MXPA00008527A - Impregnated glass fiber strands and products including the same - Google Patents

Abstract

The present invention provides glass fiber strands impregnated with non-abrasive solid particles which provide interstitial spaces of at least 3 micrometers between adjacent fibers within a strand which are useful for reinforcing composites.

Description

IMPREGNATED GLASS FIBER TORONES AND PRODUCTS THAT INCLUDE THEM Cross reference to related applications This patent application is a partial continuation request of the United States serial number 09 / 034,077 by B. Novich et al. Entitled "Impregistered fiberglass strands and products that include them" filed on March 3 of 1998. This patent application is related to the United States patent application serial number of B. Novich et al entitled "Methods to inhibit abrasive wear of fiberglass strands", which is a partial continuation application of the United States request serial number 09 / 034,078 filed on March 3, 1998; US patent application serial number of B. Novich et al. entitled "Fiberglass strands coated with inorganic thermal conductive solid particles and products that include them", which is a partial continuation application of the United States application number of series 09 / 034,663 filed on March 3, 1998; US patent application serial number of B. Novich et al. entitled "Fiberglass strands coated with inorganic lubricant and products that include them", which is a partial continuation application of the United States application number. series 09 / 034,525 filed on March 3, 1998; the United States patent application serial number of B.

Novich et al. Entitled "Fiberglass strands coated with inorganic particles and products that include them", which is a partial continuation application of United States application serial number 09 / 034,056 filed March 3, 1998; and the United States patent application serial number of B. Novich et al. entitled "Fiberglass-reinforced mines, electronic circuit boards and methods for assembling a cloth", which is a partial continuation of the application for United States serial number 09 / 130,270 filed on August 6, 1998, each of which has been filed concurrently with the present application. FIELD OF THE INVENTION This invention relates generally to coated fiberglass strands for reinforcing compounds and, more specifically, to fiberglass strands impregnated with solid particles that provide interstitial spaces between adjacent glass fibers of the strand, having the solid particles have a minimum average particle size of at least 3 microns.

BACKGROUND OF THE INVENTION Good heat-setting properties (penetration of the matrix polymer material through the mat) and "soaking" (penetration of the polymer matrix material through individual bundles or strands) are desirable in thermosetting operations. of fibers in the mat). In contrast, good dispersion properties are of predominant importance in typical thermoplastic molding operations. To improve resin impregnation, Japanese Patent Application No. 9-208,268 discloses a fabric having yarn formed from coated glass fibers 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 with average particle sizes of 5 to 2000 nanometers (0.05 to 2 microns). In paragraph 13 of the detailed description of the invention, it is described that such coatings with more than 20 weight percent of inorganic solid particles can not be applied to the glass fiber. To improve the penetration of resin between glass reinforcing fibers during the formation of a composite, US Pat. No. 3,312,569 discloses alumina particles that adhere to the surfaces of glass fibers. However, the Mohs hardness value of the alumina is greater than about 91, which can cause abrasion of the softer glass fibers. The Soviet Union patent number 859400 describes an impregnating composition for manufacturing glass fiber cloth laminates, the composition containing an alcoholic solution of phenol-formaldehyde resin, graphite, molybdenum disulfide, polyvinyl butyral and surfactant. Volatile alcohol solvents are not desirable for fiberglass production applications. To improve, reduce or modify the friction characteristics of a composite, U.S. Patent No. 5,217,778 discloses a dry clutch coating that includes a yarn composed of glass fibers, metallic yarn and polyacrylonitrile fibers that are impregnated and coated. with a thermosetting cement or binder system. The binder may include friction particles such as carbon black, graphite, metal oxides, barium sulfate, aluminum silicate, crushed rubber particles, crushed organic resins, polymerized cashew nut oil, clay, silica or cryolite (see column 2, lines 55-66). Coatings are needed to inhibit abrasion and breakage of glass fibers that are compatible with a wide variety of polymeric matrix materials. 1 See R. Weast (ed.), Handbook of Chemistry and Physics, CRC Press (1975), page F-22, which is incorporated herein by reference.

SUMMARY OF THE INVENTION The present invention provides a coated fiber core including a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the strand being impregnated at least partially with a dried residue of an aqueous composition of The sizing includes solid particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns and a hardness not exceeding the hardness of the plurality of glass fibers. Another aspect of the present invention is a coated fiber strand which includes a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the strand being impregnated at least partially with (1) a primary layer of a dried residue of a size composition applied to at least a portion of the surfaces of the plurality of glass fibers and (2) a secondary layer of an aqueous secondary coating composition applied over at least a portion of the primary layer, including the secondary coating composition solid particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3-5 microns. Another aspect of the present invention is a coated fiber strand that includes a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the strand being impregnated at least partially with (1) a primary layer of a waste. drying a sizing composition applied to at least a portion of the surfaces of the plurality of glass fibers and (2) a secondary layer of a dried residue of an aqueous secondary coating composition applied over at least a portion of the primary layer , the secondary coating composition including hydrophilic solid particles providing interstitial spaces between adjacent glass fibers of the strand, the hydrophilic solid particles having a minimum average particle size of at least 3 microns and which, after exposure to water, absorb and they retain water in the interstices inside the hydrophilic solid particles. Another aspect of the present invention is a coated fiber strand that includes a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the strand being impregnated at least partially with (1) a primary layer of a waste. drying a sizing composition applied to at least a portion of the surfaces of the plurality of glass fibers; (2) a secondary layer of a secondary coating composition applied on at least a portion of the primary layer, the secondary coating composition comprising a polymeric material; and a tertiary layer including solid powder particles applied on at least a portion of the secondary layer providing interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns. Another aspect of the present invention is a reinforced polymeric composite that includes: (a) a coated fiber strand that includes a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the strand being impregnated with less partially with a dried residue of an aqueous sizing composition including solid particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns and a hardness not exceeding the hardness of the plurality of glass fibers; and (b) a polymeric matrix material.

