acrylic polymers (such as polyacrylic acid) and mixtures thereof.
  • the preferred polymeric film-forming material is a vinyl polymer.
  • Useful vinyl polymers in the present invention include, but are not limited to, polyvinyl pyrrolidones such as PVP K-15, PVP K-30, PVP K-60 and PVP K-90, each of which is commercially available from ISP Chemicals of Wayne, New Jersey.
  • Other suitable vinyl polymers include Resyn 2828 and Resyn 1037 vinyl acetate copolymer emulsions which are commercially available from National Starch Starch and Chemical of Bridgewater, New Jersey, other polyvinyl acetates such as are commercially available from H. B. Fuller and Air Products and Chemicals Company of Allentown, Pennsylvania, and polyvinyl alcohols which are also available from Air Products and Chemicals Company.
  • Thermoplastic polyesters useful in the present invention include DESMOPHEN 2000 and DESMOPHEN 2001 KS, both of which are commercially available from Bayer of Pittsburgh, Pennsylvania.
  • Preferred polyesters include RD-847A polyester resin which is commercially available from Borden Chemicals of Columbus, Ohio, and DYNAKOLL SI 100 resin which is commercially available from Eka Chemicals AB, Sweden.
  • Useful polyamides include the VERSAMID products that are commercially available from General Mills Chemicals, Inc.
  • Useful thermoplastic polyurethanes include WITCOBOND® W-290H, which is commercially available from Witco Chemical Corp. of Chicago, Illinois, and RUCOTHANE® 2011 L polyurethane latex, which is commercially available from Ruco Polymer Corp. of Hicksville, New York.
  • the aqueous sizing composition of the present invention can comprise a mixture of one or more thermosetting polymeric materials with one or more thermoplastic polymeric materials.
  • the polymeric materials of the aqueous sizing composition comprise a mixture of RD-847A polyester resin, PVP K-30 polyvinyl pyrrolidone, DESMOPHEN 2000 polyester and VERSAMID polyamide.
  • the polymeric materials of the aqueous sizing composition comprise PVP K-30 polyvinyl pyrrolidone, optionally combined EPON 826 epoxy resin.
  • Semisynthetic polymeric materials suitable for use as polymeric film- formers include but are not limited to cellulosics such as hydroxypropylcellose and modified starches such as KOLLOTEX 1250 (a low viscosity, low amylose potato-based starch etherified with ethylene oxide) which is commercially available from AVEBE of the Netherlands
  • Natural polymeric materials suitable for use as polymeric film-formers include but are not limited to starches prepared from potatoes, corn, wheat, waxy maize, sago, rice, milo and mixtures thereof.
  • the starch can function as both a particle 18 and/or a film former. More specifically, some starches will dissolve completely in a solvent, and in particular water, and function as a film forming material while others will not completely dissolve and will maintain a particular grain size and function as a particle 18.
  • starches both natural and semisynthetic
  • the coating composition of the present invention is preferably essentially free of starch materials.
  • the term "essentially free of starch materials" means that the coating composition comprises less than 20 weight percent on a total solids basis of the coating composition, preferably less than 5 weight percent and more preferably is free of starch materials.
  • Primary sizing compositions containing starches that are applied to fiber strands to be incorporated into laminates for printed circuit boards are typically not resin compatible and must be removed prior to incorporation into the polymeric matrix material.
  • the coating compositions of the present invention are resin compatible and do not require removal. More preferably, the coating compositions of the present invention are compatible with matrix materials used to make printed circuit boards (discussed below) and most preferably are epoxy resin compatible.
  • the polymeric film-forming materials can be water soluble, emulsifiable, dispersible and/or curable. As used herein, "water soluble" means that the polymeric materials are capable of being essentially uniformly blended and/or molecularly or ionically dispersed in water to form a true solution.
  • Embodiable means that the polymeric materials are capable of forming an essentially stable mixture or being suspended in water in the presence of an emulsifying agent. See Hawley's at page 461 , which is hereby incorporated by reference. Non-limiting examples of suitable emulsifying agents are set forth below.
  • Disposible means that any of the components of the polymeric materials are capable of being distributed throughout water as finely divided particles, such as a latex. See Hawley's at page 435, which is hereby incorporated by reference.
  • the uniformity of the dispersion can be increased by the addition of wetting, dispersing or emulsifying agents (surfactants), which are discussed below.
  • “Curable” means that the polymeric materials and other components of the sizing composition are capable of being coalesced into a film or crosslinked to each other to change the physical properties of the polymeric materials. See Hawley's at page 331 , which is hereby incorporated by reference.
  • the coating composition preferably comprises one or more glass fiber coupling agents such as organo-silane coupling agents, transition metal coupling agents, phosphonate coupling agents, aluminum coupling agents, amino-containing Werner coupling agents and mixtures thereof. These coupling agents typically have dual functionality.
  • Each metal or silicon atom has attached to it one or more groups which can either react with or compatibilize the fiber surface and/or the components of the resin matrix.
  • the term "compatibilize” means that the groups are chemically attracted, but not bonded, to the fiber surface and/or the components of the coating composition, for example by polar, wetting or solvation forces.
  • each metal or silicon atom has attached to it one or more hydrolyzable groups that allow the coupling agent to react with the glass fiber surface, and one or more functional groups that allow the coupling agent to react with components of the resin matrix. Examples of hydrolyzable groups include:
  • R 1 is C r C 3 alkyl
  • R 2 is H or C C 4 alkyl
  • R 3 and R 4 are independently selected from H, C C 4 alkyl or C 6 -C 8 aryl
  • R 5 is C 4 -C 7 alkylene.
  • suitable compatibilizing or functional groups include epoxy, glycidoxy, mercapto, cyano, allyl, alkyl, urethano, halo, isocyanato, ureido, imidazolinyl, vinyl, acrylato, methacrylato, amino or polyamino groups.
  • Functional organo-silane coupling agents are preferred for use in the present invention.
  • useful functional organo silane coupling agents include gamma-aminopropyltrialkoxysilanes, gamma- isocyanatopropyltriethoxysilane, vinyl-trialkoxysilanes, glycidoxypropyltrialkoxysilanes and ureidopropyltrialkoxysilanes.
  • Preferred functional organo-silane coupling agents include A-187 gamma-glycidoxy- propyltrimethoxysilane, A-174 gamma-methacryloxypropyltrimethoxysilane, A-1100 gamma-aminopropyltriethoxysilane silane coupling agents, A-1108 amino silane coupling agent and A-1160 gamma-ureidopropyltriethoxysilane (each of which are commercially available from Witco Corporation OSi Specialties, Inc. of Tarrytown, New York).
  • the organo silane coupling agent can be at least partially hydrolyzed with water prior to application to the fibers, preferably at about a 1 :1 stoichiometric ratio or, if desired, applied in unhydrolyzed form.
  • the pH of the water can be modified by the addition of an acid or a base to initiate or speed the hydrolysis of the coupling agent as is well known in the art.
  • Suitable transition metal coupling agents include titanium, zirconium, yttrium and chromium coupling agents.
  • Suitable titanate coupling agents and zirconate coupling agents are commercially available from Kenrich
  • Suitable chromium complexes are commercially available from E.I. duPont de Nemours of Wilmington, Delaware.
  • the amino- containing Werner-type coupling agents are complex compounds in which a trivalent nuclear atom such as chromium is coordinated with an organic acid having amino functionality.
  • Other metal chelate and coordinate type coupling agents known to those skilled in the art can be used herein.
  • the amount of coupling agent can range from about 1 to about 30 weight percent of the coating composition on a total solids basis, preferably about 1 to about 10 weight percent, and more preferably about 2 to about 8 weight percent.