Another aspect of the present invention is a fabric that includes a coated fiber strand that includes a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the strand being impregnated at least partially with a dried residue of a aqueous sizing composition which includes solid particles which provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns and a hardness not exceeding the hardness of the plurality of f » Glass fibers Another aspect of the present invention is an electronic support including: (a) a fabric including a coated fiber strand including a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the fiber impregnated with at least partially with a dried residue of an aqueous sizing composition including solid particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns and a hardness which does not exceed the hardness of the plurality of glass fibers; and (b) a layer of a polymeric matrix material applied on at least a portion of the fabric. Another aspect of the present invention is an electronic circuit board including: (a) an electronic support including: (i.) A fabric including a coated fiber strand including a plurality of glass fibers with an average nominal diameter of fibers greater than 5 microns, the strand being impregnated at least partially with a dried residue of an aqueous sizing composition including solid particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a mean particle size minimum of at least 3 microns and a hardness not exceeding the hardness of the plurality of glass fibers; and (ii) a layer of a polymeric matrix material applied on at least a portion of the fabric; and (b) an electrical conductive layer placed adjacent to selected portions of selected sides of the electronic support. Another aspect of the present invention is an electronic support comprising: (a) a first composite layer comprising: (i) a fabric including a coated fiber strand including a plurality of glass fibers with an average nominal fiber diameter greater than 5 microns, the strand being impregnated at least partially with a dried residue of an aqueous sizing composition including solid particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns and a hardness that does not exceed the hardness of the plurality of glass fibers; and (ii) a layer of a polymeric matrix material applied on at least a portion of the fabric; and (b) a second composite layer different from the first composite layer. Another aspect of the present invention is an electronic circuit board including: (a) an electronic support including: (i) a first composite layer comprising: (1) a fabric including a coated fiber strand including a plurality of glass fibers with a mean nominal diameter of the fibers greater than 5 microns, the strand being impregnated at least partially with a dried residue of an aqueous sizing composition including solid particles that provide interstitial spaces between adjacent glass fibers of the strand, having the solid particles a minimum average particle size of at least 3 microns and a hardness not exceeding the hardness of the plurality of glass fibers; and (2) a layer of a polymeric matrix material applied on at least one "portion of the fabric, and (ii) a second composite layer different from the first composite layer, and (b) an electrically conductive layer placed adjacent to portions thereof. selected from selected sides of the first and / or second composite layers.

BRIEF DESCRIPTION OF THE DRAWINGS The above summary, as well as the following detailed description of the preferred embodiments, will be better understood when read in conjunction with the accompanying drawings. In the drawings: Figure 1 is a perspective view of a coated fiber strand having a primary layer of a dried residue of an aqueous size composition according to the present invention. Figure 2 is a perspective view of a coated fiber strand having a primary layer of a dried residue of a size composition and on top of it a secondary layer of an aqueous secondary coating composition according to the present invention. Figure 3 is a perspective view of a coated fiber strand having a primary layer of a dried residue of a size composition, a secondary layer of an aqueous secondary coating composition, and a tertiary layer on top of the present invention. - Figure 4 is a top plan view of a compound according to the present invention. Figure 5 is a top plan view of a fabric according to the present invention. Figure 6 is a cross-sectional view of an electronic support according to the present invention. And Figures 7 and 8 are cross-sectional views of alternative embodiments of an electronic support according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION The fiberglass strands of the present invention have a unique coating that not only inhibits abrasion and breakage of the fibers during processing, but can provide good stamping, soaking and dispersion properties in the formation of compounds Good rolling resistance, good thermal stability, good hydrolytic stability, low corrosion and reactivity in presence of high humidity, reactive acids and alkalis and compatibility with a variety of polymeric matrix materials, which can eliminate the need for heat cleaning before lamination, there are other desirable characteristics that can be exhibited by the fiberglass strands coated with the pre-senté invention. Another considerable advantage of the coated fiberglass strands of the present invention is good processability in weaving and knitting. Little fluff and halos, few broken filaments, low strand tension, high plegabi-lity and little insertion time are features that the coated fiberglass strands of the present invention can provide for weaving and tri-rotating and providing coherently a fabric with few surface defects for printed circuit board applications. Referring now to Figure 1, where analogous numbers indicate analogous elements from beginning to end, a coated fiber strand 10 including a plurality of glass fibers 12 or quartz fibers according to the present invention is shown in Figure 1. In the sense in which it is used herein, "strand" means a plurality of individual fibers. The term "fiber" means an individual filament. The fibers 12 have a nominal average fiber diameter greater than 5 microns, preferably greater than 7 microns, and more preferably greater than 9 microns. The glass fibers 12 can be formed from any type of fibrillable glass composition known to those skilled in the art, including those prepared from fiber-curable glass compositions such as "E glass", "glass A", "glass C", and "," glass D "," glass R "," glass S "and glass derivatives E. In the sense in which it is used herein," glass derivatives E "means glass compositions that include small amounts of fluorine and / or boron and preferably are free of fluorine and / or boron free. Also, in the sense in which it is used herein, small means less than about 1 weight percent of fluorine and less than about 5 weight percent of boron. The basalt and mineral wool fibers are examples of other glass fibers useful in the present invention. Preferred glass fibers are formed from glass E and glass derivatives E. Such compositions and methods of making glass filaments therefrom are known to those skilled in the art and their further explanation is not considered necessary in view to the present description. If additional information is needed, such glass compositions and methods of fiberization are described in K, Loewenstein, The Manufacturing Technology of Glass Fibers, (3rd ed., 1993), pages 30-44, 47-60, 115-122 and 126-135, and Patents United States Nos. 4,542,106 and 5,789,329, which are incorporated herein by reference. In addition to glass fibers, the coated fiber strand 10 may further include fibers formed from other natural or artificial fibrillatable materials, such as inorganic non-glass materials, natural materials, organic polymeric materials and combinations thereof. In the sense in which it is used herein, the term "fibrizable" means a material capable of becoming a generally continuous filament, fiber, strand or thread.