  • the coating composition can further comprise one or more softening agents or surfactants that impart a uniform charge to the surface of the fibers causing the fibers to repel from each other and reducing the friction between the fibers, so as to function as a lubricant.
  • the softening agents are chemically different from other components of the coating composition.
  • Such softening agents include cationic, non-ionic or anionic softening agents and mixtures thereof, such as amine salts of fatty acids, alkyl imidazoline derivatives such as CATION X, which is commercially available from Rhone Poulenc of Princeton, New Jersey, acid solubilized fatty acid amides, condensates of a fatty acid and polyethylene imine and amide substituted polyethylene imines, such as EMERY® 6717, a partially amidated polyethylene imine commercially available from Henkel Corporation of Kankakee, Illinois.
  • the coating composition can comprise up to about 60 weight percent of softening agents, preferably the coating composition comprises less than about 20 weight percent and more preferably less than about 5 weight percent of the softening agents.
  • the coating composition can further include one or more lubricious materials that are chemically different from the polymeric materials and softening agents discussed above to impart desirable processing characteristics to the fiber strands during weaving.
  • Suitable lubricious materials can be selected from the group consisting of oils, waxes, greases and mixtures thereof.
  • wax materials useful in the present invention include aqueous soluble, emulsifiable or dispersible wax materials such as vegetable, animal, mineral, synthetic or petroleum waxes, e.g. paraffin.
  • Oils useful in the present invention include both natural oils, semisynthetic oils and synthetic oils.
  • the amount of wax or other lubricious material can range from 0 to about 80 weight percent of the sizing composition on a total solids basis, preferably from about 1 to about 50 weight percent, more preferably from about 20 to about 40 weight percent, and most preferably from about 25 to about 35 weight percent.
  • Preferred lubricious materials include waxes and oils having polar characteristics, and more preferably include highly crystalline waxes having polar characteristics and melting points above about 35°C and more preferably above about 45°C.
  • Such materials are believed to improve the wet-out and wet-through of polar resins on fiber strands coated with sizing compositions containing such polar materials as compared to fiber strands coated with sizing compositions containing waxes and oils that do not have polar characteristics.
  • Preferred lubricious materials having polar characteristics include esters formed from reacting (1) a monocarboxlyic acid and (2) a monohydric alcohol.
  • Non-limiting examples of such fatty acid esters useful in the present invention include cetyl palmitate, which is preferred (such as is available from Stepan Company of Maywood, New Jersey as KESSCO 653 or STEPANTEX 653), cetyl myristate (also available from Stepan Company as STEPANLUBE 654), cetyl laurate, octadecyl laurate, octadecyl myristate, octadecyl palmitate and octadecyl stearate.
  • fatty acid ester, lubricious materials useful in the present invention include trimethylolpropane tripelargonate, natural spermaceti andtriglyceride oils, such as but not limited to soybean oil, linseed oil, epoxidized soybean oil, and epoxidized linseed oil.
  • the coating composition can include one or more other lubricious materials, such as non-polar petroleum waxes, in lieu of or in addition to of those lubricious materials discussed above.
  • non-polar petroleum waxes include MICHEM® LUBE 296 microcrystalline wax, POLYMEKON® SPP-W microcrystalline wax and PETROLITE 75 microcrystalline wax which are commercially available from Michelman Inc. of Cincinnati, Ohio and the Petrolite Corporation of Tulsa, Oklahoma, respectively.
  • the coating composition can also include a resin reactive diluent to further improve lubrication of the coated fiber strands of the present invention and provide good processability in weaving and knitting by reducing the potential for fuzz, halos and broken filaments during such manufacturing operations, while maintaining resin compatibility.
  • resin reactive diluent means that the diluent includes functional groups that are capable of chemically reacting with the same resin with which the coating composition is compatible.
  • the diluent can be any lubricant with one or more functional groups that react with a resin system, preferably functional groups that react with an epoxy resin system, and more preferably functional groups that react with an FR-4 epoxy resin system.
  • Non-limiting examples of suitable lubricants include lubricants with amine groups, alcohol groups, anhydride groups, acid groups or epoxy groups.
  • a non-limiting example of a lubricant with an amine group is a modified polyethylene amine, e.g. EMERY 671 7, which is a partially amidated polyethylene imine commercially available from Henkel Corporation of Kankakee, Illinois.
  • a non-limiting example of a lubricant with an alcohol group is polyethylene glycol, e.g. CARBOWAX 300, which is a polyethylene glycol that is commercially available from Union Carbide of Danbury, Connecticut.
  • a non-limiting example of a lubricant with an acid group is fatty acids, e.g.
  • Non-limiting examples of lubricants with an epoxy group include epoxidized soybean oil and epoxidized linseed oil, e.g. FLEXOL LOE, which is an epoxidized linseed oil, and FLEXOL EPO, which is an epoxidized soybean oil, both commercially available from Union Carbide of Danbury, Connecticut, and LE-9300 epoxidized silicone emulsion, which is commercially available from Witco Corporation OSi Specialties, Inc. of
  • the sizing composition can include a resin reactive diluent as discussed above in an amount up to about 1 5 weight percent of the sizing composition on a total solids basis.
  • the coating composition can include one or more emulsifying agents for emulsifying or dispersing components of the sizing composition, such as the particles 18 and/or lubricious materials.
  • Non-limiting examples of suitable emulsifying agents or surfactants include polyoxyalkylene block copolymers (such as PLURONICTM F-108 polyoxypropylene-polyoxyethylene copolymer which is commercially available from BASF Corporation of Parsippany, New Jersey), ethoxylated alkyl phenols (such as IGEPAL CA-630 ethoxylated octylphenoxyethanol which is commercially available from GAF Corporation of Wayne, New Jersey), polyoxyethylene octylphenyl glycol ethers, ethylene oxide derivatives of sorbitol esters (such as TMAZ 81 which is commercially available BASF of Parsippany, New Jersey), polyoxyethylated vegetable oils (such as ALKAMULS EL-719, which is commercially available from Rhone- Poulenc), ethoxylated alkylphenols (such as MACOL OP-10 which is also commercially available from BASF) and nonylphenol surfactants (such as MA
  • Crosslinking materials such as melamine formaldehyde
  • plasticizers such as phthalates, trimellitates and adipates
  • the amount of crosslinker or plasticizer can range from about 1 to about 5 weight percent of the coating composition on a total solids basis.
  • silicones such as silicones, fungicides, bactericides and anti-foaming materials, generally in an amount of less than about 5 weight percent.
  • Organic and/or inorganic acids or bases in an amount sufficient to provide the coating composition with a pH of about 2 to about 10 can also be included in the coating composition.
  • a non-limiting example of a suitable silicone emulsion is LE-9300 epoxidized silicone emulsion, which is commercially available from Witco Corporation OSi Specialties, Inc. of Danbury, Connecticut.
  • An example of a suitable bactericide is Biomet 66 antimicrobial compound, which is commercially available from M & T Chemicals of Rahway, New Jersey.
  • Suitable anti- foaming materials are the SAG materials, which are commercially available from OSi Specialties, Inc. of Danbury, Connecticut and MAZU DF-136, which is available from BASF Company of Parsippany, New Jersey.
  • Ammonium hydroxide can be added to the coating composition for coating stabilization, if desired.
  • Preferably water and more preferably deionized water is included in the coating composition in an amount sufficient to facilitate application of a generally uniform coating upon the strand.
  • the weight percentage of solids of the coating composition generally ranges from about 1 to about 20 weight percent.
  • the coating composition is preferably essentially free of glass materials.
  • "essentially free of glass materials” means that the sizing composition comprises less than 20 volume percent of glass matrix materials for forming glass composites, preferably less than about 5 volume percent, and more preferably is free of glass materials.