Suitable non-glass inorganic fibers include ceramic fibers formed from silicon carbide, carbon, graphite, mullite, aluminum oxide and piezoelectric ceramic materials. Non-limiting examples of natural fibers derived from suitable animals and vegetables include cotton, cellulose, natural rubber, flax, ramie, hemp, sisal and wool. Suitable man-made fibers include those formed from polyamides (such as nylon and aramides), thermoplastic polyesters (such as polyethylene terephthalate and polybutylene terephthalate), acrylics (such as polyacrylonitriles), polyolefins, polyurethanes and vinyl polymers (such as as polyvinyl alcohol). Non-glass fibers that are considered useful in the present invention and methods for preparing and treating such fibers are amply explained in the Encyclopedia of Polymer Science and Technology, vol. 6 (1967), pages 505-712, which is incorporated herein by reference. It is understood that mixtures or copolymers of any of the above materials and combinations of fibers formed from any of the above materials may be used in the present invention, if desired. The present invention will now be explained generally in the context of fiberglass strands, although those skilled in the art will understand that strand 10 may further include one or more of the non-glass fibers discussed above. With continued reference to Figure 1, in a preferred embodiment, fibers 12 of fiber strand 10 of the present invention are impregnated with a primary layer 14 of a dried residue of an aqueous sizing composition applied to at least a portion 17 of the surfaces 16 of the fibers 12 to protect the surfaces of the fiber 16 against abrasion during processing and to inhibit the breakage of the fibers 12. Preferably, the dried residue of the aqueous sizing composition is applied to the entire outer surface 16 or the periphery of the fibers 12. In the sense in which it is used herein, in a preferred embodiment the terms "sizing", "apres-to" or "sizing" refer to the coating composition applied to the fibers immediately after the formation of the fibers. In an alternative embodiment, the terms "sizing", "sizing" or "sizing" also refer to a coating composition (also known as "finishing sizing") applied to the fibers after having removed by heat or chemical treatment a conventional primary coating composition, that is, finishing sizing is applied to bare glass fibers incorporated in fabric form. The aqueous sizing composition includes one or more, and preferably a plurality, of solid particles 18 placed between or adhered to the outer surfaces 16 of the fibers 12 that provide interstitial spaces 21 between adjacent glass fibers 23, 25 of the strand 10. These interstitial spaces 21 correspond in general to the average particle size 19 of the solid particles 18 placed between the adjacent fibers. As used herein, "solid" means a substance that does not flow perceptibly under moderate stress, has a defined capacity to resist forces that tend to deform it, and in ordinary conditions retains a defined size and shape. See Webster's Third International Dictionary of the English Language - Unabridged (1971), page 2169. Further, in the sense in which it is used herein, the term "solid" includes both crystalline and non-crystalline materials. The solid particles 18 have a minimum average particle size 19 (equivalent spherical diameter) of at least 3 microns, preferably at least about 5 microns, and of the order of 3 to about 1000 microns, preferably from about 5 to about 1000 microns, and more preferably from about 10 to about 25 microns. Preferably, each of the solid particles has a minimum particle size of at least 3 microns, and preferably at least about 5 microns. It is also preferred that the minimum average particle size 19 of the solid particles generally corresponds to the average nominal diameter of the glass fibers. It should be appreciated that the above-mentioned particle sizes are preferred over the smaller particle sizes, partly because they are generally less expensive and are easier to disperse. In addition, fabrics made with strands coated with the particles of the sizes discussed above exhibit better "stamping" and "steeping" characteristics when impregnated with a matrix polymeric material compared to fabrics made with strands coated with particles of smaller size. The configuration or shape of the solid particles 18 may be generally spherical (such as beads, microbeads or solid hollow spheres), cubic, laminar or acicular (elongated or fibrous), as desired. For more information on the proper characteristics of the particles see H. Katz et al., (Ed.), Handbook of Fillers and Plastics, (1987), pages 9-10, which are incorporated herein by reference. The solid particles 18 must maintain their minimum average particle size (equivalent spherical diameter) of at least 3 microns, and preferably at least about 5 microns, and maintain more particularly their minimum particle size (equivalent spherical diameter) of at least 3 microns. microns, and preferably at least about 5 microns, under treatment conditions, such that the forces generated between adjacent fibers during weaving, wicking and other processing operations, maintain the interstitial spaces between adjacent fibers 23, 25. In other terstitials between adjacent fibers 23, 25. In other words, the solid particles do not crumble, deform or dissolve in the aqueous sizing composition at a particle size lower than their minimum average particle size under the typical conditions of glass fiber processing , such as exposure to temperatures up to about 25 ° C, and more preferably up to approximately 400 ° C. The glass fibers are subjected to abrasive wear by contact with rough edges of the adjoining glass fibers and / or other solid objects or materials with which the glass fibers come into contact during formation and subsequent treatment, such as interlacing. or wick. "Abrasive wear", in the sense in which it is used herein, means scraping or cutting off pieces of the surface of the fiberglass or the breakage of glass fibers by frictional contact with particles, edges or entities of materials that are sufficiently hard to produce damage to glass fibers. See K. Ludema, Friction, Wear, Lubrication, (1996), page 129, which is incorporated herein by reference. Abrasive wear of fiberglass strands results in breakage of the strand during treatment and surface defects in the products, such as woven fabric and composites, which increase the waste and manufacturing cost. To minimize abrasive wear, the solid particles have a hardness value that does not exceed, that is, is less than or equal to a hardness value of the glass fiber (s). The hardness values of the solid particles and glass fibers can be determined by any conventional method of measuring hardness, such as Vic-kers or Brinell hardness, but is preferably determined according to the original Mohs hardness scale indicating strength relative to the scratching 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), page F-22, which is incorporated herein by reference. The Mohs hardness value of the solid particles is preferably of the order of about 0, 5 to about 6. The Mohs hardness values of several non-limiting examples of solid particles suitable for use in the present invention are set forth in Table A below. Table A 2 K. Ludema, Friction, Wear, Lubrication, (1996), page 27, which is incorporated herein by reference.

R. Weast (Ed.), Handbook of Chemistry and Physics, CRC Press (1975), page F-22. R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th ed., 1993), page 793, which is incorporated herein by reference. Hawley's Condensed Chemical Dictionary, (12th ed., 1993), page 1113, which is incorporated herein by reference. Hawley's Condensed Chemical Dictionary, (12th ed., 1993), page 784, which is incorporated herein by reference. Handbook of Chemistry and Physics, page F-22. Handbook of Chemistry and Physics, page F-22. 9 Friction, Wear, Lubrication, page 27. 10 Friction, Wear, Lubrication, page 27. 11 Friction, Wear, Lubrication, page 27. 12 Friction, Wear, Lubrication, page 27. 13 Handbook of Chemistry and Physics, page F- 22 14 Handbook of Chemistry and Physics, page F-22. 15 Handbook of Chemistry and Physics, page F-22. 16 Handbook of Chemistry and Physics, page F-22. 17 Handbook of Chemistry and Physics, page F-22. 18 Handbook of Chemistry and Physics, page F-22. 11 Handbook of Chemistry and Physics, page F-22.