  • glass matrix materials include black glass ceramic matrix materials or aluminosilicate matrix materials such as are well known to those skilled in the art.
  • glass fibers of the coated fiber strand of the present invention have a primary layer of a dried residue of an aqueous primary sizing composition comprising ROPAQUE® HP-1055 or ROPAQUE® OC-96 styrene acrylic polymeric synthetic pigments, PVP K-30 polyvinyl pyrrolidone, A-174 acrylic- functional organo silane coupling agents and A-187 epoxy-functional organo silane coupling agents, EMERY® 6717 partially amidated polyethylene imine, STEPANTEX 653 cetyl palmitate, TMAZ 81 ethylene oxide derivatives of sorbitol esters, MACOL OP-10 ethoxylated alkylphenol and MAZU DF-136 anti-foaming material.
  • an aqueous primary sizing composition comprising ROPAQUE® HP-1055 or ROPAQUE® OC-96 styrene acrylic polymeric synthetic pigments, PVP K-30 polyvinyl pyrrolidone, A-174 acrylic- functional organo silane
  • glass fibers of the coated fiber strand of the present invention have applied thereto a primary layer of a dried residue of an aqueous primary sizing composition
  • an aqueous primary sizing composition comprising ROPAQUE® HL-1055 or ROPAQUE® OC-96 styrene-acrylic copolymer hollow spheres, PolarTherm® 160 boron nitride powder and/or ORPAC BORON NITRIDE RELEASECOAT- CONC dispersion, PVP K-30 polyvinyl pyrrolidone, A-174 acrylic-functional organo silane coupling agents and A-187 epoxy-functional organo silane coupling agents, EMERY® 6717 partially amidated polyethylene imine, STEPANTEX 653 cetyl palmitate, TMAZ 81 ethylene oxide derivatives of sorbitol esters, MACOL OP-10 ethyoxylated alkylphenol, and MAZU DF-136 anti-foaming material.
  • fiber strands having a residue of a coating composition similar to those described above that are free of particles 18 can be made in accordance with the present invention.
  • aqueous, resin compatible sizing compositions including one or more film-forming polymeric materials, such as PVP K-30 polyvinyl pyrrolidone; one or more silane coupling agents, such as A-174 acrylic- functional organo silane coupling agents and A-187 epoxy-functional organo silane coupling agents; and at least about 25 percent by weight of the sizing composition on a total solids basis of a lubricious material having polar characteristics, such as STEPANTEX 653 cetyl palmitate, can be made in accordance with the present invention.
  • fiber strands having a residue of an aqueous, resin compatible sizing composition that is essentially free of particles 18 can be woven into fabrics and made into electronic supports and electronic circuit boards (as described below) in accordance with the present invention.
  • the coating compositions of the present invention can be prepared by any suitable method such as conventional mixing well known to those skilled in the art. Preferably the components discussed above are diluted with water to have the desired weight percent solids and mixed together. The particles 18 can be premixed with water, emulsified or otherwise added to one or more components of the coating composition prior to mixing with the remaining components of the coating.
  • Sizing compositions according to the present invention can be applied in many ways, for example by contacting the filaments with a roller or belt applicator, spraying or other means.
  • the sized fibers are preferably dried at room temperature or at elevated temperatures. The dryer removes excess moisture from the fibers and, if present, cures any curable sizing composition components. The temperature and time for drying the glass fibers will depend upon such variables as the percentage of solids in the sizing composition, components of the sizing composition and type of glass fiber.
  • the amount of the coating composition present as a dried residue on the fiber strand is preferably less than about 30 percent by weight, more preferably less than about 10 percent by weight and most preferably less than about 5 percent by weight as measured by loss on ignition (LOI). In one embodiment of the invention, the LOI is less than 1 percent by weight.
  • the term "loss on ignition” means the weight percent of dried coating composition present on the surface of the fiber strand as determined by the following equation (Eq.1):
  • LOI 100 x [(W dry -W bare )/W dry ] Eq. 1 wherein W dry is the weight of the fiber strand plus the residue of the coating composition after drying in an oven at about 220°F (about 104°C) for about 60 minutes and W bar ⁇ is the weight of the bare fiber strand after removal of residue of the coating composition by heating the fiber strand in an oven at about 1150°F (about 621 °C) for about 20 minutes. After the application of the primary size, the fibers are gathered into strands having 2 to about 15,000 fibers per strand, and preferably about 100 to about 1600 fibers per strand..
  • a secondary layer of a secondary sizing or secondary coating composition can be applied over the primary layer in an amount effective to coat or impregnate the portion of the strands, for example by dipping the coated strand in a bath containing the secondary coating composition, spraying the secondary coating composition upon the coated strand or by contacting the coated strand with an applicator as discussed above.
  • the coated strand can be passed through a die to remove excess coating composition from the strand and/or dried as discussed above for a time sufficient to at least partially dry or cure the secondary coating composition.
  • the method and apparatus for applying the secondary coating composition to the strand is determined in part by the configuration of the strand material.
  • the strand is preferably dried after application of the secondary coating composition in a manner well known in the art.
  • Suitable secondary coating compositions can include one or more film- forming materials, lubricants and other additives such as are discussed above.
  • the secondary coating is preferably different from the primary sizing composition, i.e. it (1) contains at least one component which is chemically different from the components of the sizing composition; or (2) contains at least one component in an amount which is different from the amount of the same component contained in the sizing composition.
  • suitable secondary coating compositions including polyurethane are disclosed in U.S. Patent Nos. 4,762,750 and 4,762,751 , which are hereby incorporated by reference.
  • the glass fibers 212 of the coated fiber strand 210 can having applied thereto a primary layer 214 of a dried residue of a primary sizing composition which can include any of the sizing components in the amounts discussed above.
  • a primary sizing composition which can include any of the sizing components in the amounts discussed above. Examples of suitable sizing compositions are set forth in Loewenstein at pages 237-291 (3d Ed. 1993) and U.S. Patent Nos. 4,390,647 and 4,795,678, each of which is hereby incorporated by reference.
  • a secondary layer 215 of a secondary coating composition is applied to at least a portion, and preferably over the entire outer surface, of the primary layer 214.
  • the secondary coating composition comprises one or more types of discrete particles 216 such as are discussed in detail above.
  • the amount of particles in the secondary coating composition can range from about 1 to about 99 weight percent on a total solids basis and preferably about 20 to about 90 weight percent.
  • the particles of the secondary coating composition comprise hydrophilic inorganic solid particles that absorb and retain water in the interstices of the hydrophilic particles.
  • the hydrophilic inorganic solid particles can absorb water or swell when in contact with water or participate in a chemical reaction with the water to form, for example, a viscous gel-like solution which blocks or inhibits further ingress of water into the interstices of a telecommunications cable which the coated glass fiber strand is used to reinforce.
  • “absorb” means that the water penetrates the inner structure or interstices of the hydrophilic material and is substantially retained therein. See Hawley's Condensed Chemical Dictionary at page 3, which is hereby incorporated by reference.
  • “Swell” means that the hydrophilic particles expand in size or volume. See Webster's New Collegiate Dictionary (1977) at page 1178, which is hereby incorporated by reference.
  • the hydrophilic particles swell after contact with water to at least one and one-half times their original dry weight, and more preferably about two to about six times their original weight.
  • Non-limiting examples of hydrophilic inorganic solid lubricant particles that swell include smectites such as vermiculite and montmorillonite, absorbent zeolites and inorganic absorbent gels.
  • these hydrophilic particles are applied in powder form over tacky sizing or other tacky secondary coating materials.
  • the amount of hydrophilic inorganic particles in this embodiment of the secondary coating composition can range from about 1 to about 99 weight percent on a total solids basis and preferably about 20 to about 90 weight percent.