As mentioned above, the Mohs hardness scale refers to the resistance of a material to scratching. Therefore, the present invention contemplates particles having a surface hardness that differs from the hardness of the internal portions of the particle below its surface. More specifically, the surface of the particle can be modified in a manner known in the art, including, but not limited to, coating, coating or encapsulating the particle or chemically changing its surface characteristics using techniques known in the art, such that The surface hardness of the particle does not exceed the hardness of the glass fibers, while the hardness of the particle below the surface is greater than the hardness of the glass fibers. For example, but without limiting the present invention, the inorganic particles, such as silicon carbide and aluminum nitride, may be provided with a silica, carbonate or nanoclay coating. In addition, Si-coupling agents with alkyl side chains can be reacted with the surface of many oxide particles to obtain a "softer" surface. In general, the solid particles 18 useful in the present invention can be formed from inorganic materials, organic materials or mixtures thereof. Preferably, the solid particles 18 are formed from inorganic materials selected from the group consisting of ceramic materials and metallic materials. Suitable ceramics include metal nitrides, metal oxides, metal carbides, metal sulfides, metal borides, metal silicates, metal carbonates and mixtures thereof. A non-limiting example of a suitable metal nitride is boron nitride, which is the preferred inorganic material from which solid particles useful in the present invention are formed. A non-limiting example of a useful metal oxide is zinc oxide. Suitable metal sulfides include molybdenum disulfide, tantalum disulfide, tungsten disulfide and zinc sulfide. Useful metal silicates include aluminum silicates and magnesium silicates, such as vermiculite. Suitable metallic materials include graphite, molybdenum, platinum, palladium, nickel, aluminum, copper, gold, iron, silver and mixtures thereof. The inorganic solid particles 18 are also preferably solid lubricants. As used herein, "solid lubricant" means that the inorganic solid particles 18 have a characteristic crystalline habit that causes them to tear into thin flat plates that easily slide over one another and thus produce a lubricating effect. between the fiberglass surface and an adjacent solid surface, of which at least one is in motion. See R. Lewis, Sr., Haw-law's Condensed Chemical Dictionary, (12th ed., 1993), page 712, which is incorporated herein by reference. Friction is the resistance to sliding one solid over another. F. Clauss, Solid Lubricants and Self-Lubricating Solids, (1972), page 1, which is incorporated herein by reference. In a preferred embodiment, the solid lubricating particles have a lamellar structure. Particles having a lamellar or hexagonal crystal structure are composed of sheets or plates of atoms in hexagonal arrangement, with strong bond within the sheet and weak van der Waals binding between sheets, providing low shear strength between sheets. Friction, Wear, Lubrication, page 125; Solid Lubricants and Self-Lubricating Solids, pages 19-22, 42-54, 75-77, 80-81, 82, 90-102, 113-120 and 128; and W. Campbell "Solid Lubricants", Boundary Lubrication; An Appraisal of World Literature, ASME Research Committee on Lubrication (1969, pages 202-203, which are incorporated herein by reference.) Inorganic solid particles having a lamellar fullerene structure (soccer ball) are also useful in the present invention. non-limiting examples of suitable lubricants solid particles inorganic having a lamellar structure include boron nitride, graphite, metal dicalcogenidos, mica, talc, gypsum, kaolinite, calcite, cadmium iodide, silver sulfide and mixtures thereof. the preferred inorganic solid lubricant particles include boron nitride, gra-phyto, dicalcogenidos metal and mixtures thereof. the metal dicalcogenidos suitable include molybdenum disulfide, molybdenum diselenide, tantalum disulfide, diselenide, tantalum disulfide, tungsten diselenide, tungsten and its mixtures: boron nitride particles that have a crystal structure Hexagonal agents are highly preferred for use in the aqueous sizing composition. The particles of boron nitride, zinc sulphide and montmorillonite also provide good whiteness in compounds with polymeric matrix materials such as nylon 6,6. Non-limiting examples of boron nitride particles suitable for use in the present invention are PolarTherm® 100 boron nitride powder particles (PT 120, PT 140, PT 160 and PT 180), series 300 (PT 350) and 600 series (PT 620, PT 630, PT 640 and PT 670) marketed by Advanced Ceramics Corporation of Lakewood, Ohio. "PolarTherm® Conductive Fillers for Polymeric Materials", Technical Bulletin of Advanced Ceramics Corporation of Lakewood, Ohio (1996), which is incorporated herein 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 1015 ohm-centimeter. The series 100 powder has an average particle size of the order of from about 5 to about 14 microns, the 300 series has an average particle size of the order of from about 100 to about 150 microns and the 600 series has an average size of particle of the order of from about 16 to more than about 200 microns. The solid lubricating 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 percent by weight), can be included in the sizing composition, if desired. A non-limiting example of a preferred dispersion of about 25 weight percent boron nitride particles in water is ORPAC BORON NITRIDE RELEASECOAT-CONC which is commercially available from ZYP Coatings, Inc., of Oak Ridge, Tennessee. "ORPAC BORON NITRIDE RELEASECOAT-CONC", technical bulletin of ZYP Coatings, Inc., which is incorporated herein by reference. According to the supplier, the boron nitride particles in this product have an average particle size of less than about 3 microns. This dispersion has about 1 percent magnesium aluminum silicate, which according to the supplier binds the boron nitride particles to the substrate to which the dispersion is applied. Other useful products sold by ZYP Coatings include BORON NITRIDE LUBRICOAT® paint, BRAZE STOP and WELD RELÉASE products. Preferably, the sizing composition is essentially free of hydratable lubricating solid particles inorganic or abrasive silica particles or lime-cico, ie carbonate, includes less than about 20 percent by weight of inorganic lubricant particles hydratable, abrasive silica particles or carbonate Calcium based on total solids, more preferably less than about 5 weight percent, and most preferably less than 0.001 weight percent. In the sense in which it is used herein, "hydratable" means that the solid inorganic lubricant particles react with water molecules to form hydrates and contain water of hydration or water of crystallization. A "hydrate" is produced by the reaction of water molecules with a substance in which the H-OH bond is not divided. See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th ed., 1993), pages 609-610 and T. Perros, Chemistry (1967), pages 186-187, which are incorporated into the pre-senté memory by reference . In the chemical formulas of hydrates, the addition of water molecules is conventionally indicated by a centered point, for example, 3MgO-SiO2-H20 (talc), A1203 • 2Si02 • 2H20 (kaolinite). The hydrates contain coordinated water, which coordinates the cations in the hydrated material and can not be removed without breaking the structure, and / or structural water, which occupies the interstices in the structure increasing the electrostatic energy without disturbing the load balance. R. Evans, An Introduction to Crystal Chemistry, (1948), page, 276, which is incorporated herein by reference. Although not preferred, the aqueous sizing composition may contain hydratable or hydrated inorganic solid lubricating materials in addition to the inorganic solid non-hydratable lubricating materials discussed above. Non-limiting examples of such hydratable inorganic solid lubricating materials are mineral clay phyllosilicates, including micas (such as muscovite), talc, montmorillonite, kaolinite and gypsum (CaS04-2H20). In an alternative embodiment, the solid particles 18 can be formed from organic polymeric materials selected from the group consisting of thermoset materials, thermoplastics, starches and mixtures thereof. Suitable thermosetting materials include thermoset polyesters, vinyl esters, epoxy, phenolic, aminoplast, thermosetting polyurethanes and mixtures thereof, such as those explained below. Suitable thermoplastic materials include vinyl polymers, thermoplastic polyesters, polyolefins, polyamides, thermoplastic polyurethanes, acrylic polymers and mixtures thereof. The preferred organic solid particles are in the form of microbeads or hollow spheres. In an alternative preferred embodiment, the solid particles 18 are thermal conductors, that is, they have a thermal conductivity greater than about 30 watts per meter K, such as for example boron nitride, graphite, and the above indicated inorganic solid metal lubricants. The thermal conductivity of a solid material can be determined by any method known to those skilled in the art, such as the hot sheet method protected according to ASTM C-177-85 (which is incorporated herein by reference) at a temperature of approximately 300K. In another alternative preferred embodiment, the inorganic solid particles 18 are electrical insulators or have high electrical resistivity, that is, they have an electrical resistivity greater than about 1000 microohm-cm, such as for example boron nitride. The solid lubricant particles include from about 0.001 to about 99 weight percent of the size composition based on the total solids, preferably, from about 1 to about 80 weight percent, and more preferably from about 1 to about 40 percent by weight. In a preferred embodiment, the size composition may contain more than 20 to about 40 weight percent boron nitride based on total solids. In addition to the solid particles, the aqueous sizing composition preferably includes one or more polymeric film-forming materials, such as thermosetting materials., thermoplastic materials, starches and their mixtures. Preferably the polymeric film-forming materials form a generally continuous film when applied to the surface 16 of the glass fibers. Generally, the amount of polymeric film-forming materials can range from about 1 to about 99 weight percent of the aqueous sizing composition based on the total solids, preferably from about 20 to about 99 weight percent and more preferably about 20 weight percent. 60 to about 80 percent by weight. Polymeric thermosetting film materials are the preferred polymeric film materials for use in the aqueous sizing composition for coating glass fiber strands of the present invention. Such materials are compatible with the thermosetting matrix materials used as laminates for printed circuit boards, such as epoxy resins FR-4, which are polyfunctional epoxy resins and in a particular embodiment of the invention are difunctional brominated epoxy resins. See 1 Electronic Materials Handbook ™, ASM Jnternational (1989), pages 534-537, which are incorporated herein by reference. Useful thermosetting materials include thermoset polyesters, epoxy materials, vinyl esters, phenolics, aminoplastics, thermosetting polyurethanes, and mixtures thereof. Suitable thermoset polyesters include STYPOL polyesters sold by Cook Composites and Polymers of Port Washington, Wisconsin. and NEOXIL polyesters marketed by DSM B.V. of Como, Italy. In a preferred embodiment, the thermoset 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. Examples of suitable epoxy film-forming polymers include EPON® 826 and EPON® 880 epoxy resins, available from the Shell Chemical Company of Houston, Texas. Useful thermoplastic polymeric materials include vinyl polymers, thermoplastic polyesters, polyolefins, polyamides (for example, aliphatic polyamides or aromatic polyamides such as aramid), thermoplastic polyurethanes, acrylic polymers and mixtures thereof. Preferred vinyl polymers useful in the present invention include polyvinyl pyrrolidones such as PVP K-15, PVP K-30, PVP K-60 and PVP K-90, each of which can be obtained from the ISP Chemicals market. Wayne, New Jersey. Other suitable vinyl polymers include emulsions of vinyl acetate copolymer Resyn 2828 and Resyn 1037 which is marketed by National Starch, and other polyvinyl acetates such as those marketed by H. B. Fuller and Air Products and Chemicals Co. of Allentown, Pennsylvania. The thermoplastic polyesters useful in the present invention include DESMOPHEN 2000 and DESMOPHEN 2001KS, marketed by Bayer of Pittsburgh, Pennsylvania. A preferred polyester is RD-847A polyester resin obtainable from the Borden Chemicals market in Columbus, Ohio. Useful polyamides include VERSAMID products marketed by General Mills Chemicals, Inc. Useful thermoplastic polyurethanes include WITCOBOND® W-290H which can be purchased on the market from Witco Chemical Corp., of Chicago, Illinois, and latex RUCOTHANE® 2011L polyurethane available from the Ruco Polymer Corp. market in Hicksvi-lle, New York. The aqueous sizing composition may include a mixture of one or more thermoset polymeric materials with one or more thermoplastic polymeric materials. In a preferred embodiment for laminates for printed circuit boards, the polymeric materials of the aqueous sizing composition include a mixture of polyester resin RD-847A, polyvinyl pyrrolidone PVP K-30, polyester DESMOPHEN 2000 and polyamide VERSAMID. In a preferred alternative embodiment suitable for laminates for printed circuit boards, the polymeric materials of the aqueous sizing composition include a mixture of epoxy resin EPON 826 and polyvinyl pyrrolidone PVP K-30. Useful starches include those prepared from potatoes, corn, wheat, waxy corn, sago, rice, milo and mixtures thereof. A non-limiting example of a useful starch is Kollo-tex 1250 (a low viscosity, low viscosity amylose-based potato starch, etherified with ethylene oxide) available from the AVEBE market in the Netherlands. The polymeric materials can be water soluble, emulsifiable, dispersible and / or curable. As used herein, "water soluble" means that the polymeric materials are capable of essentially uniform mixing and / or molecular or ionic dispersion in water to form a true solution. See Hawley 's, page 1075, which is incorporated herein by reference. "Emulsifiable" means that the polymeric materials are capable of forming an essentially stable mixture or suspended in water in the presence of an emulsifying agent. See Hawley 's, page 461, which is incorporated herein by reference. Non-limiting examples of suitable emulsifying agents are set forth below. "Dispersible" means that any of the components of the polymeric materials is capable of being distributed throughout the water as finely divided particles, such as a latex. See Hawley 's, page 435, which is incorporated herein by reference. The uniformity of the dispersion can be increased by the addition of wetting, dispersing or emulsifying agents (surfactants), which are explained below. "Curable" means that the polymeric materials and other components of the sizing composition are capable of coalescing in a film or crosslinking each other to change the physical properties of the polymeric materials. See Hawley 's, page 331, which is incorporated herein by reference. In addition or in place of the polymeric materials explained above, the aqueous sizing composition preferably includes one or more glass fiber coupling agents such as organosilane coupling agents, transition metal coupling agents, coupling agents. of phosphonate, aluminum coupling agents, Werner coupling agents containing amino and their mixtures. These coupling agents typically have dual functionality. Each metal or silicon atom has one or more groups that can react or compatibilize with the fiber surface and / or the components of the aqueous sizing composition. As used herein, the term "compatibili-zar" means that the groups are chemically attracted, but not bound, to the surface of the fiber and / or the components of the sizing composition, by example by polar, wetting or dissolving forces. Examples of hydrolysable groups include: O H O RJ -OR1, -OC-R2, -N-C-R2, -0-N = C-R4, -0-N = C-R5, and the monohydroxy and / or cyclic residue C2-C3 of 1.2 or 1,3 glycol, wherein R 1 is C 1 -C 3 alkyl; R2 is H or C? -C alkyl; R3 and R4 are independently selected from H, C1-C4 alkyl or C6-Ca aryl; and R5 is C-C7 alkylene. Examples of suitable comparative or functional groups include epoxy, glycidoxy, mercapto, cyano, allyl, alkyl, urethane, halo, isocyanate, ureido, imidazolinyl, vinyl, acrylate, methacrylate, amino or polyamino groups. The functional silane organ coupling agents are preferred for use in the present invention. Examples of useful silane functional coupling agents include gamma-aminopropyl trialkoxysilanes, gamma-isocyanatopropyltriethoxysilane, vinyl trialkoxysilanes, glycidoxypropyltrialkoxysilanes and ureidopropyltrialkoxysilanes. Preferred functional silane organ coupling agents include A-187 gamma-glycidoxypropyl-pyrimethoxysilane, A-174 gamma-methacryloxypropyltrimethoxysilane, coupling agents A-1100 gamma-aminopro-pyriethoxysilane, amino silane A-1108 and A-1160 gamma-ureidopropyltriethoxysilane (each of which is commercialized by OSi Specialties, Inc., of Tarrytown, New York). The organosilane coupling agent can be at least partially hydrolysed with water before application to the fibers, preferably at a stoichiometric ratio of about 1: 1 or, if desired, applied in non-hydrolyzed form. Suitable transition metal coupling agents include coupling agents of titanium, zirconium, yttrium and chromium. Suitable titanate coupling agents and zirconate coupling agents are available from the Kenrich Petrochemical Company. E. I. DuPont de Nemours of Wilmington, Delaware, markets suitable chromium complexes. Werner-type coupling agents containing amino are complex compounds in which a trivalent nuclear atom such as chromium is coordinated with an organic acid having amino functionality. Other coupling agents of the coordinated type and metal guelate known to those skilled in the art can be used here. The amount of coupling agent can range from about 1 to