  • a tertiary layer 320 of a tertiary coating composition can be applied to at least a portion of the surface, and preferably over the entire surface, of a secondary layer 315, i.e. such a fiber strand 312 would have a primary layer 314 of a primary sizing, a secondary layer 315 of a secondary coating composition and a tertiary, outer layer 320 of the tertiary coating.
  • the tertiary coating is preferably different from the primary sizing composition and the secondary coating composition, i.e.
  • the tertiary coating composition (1) contains at least one component which is chemically different from the components of the primary sizing and secondary coating composition; or (2) contains at least one component in an amount which is different from the amount of the same component contained in the primary sizing or secondary coating composition.
  • the secondary coating composition comprises one or more polymeric materials discussed above, such as polyurethane
  • the tertiary powdered coating composition comprises solid particles, such as the PolarTherm® boron nitride particles, and hollow particles, such as ROPAQUE® pigments, which are discussed above.
  • the powdered coating is applied by passing the strand having a liquid secondary coating composition applied thereto through a fluidized bed or spray device to adhere the powder particles to the tacky secondary coating composition.
  • the strands can be assembled into a fabric 810 before the layer 812 of tertiary coating is applied, as shown in Fig. 8.
  • the weight percent of powdered solid particles adhered to the coated fiber strand 310 can range from about 0.1 to about 30 weight percent of the total weight of the dried strand.
  • the tertiary powdered coating can also include one or more polymeric materials such as are discussed above, such as acrylic polymers, epoxies, or polyolefins, conventional stabilizers and other modifiers known in the art of such coatings, preferably in dry powder form.
  • polymeric materials such as are discussed above, such as acrylic polymers, epoxies, or polyolefins, conventional stabilizers and other modifiers known in the art of such coatings, preferably in dry powder form.
  • coated fiber strands 10, 210, 310 discussed above can be used as continuous strand or further processed into diverse products such as chopped strand, twisted strand, roving and/or fabric, such as wovens, nonwovens, knits and mats.
  • the coated fiber strands used as warp and weft (i.e. fill) strands of a fabric can be non-twisted (also referred to as untwisted or zero twist) or twisted prior to weaving and the fabric can include various combinations of both twisted and non-twisted warp and weft strands.
  • the present invention also includes an embodiment wherein the coating composition of the present invention is applied to a fabric after it has been manufactured using various techniques well known in the art.
  • the coating composition of the present invention can be applied either directly to the glass fibers in the fabric or to another coating already on the glass fibers and/or fabric.
  • the glass fibers can be coated with a conventional starch-oil sizing after forming and woven into a fabric. The fabric can then be treated to remove starch-oil sizing prior to applying the coating composition of the present invention.
  • This sizing removal can be accomplished using techniques well known in the art, such as thermal treatment or washing of the fabric.
  • the coating composition would directly coat the surface of the fibers of the fabric. If any portion of the sizing composition initially applied to the glass fibers after forming is not removed, the coating composition of the present invention would then be applied over the remaining portion of the sizing composition rather than directly to the fiber surface.
  • selected components of the coating composition of the present invention can be applied to the glass fibers immediately after forming and the remaining components of the coating composition can be applied to the fabric after it is made. In a manner similar to that discussed above, some or all of the selected components can be removed from the glass fibers prior to coating the fibers and fabric with the remaining components. As a result, the remaining components will either directly coat the surface of the fibers of the fabric or coat those selected components that were not removed from the fiber surface.
  • coated fiber strands 10, 210, 310 and products formed therefrom can be used in a wide variety of applications, but are preferably used as reinforcements 410 for reinforcing polymeric matrix materials 412 to form a composite 414, such as is shown in Fig. 4, which will be discussed in detail below.
  • Such applications include but are not limited to laminates for printed circuit boards, reinforcements for telecommunications cables, and various other composites.
  • coated strands of the present invention are compatible with typical polymeric matrix resins used to make electronic supports and printed circuit board and are suitable for use on air-jet looms, which are commonly used to make the reinforcing fabrics for such applications.
  • Conventional sizing compositions applied to fibers to be woven using air-jet looms include components (such as starches and oils) that are generally not compatible with such resin systems. It has been observed that weaving characteristics of fiber strands coated with a residue of a primary sizing composition comprising particles 18 in accordance with the present invention approximate the weaving characteristics of fiber strands coated with conventional starch/oil based sizing compositions and are compatible with FR-4 epoxy resins.
  • the particles 18 of the instant invention function in a manner similar to the starch component of conventional starch/oil sizing compositions during processing and air-jet weaving by providing the necessary fiber separation and air drag for the air jet weaving operation while further providing compatibility with the epoxy resin system that is not typical of conventional starch/oil sizing compositions. More specifically, the particles 18 contribute a dry, powder characteristic to the coating similar to the dry lubricant charactistics of a starch coating.
  • the coated strands of the present invention provides interstices between the fibers of the strand which facilitate flow of the matrix materials therebetween to more quickly and/or uniformly wet-out and wet-through the fibers of the strand.
  • the amount of particles can exceed 20 weight percent of the total solids of the coating composition applied to the fibers, yet still be adequately adhered to the fibers and provide strands having handling characteristics at least comparable to strands without the particle coating.
  • coated fiber strands 510 made according to the present invention can be used as warp and/or weft strands 514, 516 in a knit or woven fabric 512 reinforcement, preferably to form a laminate for a printed circuit board (shown in Figs. 6-8).
  • the warp strands 514 can be twisted prior to use by any conventional twisting technique known to those skilled in the art, for example by using twist frames to impart twist to the strand at about 0.5 to about 3 turns per inch.
  • the reinforcing fabric 512 can include about 5 to about 100 warp strands 514 per centimeter (about 13 to 254 warp strand per inch) and preferably has about 6 to about 50 weft strands per centimeter (about 15 to about 127 weft strands per inch).
  • the weave construction can be a regular plain weave or mesh (shown in Fig. 5), although any other weaving style well known to those skilled in the art, such as a twill weave or satin weave, can be used.
  • a suitable woven reinforcing fabric 512 can be formed by using any conventional loom well known to those skilled in the art, such as a shuttle loom, air jet loom or rapier loom, but preferably is formed using an air jet loom (discussed above).
  • Preferred air jet looms are commercially available from Tsudakoma of Japan as Model Nos. 103, 1031 1033 or ZAX; Sulzer Ruti Model Nos. L-5000, L-5100 or L-5200 which are commercially available from Sulzer Brothers LTD. of Zurich, Switzerland; and Toyoda Model No. JAT610.
  • the fabric of the present invention is preferably woven in a style which is suitable for used in a laminate for an electronic support or printed circuit board, such as are disclosed in "Fabrics Around the World”, a technical bulletin of Clark-Schwebel, Inc. of Anderson, South Carolina (1 995), which is hereby incorporated by reference.
  • a non-limiting fabric style using E225 E-glass fiber yarns is Style 21 1 6, which has 1 1 8 warp yarns and 1 14 fill (or weft) yarns per 5 centimeters (60 warp yarns and 58 fill yarns per inch); uses 7 22 1 x0 (E225 1 /0) warp and fill yarns; has a nominal fabric thickness of about 0.094 millimeters (about 0.037 inches); and a fabric weight (or basis weight) of about 103.8 grams per square meter (about 3.06 ounces per square yard).
  • a non-limiting example of a fabric style using G75 E-glass fiber yarns is
  • Style 7628 which has 87 warp yarns and 61 fill yarns per 5 centimeters (44 warp yarns and 31 fill yarns per inch); uses 9 68 1 x0 (G75 1 /0) warp and fill yarns; has a nominal fabric thickness of about 0.1 73 millimeters (about 0.0068 inches); and a fabric weight of about 203.4 grams per square meter (about 6.00 ounces per square yard).