about 99 weight percent of the aqueous sizing composition based on the total solids, and preferably from about 1 to about 10 weight percent. The aqueous sizing composition may further include one or more organic lubricants that are chemically different from the polymer materials discussed above. Although the aqueous sizing composition may include up to about 60 weight percent organic lubricants, preferably the sizing composition is essentially free of organic lubricants, ie, it contains less than about 20 weight percent organic lubricants, and more preferably it is free of organic lubricants. Such organic lubricants include cationic, nonionic or anionic lubricants and mixtures thereof, such as amine salts of fatty acids, alkyl imidazoline derivatives such as CATIÓN X, which is available commercially from Rhone Poulenc of Princeton, New Jersey, amides of acid-solubilized fatty acids, condensates of a fatty acid and polyethylene imine and substituted amide polyethylene imines, such as EMERY® 6717, a partially amidated polyethylene imine obtainable commercially from Henkel Corporation of Kanta-kee, Illinois. The aqueous sizing composition may include one or more emulsifying agents for emulsifying or dispersing components of the aqueous sizing composition, such as inorganic particles. Non-limiting examples of suitable emulsifying agents or surfactants include polyoxyalkylene block copolymers (such as PLURONIC ™ F-108 polyoxypropylene-polyoxyethylene copolymer which is commercially available from BASF Corporation of Parsippany, New Jersey), ethoxylated alkyl phenols (such as IGEPAL CA-630 octylphene-ethanol ethoxylate available commercially from GAF Corporation of Wayne, New Jersey), polyoxyethylene octylphenyl glycol ethers, ethylene oxide derivatives of sorbitol esters , polyoxyethylated vegetable oils (such as ALKA-MULS ES-719, available from the Rhone Poulenc market) and nonylphenol surfactants (such as MACOL NP-6 available from the BASF market in Parsippany, New Jersey) ). Generally, the amount of emulsifying agent can range from about 1 to about 30 weight percent of the aqueous base-sizing composition to the total solids. The aqueous sizing composition may include one or more soluble, emulsifiable or dispersible aqueous wax materials such as vegetable, animal, mineral, synthetic or petroleum waxes. Preferred waxes are petroleum waxes such as MICHEM® LUBE 296 microcrystalline wax, POLYMEKON® SPP-W microcrystalline wax and PE-TROLITE 75 microcrystalline wax obtainable on the market from Michelman Inc., of Cincinnati, Ohio, and Petrolite Corporation. of Tulsa, Oklahoma, respectively. In general, the amount of wax may be from about 1 to about 10 weight percent of the sizing composition based on the total solids. It is also possible to include crosslinking materials, such as melamine formaldehyde, and plasticizers, such as phthalates, trimellitates and adipates, in the aqueous sizing composition. The amount of crosslinker or plasticizer may range from about 1 to about 5 weight percent of the sizing composition based on the total solids. Other additives may be included in the aqueous sizing composition, such as silicones, fungicides, bactericides and antifoaming materials, generally in an amount of less than about 5 weight percent. Organic and / or inorganic acids or bases may also be included in the sizing composition in an amount sufficient to give the aqueous sizing composition a pH of about 2 to about 10. A non-limiting example of a suitable silicone emulsion is emulsion LE-9300 epoxidized silicone that can be purchased from OSi Specialties, Inc., of Danbury, Connecticut. An example of a suitable bactericide is Biomet 66 antimicrobial compound, which can be obtained from the M &; T Chemicals of Rahway, New Jersey. Suitable defoaming materials are the SAG materials sold by OSi Specialties, Inc., of Danbury, Connecticut and MAZU DF-136 which can be obtained from BASF Company of Parsippany, New Jersey. Ammonium hydroxide can be added to the sizing composition to stabilize the size, if desired. Water (preferably deionized) is included in the aqueous sizing composition in an amount sufficient to facilitate the application of a generally uniform coating on the strand. The weight percent solids of the aqueous sizing composition is generally in the range of about 1 to about 20 weight percent. The aqueous sizing composition is preferably essentially free of glass materials. As used herein, "essentially free of glass materials" means that the sizing composition includes less than 20 volume percent of glass matrix materials to form glass compounds, preferably less than about 5 percent by volume, and more preferably is free of glass materials. Examples of such glass matrix materials -include black glass ceramic matrix materials or aluminosilicate matrix materials such as those known to those skilled in the art. In a preferred embodiment for weaving fabric for laminated printed circuit boards, the glass fibers of the coated fiber strands of the present invention are applied to a primary layer of a dry residue of an aqueous sizing composition that includes nitride powder of boron PolarTherm® 160 and / or dispersion BORON NITRIDE RELEASECOAT, epoxy film-forming material EPON 826, polyvinyl pyrrolidone PVP K-30, coupling agent for epoxy functional organ A-187, polyoxyethylated vegetable oil ALKAMULS EL-719, octyl-phenoxyethanol ethoxylated IGEPAL CA-630, KESSCO PEG 600 polyethylene glycol monolaurate ester commercially available from the Stephan Company of Chicago, Illinois, and EMERY® 6717 partially amidated polyethylene imine. In a more preferred embodiment for knitting fabric, the fibers of Glass of the coated fiber strands of the present invention has been applied a primary layer of a dried residue of an aqueous composition of this includes PolarTherm® boron nitride powder and / or BORON NITRIDE RELEASECOAT dispersion, RD-847A polyester, polyvinyl pyrrolidone PVP K-30, DESMOPHEN 2000 polyester, functional acrylic silane coupling agents A-174 and agents of coupling of functional epoxy silane organ A-187, polyoxypropylene-polyoxyethylene copolymer PLURONIC F-108, nonylphenol surfactant MACOL NP-6, VERSAMID 140 and emulsion epoxy silicone LE-9300. The aqueous sizing compositions of the present invention can be prepared by another suitable method such as conventional mixture known to those skilled in the art. Preferably the above-explained components are diluted with water so that they have the desired weight percentage of solids and are mixed. Powdered solid particles can be premixed with water or added to the polymeric material before mixing with the other components of the sizing. The primary size coat can be applied to fiberglass surfaces in many ways, for example by contacting the fibers with a roller or belt applicator, spraying or other means. Sized fibers are dried at least partially at room temperature or at elevated temperatures. The dryer removes excessive moisture from the fibers and, if present, cures the curable components of the sizing composition. The temperature and time to dry the glass fibers will depend on variables such as the percentage of solids in the sizing composition, the components of the sizing composition and the type of glass fiber. The sizing composition is typically present as dried residue in the fibers in an amount between about 0, 1 percent and approximately 5 percent by weight after drying. The fibers are collected in strands having from 2 to about 15,000 fibers per strand, and preferably from about 100 to about 1600 strands per strand. The average diameter of the filament of the fibers can range from about 3 to about 30 microns. A secondary layer of a secondary coating composition can be applied on the primary layer in an amount effective to coat or impregnate the portion of the strands, for example by immersing the strand in a bath containing the composition, spraying the composition on the strand or laying the strand in contact with an applicator as explained above. The coated strand can be passed through a die to remove the excessive coating composition from the strand and / or dry as explained above for a sufficient time 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 preferably dries after application of the secondary coating composition in a manner known in the art. Suitable secondary coating compositions may include one or more film-forming materials, lubricants and other additives as explained above. The secondary coating is different from the sizing composition, i.e., (1) it contains at least one component that is chemically different from the components of the sizing composition.; or (2) contains at least one component in an amount that differs from the amount of the same component contained in the sizing composition. Non-limiting examples of suitable secondary coating compositions including polyurethane are disclosed in U.S. Patent Nos. 4,762,750 and 4,762,751, which are incorporated herein by reference. Referring now to Figure 2, in an alternate preferred embodiment according to the present invention, the glass fibers 212 of the coated fiber strand 210 may have been applied a primary layer 214 of a dried residue of a sizing composition. which may include any of the sizing components in the amounts explained above. Examples of suitable sizing compositions are set forth in Loewenstein, pages 237-291 (3rd ed., 1993) and U.S. Patent Nos. 4,390,647 and 4,795,678, each of which is incorporated herein by reference. A secondary or main layer 215 of an aqueous secondary coating composition is applied to at least a portion, and preferably on the entire outer surface, of the primary layer 214. The secondary coating aqueous composition includes one or more types of solid particles 216 as explained in detail above. Preferably, the solid particles in the secondary coating composition are non-hydratable lamellar inorganic lubricating particles, such as boron nitride, which have been explained above. The amount of inorganic lubricant particles in the secondary coating composition can range from about 1 to about 99 weight percent based on total solids and preferably from about 20 to about 90 weight percent. The percentage of solids of the aqueous secondary coating composition is generally from about 5 to about 50 weight percent. In an alternative embodiment, the solid particles of the secondary coating composition include hydrophilic inorganic solid particles that absorb and retain water in the interstices of the hydrophilic particles. Hydrophilic inorganic solid particles can absorb water or swell when they come in contact with water or participate in a chemical reaction with water to form, for example, a viscous gel-like solution that blocks or inhibits the further entry of water into the interstices of a telecommunications cable for whose reinforcement the fiberglass coated strand is used. As used herein, "absorb" means that water penetrates the internal structure or interstices of the hydrophilic material and is substantially retained in them. See Hawley's Condensed Chemical Dictionary, page 3, which is incorporated herein by reference. "Swelling" means that the hydrophilic particles expand in size or volume. See Webster's New Collegate Dictionary (1977), page 1178, which is incorporated herein by reference. Preferably, the hydrophilic particles swell after contact with water at least one and a half times their original dry weight, and more preferably from about two to about six times their original weight. Non-limiting examples of swollen hydrophilic inorganic solid lubricating particles include smectites such as vermiculite and montmorillonite, absorbent zeolites and inorganic sorbent gels. Preferably, these hydrophilic particles are applied in powder form over sticky sizing or other sticky 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 based on total solids and preferably from about 20 to about 90 weight percent. In an alternative embodiment shown in figure 3, 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, ie, such fiber strand 312 would have a primary layer 314 of sizing, a secondary layer 315 of a secondary coating composition and a tertiary outer layer 320 of the tertiary coating. The tertiary coating differs from the size composition and the secondary coating composition, ie, the tertiary coating composition (1) contains at least one component that is chemically different from the size components and the secondary coating composition.; or (2) contains at least one component in an amount that differs from the amount of the same component contained in the sizing or secondary coating composition. In this embodiment, the secondary coating composition includes one or more polymeric materials discussed above, such as polyurethane, and the tertiary powder coating composition includes solid particles in powder form, such as the PolarTherm® boron nitride particles discussed above. Preferably, the powder coating is applied by passing the strand to which a liquid secondary coating composition is applied, through a fluidized bed or spray device to adhere the powder particles to the sticky secondary coating composition. Alternatively, the strands can be mounted to a fabric 810 prior to applying the tertiary coating layer 812, as shown in Figure 8. The weight percentage of solid powder particles adhered to the coated fiber strand 310 can range from approximately 0.1 to about 30 weight percent of the total weight of the dried strand. The tertiary powder coating may also include one or more polymeric materials such as those discussed above, such as acrylic polymers, epoxies, or polyolefins, conventional stabilizers and other modifiers known in the art of such coatings, preferably in the form of a dry powder. The coated fiber strands 10, 210, 310 discussed above can be used as a continuous strand or further process to various products such as chopped strand, braided strand, wick and / or fabric, such as woven, non-woven, knitted and mats. The 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 compound 414, as shown in Figure 4, which will be explained in detail later. Such applications include, but are not limited to, laminates for printed circuit boards, reinforcements for telecommunications cables, and various other compounds. An advantage of the impregnated strands of the present invention is that the solid particles provide interstices between the fibers of the strand which facilitate the flow of the matrix materials therebetween to soak and more quickly and / or staple the fibers of the strand. Surprisingly, the amount of solid particles can exceed 20 percent by weight of the total solids of the coating composition applied to the fibers, and still adequately adhere to the fibers and provide strands having handling characteristics at least comparable to those of the fibers. the strands without the coating with solid particles. In a preferred embodiment shown in Figure 5, coated fiber strands 510 made according to the present invention can be used as warp and / or weft strands 514, 516 in a knitted or woven fabric reinforcement 512, preferably to form a laminate for a printed circuit board (shown in figures 6-8). The warp yarns 514 can be twisted before the secondary coating by any torsion technique known to those skilled in the art, for example using torsion frames to impart torsion from about 0.5 to about 3 turns per torsion. , 54 cm (1 inch). The reinforcing fabric 512 may include from about 5 to about 50 warp strands 514 and preferably has from about 3 to about 25 weft threads per centimeter (about 1 to about 15 weft threads per inch) of the weft 516 stitch A suitable woven fabric reinforcement 512 can be formed using any conventional loom known to those skilled in the art, such as a shuttle loom., loom of air jet or rapier loom weft. A pre-ferred loom is a Tsudakorna loom that can be purchased at the Tsudakorna market in Japan. The weaving construction can be a regular taffeta weave or mesh (shown in Figure 5), although any other weaving style known to those skilled in the art can be used, such as a loosely woven or satin weave. Referring now to Figure 6, the fabric 612 can be used to form a composite or laminate 614 by coating and / or impregnation with a thermosetting matrix or polymeric film-forming thermoplastic material 616. The composite or laminate 614 is suitable to be used as an electronic support. As used herein, "electronic support" means a structure that 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 thermoset materials such as thermoset 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 , animoplastics, thermosetting polyurethanes, derivatives and their mixtures. Preferred matrix materials for forming laminates for printed circuit boards are FR-4 epoxy resins, polyimides and liquid crystalline polymers, whose compositions are known to those skilled in the art. If more information regarding such compositions is needed, see 1 Electronic Materials HandbookTM, ASM International (1989), pages 534-537. Non-limiting examples of suitable polymeric thermoplastic matrix materials include polyolefins, polyamides, thermoplastic polyurethanes and thermoplastic polyesters, vinyl polymers and mixtures thereof. Other examples of useful thermoplastic materials include polyimides, polyether sulfones, polyphenyl sulfones, polyetherketones, polyphenylene oxides, polyphenylene sulfides, polyacetals, polyvinyl chlorides and polycarbonates. Other components that may be included with the polymeric matrix material and reinforcing material in the composite include dyes or pigments, lubricants or treatment aids, ultraviolet (UV) light stabilizers, antioxidants, other fillers and extenders. The fabric 612 can be coated and impregnated by immersing the fabric 612 in a bath of the polymeric matrix material 616, for example, as explained in R. Tummala (ed.), Microelectronics _Packaging Manual, (1989), pages 895- 896, which is incorporated herein by reference. More generally, chopped or continuous fiber strand reinforcement material may be dispersed in the matrix material by hand or suitable automatic feed or mixing device which distributes the reinforcing material in a generally uniform manner throughout the polymeric matrix material. . For example, the reinforcing material can be dispersed in the polymeric matrix material by dry blending simultaneously or sequentially all the components.