  • a non-limiting example of a fabric style using D450 E-glass fiber yarns is Style 1 080, which has 1 1 8 warp yarns and 93 fill yarns per 5 centimeters (60 warp yarns and 47 fill yarns per inch); uses 5 1 1 1 x0 (D450 1 /0) warp and fill yarns; has a nominal fabric thickness of about 0.053 millimeters (about 0.0021 inches); and a fabric weight of about 46.8 grams per square meter (about 1 .38 ounces per square yard).
  • a non-limiting example of a fabric style using D900 E-glass fiber yarns is Style 1 06, which has 1 1 0 warp yarns and 1 1 0 fill yarns per 5 centimeters (56 warp yarns and 56 fill yarns per inch); uses 5 5.5 1 x0 (D900 1 /0) warp and fill yarns; has a nominal fabric thickness of about 0.033 millimeters (about 0.01 3 inches); and a fabric weight of about 24.4 grams per square meter (about 0.72 ounces per square yard).
  • Style 108 Another non-limiting example of a fabric style using D900 E-glass fiber yarns is Style 108, which has 1 1 8 warp yarns and 93 fill yarns per 5 centimeters (60 warp yarns and 47 fill yarns per inch); uses 5 5.5 1 x2 (D900 1 /2) warp and fill yarns; has a nominal fabric thickness of about 0.061 millimeters (about 0.0024 inches); and a fabric weight of about 47.5 grams per square meter (about 1 .40 ounces per square yard).
  • a non-limiting example of a fabric style using both E225 and D450 E-glass fiber yarns is Style 21 1 3, which has 1 1 8 warp yarns and 1 1 0 fill yarns per 5 centimeters (60 warp yarns and 56 fill yarns per inch); uses 7 22 1 x0 (E225 1 /0) warp yarn and 5 1 1 1 x0 (D450 1 /0) fill yarn; has a nominal fabric thickness of about 0.079 millimeters (about 0.0031 inches); and a fabric weight of about 78.0 grams per square meter (about 2.30 ounces per square yard).
  • a non-limiting example of a fabric style using both G50 and G75 E-glass fiber yarns is Style 7535 which has 87 warp yarns and 57 fill yarns per 5 centimeters (44 warp yarns and 29 fill yarns per inch); uses 9 68 1 x0 (G75 1 /0) warp yarn and 9 99 1 x0 (G50 1 /0) fill yarn; has a nominal fabric thickness of about 0.201 millimeters (about 0.0079 inches); and a fabric weight of about 232.3 grams per square meter (about 6.85 ounces per square yard).
  • the laminates can also be a unidirectional laminate wherein most of the fibers, yarns or strands in each layer of fabric are oriented in the same direction.
  • the fabric 612 can be used to form a composite or laminate 614 by coating and/or impregnating with a polymeric film-forming thermoplastic or thermosetting matrix material 616.
  • the composite or laminate 614 is suitable for use as a electronic support.
  • electronic support means a structure that mechanically supports and/or electrically interconnects elements including but not limited to active electronic components, passive electronic components, printed circuits, integrated circuits, semiconductor devices and other hardware associated with such elements including but not limited to connectors, sockets, retaining clips and heat sinks.
  • Matrix materials useful in the present invention include thermosetting materials such as thermosetting polyesters, vinyl esters, epoxides (containing at least one epoxy or oxirane group in the molecule, such as polyglycidyl ethers of polyhydric alcohols or thiols), phenolics, aminoplasts, thermosetting polyurethanes, derivatives and mixtures thereof.
  • thermosetting materials such as thermosetting polyesters, vinyl esters, epoxides (containing at least one epoxy or oxirane group in the molecule, such as polyglycidyl ethers of polyhydric alcohols or thiols), phenolics, aminoplasts, thermosetting polyurethanes, derivatives and mixtures thereof.
  • Preferred matrix materials for forming laminates for printed circuit boards are FR-4 epoxy resins, polyimides and liquid crystalline polymers, the compositions of which are well know to those skilled in the art. If further information regarding such compositions is needed, see Electronic Materials HandbookTM, ASM International (1989) at pages
  • suitable polymeric thermoplastic matrix materials include polyolefins, polyamides, thermoplastic polyurethanes and thermoplastic polyesters, vinyl polymers and mixtures thereof.
  • Further examples of useful thermoplastic materials include polyimides, polyether sulfones, polyphenyl sulfones, polyetherketones, polyphenylene oxides, polyphenylene sulfides, polyacetals, polyvinyl chlorides and polycarbonates.
  • Other components which can be included with the polymeric matrix material and reinforcing material in the composite include colorants or pigments, lubricants or processing aids, ultraviolet light (UV) stabilizers, antioxidants, other fillers and extenders.
  • UV ultraviolet light
  • the fabric 612 can be coated and impregnated by dipping the fabric 612 in a bath of the polymeric matrix material 616, for example, as discussed in R. Tummala (Ed.), Microelectronics Packaging Handbook. (1989) at pages 895-896, which are hereby incorporated by reference. More generally, chopped or continuous fiber strand reinforcing material can be dispersed in the matrix material by hand or any suitable automated feed or mixing device which distributes the reinforcing material generally evenly throughout the polymeric matrix material. For example, the reinforcing material can be dispersed in the polymeric matrix material by dry blending all of the components concurrently or sequentially.
  • the polymeric matrix material 616 and strand can be formed into a composite or laminate 614 by a variety of methods which are dependent upon such factors as the type of polymeric matrix material used.
  • the composite can be formed by compression or injection molding, pultrusion, filament winding, hand lay-up, spray-up or by sheet molding or bulk molding followed by compression or injection molding.
  • Thermosetting polymeric matrix materials can be cured by the inclusion of crosslinkers in the matrix material and/or by the application of heat, for example. Suitable crosslinkers useful to crosslink the polymeric matrix material are discussed above.
  • the temperature and curing time for the thermosetting polymeric matrix material depends upon such factors as the type of polymeric matrix material used, other additives in the matrix system and thickness of the composite, to name a few.
  • thermoplastic matrix material suitable methods for forming the composite include direct molding or extrusion compounding followed by injection molding. Methods and apparatus for forming the composite by the above methods are discussed in I. Rubin, Handbook of Plastic Materials and Technology (1990) at pages 955-1062. 1179-1215 and 1225-1271 , which are hereby incorporated by reference.
  • composite or laminate 710 includes fabric 712 impregnated with a compatible matrix material 714.
  • the impregnated fabric can then be squeezed between a set of metering rolls to leave a measured amount of matrix material, and dried to form an electronic support in the form of a semicured substrate or prepreg.
  • An electrically conductive layer 720 can be positioned along a portion of a side 722 of the prepreg in a manner to be discussed below in the specification, and the prepreg is cured to form an electronic support 718 with an electrically conductive layer.
  • two or more prepregs are combined with one or more electrically conductive layers and laminated together and cured in a manner well known to those skilled in the art, to form a multilayered electronic support.
  • the prepreg stack can be laminated by pressing the stack, e.g. between polished steel plates, at elevated temperatures and pressures for a predetermined length of time to cure the polymeric matrix and form a laminate of a desired thickness.
  • a portion of one or more of the prepregs can be provided with an electrically conductive layer either prior to or after lamination and curing such that the resulting electronic support is a laminate having at least one electrically conductive layer along a portion of an exposed surface (hereinafter referred to as a "clad laminate").
  • Circuits can then be formed from the electrically conductive iayer(s) of the single layer or multilayered electronic support using techniques well known in the art to construct an electronic support in the form of a printed circuit board or printed wiring board (hereinafter collectively referred to as "electronic circuit boards”).
  • apertures or holes can be formed in the electronic supports, to allow for electrical interconnection between circuits and/or components on opposing surfaces of the electronic support, by any convenient manner known in the art, including but not limited to mechanical drilling and laser drilling. More specifically, after formation of the apertures, a layer of electrically conductive material is deposited on the walls of the aperture or the aperture is filled with an electrically conductive material to facilitate the required electrical interconnection and/or heat dissipation.
  • the electrically conductive layer 720 can be formed by any method well known to those skilled in the art.
  • the electrically conductive layer can be formed by laminating a thin sheet or foil of metallic material onto at least a portion of a side of the semi- cured or cured prepreg or laminate.
  • the electrically conductive layer can be formed by depositing a layer of metallic material onto at least a portion of a side of the semi-cured or cured prepreg or laminate using well known techniques including but not limited to electrolytic plating, electroless plating or sputtering.
  • Metallic materials suitable for use as an electrically conductive layer include but are not limited to copper (which is preferred), silver, aluminum, gold, tin, tin-lead alloys, palladium and combinations thereof.
  • the electronic support can be in the form of a multilayered electronic circuit board constructed by laminating together one or more electronic circuit boards (described above) with one or more clad laminates (described above) and/or one or more prepregs (described above).
  • additional electrically conductive layers can be incorporated into the electronic support, for example along a portion of an exposed side of the multilayered electronic circuit board.
  • additional circuits can be formed from the electrically conductive layers in a manner discussed above. It should be appreciated that depending on the relative positions of the layers of the multilayered electronic circuit board, the board can have both internal and external circuits.
  • Additional apertures are formed, as discussed earlier, partially through or completely through the board to allow electrical interconnection between the layers at selected locations. It should be appreciated that the resulting structure can have some apertures that extend completely through the structure, some apertures that extend only partially through the structure, and some apertures that are completely within the structure.
  • the instant invention further contemplates the fabrication of multilayered laminates and electronic circuit boards which include at least one composite layer made according to the teachings herein and at least one composite layer made in a manner different from the composite layer taught herein, e.g. made using conventional glass fiber composite technology. More specifically and as is well known to those skilled in the art, traditionally the filaments in continuous glass fiber strands used in weaving fabric are treated with a starch/oil sizing which includes partially or fully dextrinized starch or amylose, hydrogenated vegetable oil, a cationic wetting agent, emulsifying agent and water, including but not limited to those disclosed in Loewenstein at pages 237-244 (3d Ed. 1993), which is hereby incorporated by reference.
  • a starch/oil sizing which includes partially or fully dextrinized starch or amylose, hydrogenated vegetable oil, a cationic wetting agent, emulsifying agent and water, including but not limited to those disclosed in Loewenstein at pages 237-244 (3d Ed
  • Warp yarns produced from these strands are thereafter treated with a solution prior to weaving to protect the strands against abrasion during the weaving process, e.g. poly(vinyl alcohol) as disclosed in U.S. Patent No. 4,530,876 at column 3, line 67 through column 4, line 11 , which is hereby incorporated by reference. This operation is commonly referred to as slashing.
  • the poly(vinyl alcohol) as well as the starch/oil size are generally not compatible with the polymeric matrix material used by composite manufacturers and the fabric must be cleaned to remove essentially all organic material from the surface of the glass fibers prior to impregnating the woven fabric.
  • finishing This can be accomplished in a variety ways, for example by scrubbing the fabric or, more commonly, by heat treating the fabric in a manner well known in the art.
  • a coupling agent must be applied to the glass fiber surface.
  • This operation is sometime referred to by those skilled in the art as finishing.
  • the coupling agents most commonly used in finishing operations are silanes, including but not limited to those disclosed in E. P. Plueddemann, Silane Coupling Agents (1982) at pages 146-147, which is hereby incorporated by reference. Also see Loewenstein at pages 249-256 (3d Ed. 1993).
  • the fabric After treatment with the silane, the fabric is impregnated with a compatible polymeric matrix material, squeezed between a set of metering rolls and dried to form a semicured prepreg as discussed above. It should be appreciated that depending on the nature of the sizing, the cleaning operation and/or the matrix resin used in the composite, the slashing and/or finishing steps can be eliminated.
  • One or more prepregs incorporating conventional glass fiber composite technology can then be combined with one or more prepregs incorporating the instant invention to form an electronic support as discussed above, and in particular a multilayered laminate or electronic circuit board. For more information regarding fabrication of electronic circuit boards, see Electronic Materials HandbookTM, ASM International (1989) at pages 113- 115, R.
  • the composites and laminates forming the electronic supports of the instant invention can be used to form packaging used in the electronics industry, and more particularly first, second and/or third level packaging, such as that disclosed in Tummala at pages 25-43, which is hereby incorporated by reference.
  • the present invention can also be used for other packaging levels.
  • the present invention also includes a method for reinforcing a polymeric matrix material to form a composite.
  • the method comprises: (1) applying to a glass fiber strand reinforcing material the above primary sizing, secondary coating and/or tertiary coating composition including particles which provide interstitial spaces between adjacent glass fibers of the strand, (2) drying the coating to form a substantially uniform coating upon the reinforcing material; (3) combining the reinforcing material with the polymeric matrix material; and (4) at least partially curing the polymeric matrix material to provide a reinforced polymeric composite in a manner such as is discussed in detail above.
  • the reinforcing material can be combined with the polymeric matrix material, for example by dispersing it in the matrix material.
  • the present invention also includes a method for inhibiting adhesion between adjacent glass fibers of a glass fiber strand, comprising the steps of: (1) applying to a glass fiber strand the above primary sizing, secondary coating or tertiary coating composition including particles which provide interstitial spaces between adjacent glass fibers of the strand; (2) drying the coating to form a substantially uniform coating upon the glass fibers of the glass fiber strand, such that adhesion between adjacent glass fibers of the strand is inhibited.
  • aqueous primary size compositions A, B and C were mixed to form aqueous primary size compositions A, B and C according to the present invention.
  • Each aqueous primary sizing composition was prepared in a similar manner to that discussed above. Less than about 1 weight percent of acetic acid on a total weight basis was included in each composition.
  • Each of the aqueous sizing compositions of Table 1 was coated onto fibers forming G-75 E-glass fiber strands.
  • EMERY® 6717 partially amidated polyethylene imine which is commercially available from Henkel Corporation of Kankakee, IL.
  • MACOL OP-10 ethoxylated alkylphenol which is commercially available from BASF Corp. of Parsippany, NJ.
  • ROPAQUE® HP-1055 1.0 micron particle dispersion which is commercially available from Rohm and Haas Company of Philadelphia, PA.
  • ROPAQUE® OP-96, 0.55 micron particle dispersion which is commercially available from Rohm and Haas Company of Philadelphia, PA.
  • Laminates were made by stacking 8-plies of the pre- pregged material between two layers of 1 ounce copper and laminating them together at a temperature of about 355°F (about 179°C), pressure of about 300 pounds per square inch (about 2.1 megaPascals) for about 150 minutes (total cycle time).
  • the thickness of the laminates without copper ranged from about 0.043 inches (about 0.11 centimeters) to about 0.050 inches (0.13 centimeters).
  • Laminate Sample A1 a first laminate made from glass fiber yarn coated with sizing composition Sample A
  • Laminate Sample A2 a second laminate made from glass fiber yarn coated with sizing composition Sample C
  • PolarTherm® PT 160 boron nitride powder which is commercially available from Advanced Ceramics Corporation of Lakewood, OH.
  • the warp yarn was PPG Industries, Inc.'s commercially available fiber glass yarn product designated as G-75 glass fiber yarn coated with PPG Industries, Inc.'s 1383 binder. Table 2
  • solder float test was conducted by floating an 4 inch by 4 inch square (10.16 centimeters by 10.16 centimeters) of the copper clad laminate in a eutectic lead-tin solder bath at about 550°F (about 288°C) until blistering or delamination was observed. The time until the first blister or delamination was then recorded in seconds.
  • solder dip test was conducted by cutting a sample of the laminate, removing the copper from the sample by etching, smoothing the cut edges of the sample by polishing and placing the sample in a pressure cooker at 250°F
  • the flexural testing was conducted according to the IPC standard indicated.
  • MACOL OP-10 ethoxylated alkylphenol which is commercially available from BASF of Parsippany, New Jersey
  • PolarTherm® PT 160 boron nitride powder particles which are commercially available from Advanced Ceramics Corporation of Lakewood, OH.
  • EMERY® 6717 partially amidated polyethylene imine which is commercially available from Henkel Corporation of Kankakee, I .
  • Each of the aqueous size compositions of Table 3 were use to coat glass fibers forming G-75 E-glass fiber strands. Each coated glass fiber strand was dried, twisted to form a yarn, and wound onto bobbins in a similar manner using conventional twisting equipment.
  • the yarn of Sample D was evaluated by comparing the coated yarn to yarn coated with a sizing composition similar to Sample D but without the epoxidized linseed oil (hereinafter "Comparative Sample 1 "). This comparison included visual inspection of the appearance of a 7628 style fabric woven on an air jet loom. The woven fabric used Sample D as the fill yarn a twisted G-75 E-glass fiber strand with fiber coated with a different resin compatible sizing composition 57 as the warp yarn. It was observed that fabric woven with yarn coated with Sample D exhibited less loose fuzz on
  • ROPAQUE® OP-96 0.55 micron particle dispersion which is commercially available from Rohm and Haas Company of Philadelphia, PA.
  • the warp yarn was PPG Industries, Inc.'s commercially available fiber glass yarn product designated as G-75 glass fiber yarn coated with PPG Industries, Inc.'s 1383 binder.
  • the fabric as well as less collected fuzz at contact points on the loom, especially at the yarn accumulator, when compared to fabric woven with yarn coated with Comparative Sample 1 .
  • No fabric was woven using yarn incorporating fibers coated with Samples E or F because of the high initial amount of fuzz observed on the loom. It is believed that this condition was the result of an LOI level lower than required to prevent excess fuzz formation.
  • an LOI of at least 0.40 for the sizing compositions discussed above is required to reduce fuzz formation during weaving.
  • the loss on ignition (weight percent of solids of the forming size composition divided by the total weight of the glass and dried forming size composition) of each Sample is set forth in Table 4.
  • Each yarn was evaluated for Air Drag Force or tension by feeding the yarn at a controlled feed rate of 274 meters (300 yards) per minute through a checkline tension meter, which applied a tension to the yarn, and a Ruti two millimeter diameter air nozzle at an air pressure of 138 kPa (20 pounds per square inch).
  • the Samples and Comparative Sample 2 were also evaluated for Friction Force by applying a tension of about 20 grams to each yarn sample as the sample is pulled at a rate of 274 meters (300 yards) per minute through a pair of conventional tension measurement devices having a
  • the yarn was PPG Industries, Inc.'s commercially available fiber glass yarn designated as G-75 glass fiber yarn coated with PPG Industries, Inc.'s 695 starch/oil binder. stationary chrome post of about 5 centimeters (2 inches) diameter mounted therebetween to displace the yarn about 5 centimeters from a straight line path between the tension measurement devices.
  • the difference in force in grams is set forth in Table 7 below.
  • the Friction Force test is intended to simulate the fricfional forces to which the yarn is subjected during weaving operations.
  • Samples B and 2 were tested at the same time as a first quantity of glass fiber yarn coated with sizing composition Sample A (hereinafter designated as Sample A3) and Sample C was tested at the same time as a second quantity of glass fiber yarn coated with sizing composition Sample A (hereinafter designated as Sample A4).
  • Samples A3, A4 and B were about 2.8 weight percent solids.
  • Sample C was about 3.1 weight percent solid.
  • Comparative Sample 2 was about 5.9 weight percent solid.
  • Test 2 Each yarn was further evaluated for the number of broken filaments at increasing levels of tension and abrasion (shown in Table 5 as Test 2).
  • Test 2 a sample of yarn was unwound from a bobbin at 200 meters/minute, threaded in a serpentine manner through a series of 8 ceramic pins on a uniform tension control device (sometimes refered to as a gate tensioning device), and passedthrough the Shirley broken filament detector (discussed above) to count the number of broken filaments.
  • the spacing of the pins on the tensioning device was varied using different dial settings to provide various levels of tension in the yarn.
  • This particular test used a Model UTC-2003 tensioning device commercially available from Steel Heddle Co. of South Carolina.
  • the broken filaments was reported in number of broken filaments per meter of yarn.
  • Sample A5 The results of these tests for Samples A, B and C and Comparative Sample 2 are set forth in Table 5 below.
  • Samples B and 2 were tested at the same time as a first quantity of glass fiber yarn coated with sizing composition Sample A (hereinafter designated as Sample A5) and at a latter date Sample C was tested at the same time as a second quantity of glass fiber yarn coated with sizing composition Sample A (hereinafter designated as Sample A6).
  • the present invention provides glass fiber strands having an abrasion-resistant coating which provide good thermal stability, low corrosion and reactivity in the presence of high humidity, reactive acids and alkalies and compatibility with a variety of polymeric matrix materials.
  • These strands can be twisted or chopped, formed into a roving, chopped mat or continuous strand mat or woven or knitted into a fabric for use in a wide variety of applications, such as reinforcements for composites such as printed circuit boards.
EP99952920A 1998-10-13 1999-10-08 Impregnated glass fiber strands and products including the same Withdrawn EP1124769A1 (en)

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US17056698A 1998-10-13 1998-10-13
US170566 1998-10-13
US13307699P 1999-05-07 1999-05-07
US133076P 1999-05-07
US14633799P 1999-07-30 1999-07-30
US146337P 1999-07-30
PCT/US1999/021442 WO2000021899A1 (en) 1998-10-13 1999-10-08 Impregnated glass fiber strands and products including the same

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Families Citing this family (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6593255B1 (en) * 1998-03-03 2003-07-15 Ppg Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
US6949289B1 (en) * 1998-03-03 2005-09-27 Ppg Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
US8105690B2 (en) * 1998-03-03 2012-01-31 Ppg Industries Ohio, Inc Fiber product coated with particles to adjust the friction of the coating and the interfilament bonding
MXPA01003660A (es) * 1999-07-30 2001-07-01 Torones de fibra de vidrio impregnados y productos que los inclu
MXPA02001093A (es) * 1999-07-30 2003-07-21 Ppg Ind Ohio Inc Hebras de fibra de vidrio impregnadas y productos que las incluyen.
WO2001009226A1 (en) * 1999-07-30 2001-02-08 Ppg Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
US20020051882A1 (en) * 2000-02-18 2002-05-02 Lawton Ernest L. Forming size compositions, glass fibers coated with the same and fabrics woven from such coated fibers
AU2001252911A1 (en) * 2000-03-16 2001-09-24 Ppg Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
AU2001247491A1 (en) * 2000-03-16 2001-09-24 Ppg Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
WO2001068750A1 (en) * 2000-03-16 2001-09-20 Ppg Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
AU2001252916A1 (en) * 2000-03-16 2001-09-24 Ppg Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
WO2001068755A1 (en) * 2000-03-16 2001-09-20 Ppg Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
AU2001249257A1 (en) * 2000-03-16 2001-09-24 Ppg Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
FR2860957B1 (fr) * 2003-10-20 2005-12-23 Php Textile a base d'un melange de coton et de fibres techniques resistant a l'abrasion
US7354641B2 (en) * 2004-10-12 2008-04-08 Ppg Industries Ohio, Inc. Resin compatible yarn binder and uses thereof
KR100594658B1 (ko) * 2005-01-29 2006-06-30 엘에스전선 주식회사 가공 송전선의 인장선용 섬유강화 플라스틱 선재, 그제조방법 및 이를 이용한 가공 송전선
US20070082982A1 (en) * 2005-10-11 2007-04-12 The Procter & Gamble Company Water stable compositions and articles comprising starch and methods of making the same
EP2437936B1 (en) 2009-02-27 2021-07-21 Hexion Research Belgium SA Compositions useful for non-cellulose fiber sizing, coating or binding compositions, and composites incorporating same
US20110014467A1 (en) * 2009-07-16 2011-01-20 Brown Nancy E Extrusion coated non-twisted yarn
CN101948251B (zh) * 2010-06-25 2012-07-25 巨石攀登电子基材有限公司 玻璃纤维纱的上浆浆料及使用该浆料的生产方法
RU2545476C1 (ru) * 2013-12-26 2015-03-27 Федеральное государственное бюджетное учреждение "Всероссийский научно-исследовательский институт по проблемам гражданской обороны и чрезвычайных ситуаций МЧС России" (федеральный центр науки и высоких технологий) Автомобиль мобильного учебного комплекса для подготовки населения в области гражданской защиты
CN103898761B (zh) * 2014-03-24 2016-05-25 西安工程大学 涤棉用纺织热熔浆料的制备方法
JP6413522B2 (ja) * 2014-09-09 2018-10-31 セイコーエプソン株式会社 シート製造装置、シート製造方法及びこれらにより製造されるシート、並びに、これらに用いる複合体及びその収容容器
JP6557464B2 (ja) * 2014-12-10 2019-08-07 パラマウント硝子工業株式会社 柔軟性を有する無機繊維断熱吸音材及びその製造方法
CN105153665B (zh) * 2015-08-12 2017-10-17 宁波航海纺机有限责任公司 一种玻璃纤维增强聚碳酸酯热塑性树脂复合材料制备剑杆织机用剑头的制备方法
CN105086407B (zh) * 2015-08-12 2017-03-08 宁波航海纺机有限责任公司 一种剑杆织机用剑头及其制备方法
CN105086406B (zh) * 2015-08-12 2017-07-21 宁波航海纺机有限责任公司 一种剑杆织机用的高强耐磨增韧剑头
CN108291072A (zh) * 2015-10-08 2018-07-17 Ocv智识资本有限责任公司 用于增强纤维的后-涂布组合物
CN105385145A (zh) * 2015-12-21 2016-03-09 江苏宏远新材料科技有限公司 一种耐磨型聚氨酯薄膜
CN105585257A (zh) * 2015-12-23 2016-05-18 晏玲莉 一种玄武岩纤维浸润剂
FR3052762B1 (fr) * 2016-06-17 2020-09-25 Saint Gobain Isover Installation de traitement d'un matelas de fibres minerales par detection et evacuation de defauts localises, et procede correspondant
US11001525B2 (en) * 2016-06-17 2021-05-11 Owens Corning Intellectual Capital, Llc Sizing composition for wet use chopped strand glass fibers
CN106277847A (zh) * 2016-07-29 2017-01-04 安徽丹凤集团桐城玻璃纤维有限公司 一种玻璃纤维浸润剂
US10875806B2 (en) * 2017-07-19 2020-12-29 Corning Incorporated Organic-inorganic composite fibers and methods thereof
FR3069536B1 (fr) * 2017-07-31 2020-07-17 Saint-Gobain Isover Procede de fabrication de laine minerale
CN107640913B (zh) * 2017-08-22 2019-10-01 江苏大学 一种玄武岩纤维表面改性涂层的制备方法及其应用
CN107460737A (zh) * 2017-09-22 2017-12-12 江苏欣捷衬布有限公司 一种树脂衬材料制备工艺
CN108059363A (zh) * 2017-12-25 2018-05-22 安徽同力新材料有限公司 一种玻璃纤维浸润剂组合物
CN108069625A (zh) * 2017-12-25 2018-05-25 安徽同力新材料有限公司 一种玻璃纤维纱高效浸润剂
CN108996925A (zh) * 2018-07-27 2018-12-14 苏州华龙化工有限公司 一种增强型玻璃纤维浸润剂的制备方法
CN108840581A (zh) * 2018-08-07 2018-11-20 苏州华龙化工有限公司 一种增强型玻璃纤维浸润剂及其制备方法
CN109867913A (zh) * 2018-08-11 2019-06-11 珠海市磐石电子科技有限公司 耐磨预浸料及耐磨层
CN113166563B (zh) * 2018-11-29 2022-08-26 伊斯曼柯达公司 用于制备纱和织物的水性组合物
CN109369050A (zh) * 2018-12-07 2019-02-22 河南交通职业技术学院 用于增强水泥混凝土的短切玄武岩纤维束及其制备方法
WO2020163798A1 (en) * 2019-02-08 2020-08-13 Ppg Industries Ohio, Inc. Methods of coating fiber containing materials and coated fiber containing materials
CN110685087A (zh) * 2019-11-22 2020-01-14 上海曙雀贸易有限公司 一种涂层成膜玻璃纤维纱及其制备方法和应用
RU2757922C2 (ru) * 2020-03-18 2021-10-25 Федеральное государственное бюджетное образовательное учреждение высшего образования "Кабардино-Балкарский государственный университет им. Х.М. Бербекова" (КБГУ) Углеволокнистый полимерный композиционный материал на основе полиэфирэфиркетона и способ его получения
CN111606616A (zh) * 2020-05-20 2020-09-01 中铁二局第二工程有限公司 一种填充式植物纤维、制备方法以及高强可塑吸波混凝土
RU2750160C1 (ru) * 2020-08-18 2021-06-22 Федеральное государственное бюджетное образовательное учреж-дение высшего образования "Волгоградский государственный технический университет" (ВолгГТУ) Теплозащитный материал
CN112048918B (zh) * 2020-09-12 2021-10-26 浙江省天台天峰滤料有限公司 一种耐久性电解槽专用保温盖布及制备方法
CN115679704A (zh) * 2020-12-26 2023-02-03 江苏苏净集团有限公司 一种除湿转轮用吸附除湿材料的制备方法
CN115522390B (zh) * 2022-11-23 2023-03-24 山东兴国大成电子材料有限公司 一种玻璃纤维布的制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312569A (en) * 1965-05-07 1967-04-04 Owens Corning Fiberglass Corp Compatible fibrous glass reinforcements of superior bonding and wetting characteristics
US5217778A (en) * 1982-10-21 1993-06-08 Raymark Industries, Inc. Composite fiber friction facing
JP2545957B2 (ja) * 1988-12-15 1996-10-23 日東紡績株式会社 プリント配線基板及び同基板用織物
JP3520604B2 (ja) * 1995-05-23 2004-04-19 日立化成工業株式会社 コンポジット積層板
US5773146A (en) * 1995-06-05 1998-06-30 Ppg Industries, Inc. Forming size compositions, glass fibers coated with the same and fabrics woven from such coated fibers
JPH0977937A (ja) * 1995-09-12 1997-03-25 Idemitsu Petrochem Co Ltd プリント配線板用プリプレグ及びプリント配線用基板
JP3151397B2 (ja) * 1995-10-26 2001-04-03 松下電工株式会社 プリプレグ及び金属箔張り積層板

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0021899A1 *

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CN1329580A (zh) 2002-01-02
WO2000021899A1 (en) 2000-04-20

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