The polymeric matrix material 616 and the strand can be converted to a composite or laminate 614 by various methods depending on factors such as the type of polymeric matrix material used. For example, for a thermosetting matric material, the compound can be formed by compression or injection molding, stretch extrusion, filament winding, hand laying, spraying or by sheet molding or bulk molding followed by casting. compression or injection. The thermoset 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 for crosslinking the polymer matrix material are explained above. The temperature and curing time for the thermoset polymeric matrix material depends on factors such as the type of polymeric matrix material used, other additives in the matrix system and the thickness of the composite, to name a few. For a thermoplastic matrix material, suitable methods for forming the compound include direct molding or extrusion blending followed by injection molding. The methods and apparatus for forming the compound by the above methods are explained in I. Rubin, Handbook of Plastics Materials and Technology (1990), pages 955-1062, 1179-1215 and 1225-1271, which are incorporated herein. by reference. In a particular embodiment of the invention shown in Figure 7, the composite or laminate 710 includes fabric 712 impregnated with a compatible matrix material 714. The impregnated fabric can then be compressed between a set of metering rollers to leave a measured amount of material of matrix, and dried to form an electronic support in the form of a semi-cured or prepreg substrate. An electrical conductive layer 720 may be placed along a portion of a side 722 of the prepreg in the manner that will be explained later in the specification, and the prepreg is cured to form an electronic support 718 with an electrical conductive layer. In another embodiment of the invention, and more typically in the electronic media industry, two or more prepregs are combined with an electrical conductive layer and laminated and cured in a manner known to those skilled in the art, to form a multilayer electronic support. For example, while not limiting the present invention, the stack of prepregs can be laminated by pressing the stack, for example between polished steel sheets, at elevated temperatures and pressures for a predetermined period of time to cure the polymer matrix and form a laminate. a desired thickness. A portion of one or more of the prepregs can receive an electrical conductive layer before or after the rolling and curing in such a way that the resulting electronic support is a laminate having at least one electrical conductive layer along a portion of a surface exposed (later referred to as "coating laminate"). Circuits can then be formed from the electrically conductive (s) cap (s) of the single layer or multilayer electronic support using techniques known in the art to construct an electronic support in the form of a printed circuit board or printed wiring board (hereinafter referred to as "electronic circuit boards"). If desired, holes or openings (also called "tracks") may be formed in the electronic supports, to allow electrical interconnection between circuits and / or components on opposite surfaces of the electronic support, in any convenient manner known in the art. , including, but not limited to, mechanical drilling and laser drilling. More specifically, after the formation of the holes, a layer of electrical conductive material is deposited on the walls of the hole or the hole is filled with an electrically conductive material to facilitate the necessary electrical interconnection and / or heat dissipation. The electrical conductive layer 720 can be formed by any method known to those skilled in the art. For example, but without limiting the present invention, the electrical conductive layer can be formed by laminating a thin sheet or sheet of metallic material on at least a portion of one side of the pre-preg or semi-cured or cured laminate. Alternatively, the electrical conductive layer can be formed by depositing a layer of metallic material on at least a portion of one side of the semi-cured or cured prepreg or laminate using well-known techniques including, but not limited to, electrolytic plating, non-electrolytic coating or cathodic deposition . Suitable metallic materials 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. In another embodiment of the present invention, the electronic support may be in the form of a multilayer electronic circuit layer constructed by laminating one or more layers of electronic circuits (described above) with one or more coating laminates (described above) and / or one or more. several prepregs (previously described). If desired, additional electrical conductive layers can be incorporated into the electronic support, for example along a portion of an exposed side of the multilayer electronic circuit board. In addition, if necessary, additional circuits can be formed from the electrical conductive layers in the manner explained above. It should be appreciated that, depending on the relative positions of the layers of the multilayer electronic circuit board, the board can have both internal and external circuits. Additional holes are formed, as explained above, partially or completely through the plate to allow electrical interconnection between the layers at selected positions. It should be appreciated that the resulting structure may have some holes that extend completely through the structure, some holes that extend only partially through the structure, and some holes that are completely inside the structure. The present invention also contemplates the manufacture of multilayer laminates and electronic circuit boards that include at least one composite layer made according to the ideas of the present invention and at least one composite layer made differently from the composite layer described herein, for example made using conventional technology of fiberglass composites. More specifically and as those skilled in the art are aware, filaments in continuous fiberglass strands used in weaving fabric are traditionally treated with a starch / oil size that includes partially or fully dextrinized or amylose starch, hydrogenated vegetable oil, an agent cationic humectant, emulsifying agent and water, including, but not limited to, those described in Loewenstein, pages 237-244 (3rd ed., 1993), which is incorporated herein by reference. The warp yarns produced from these strands are then treated with a solution prior to weaving to protect the strands against abrasion during the weaving process, for example polyvinyl alcohol as described in US Pat. 4,530,876, in column 3, line 67 to column 4, line 11, which is incorporated herein by reference. This operation is commonly called glued. Poly (vinyl alcohol) as well as starch / oil size are generally not compatible with the polymer matrix material used by compound manufacturers and the fabric must be cleaned to essentially remove all organic material from the surface of the the glass fibers before impregnating the woven fabric. This can be done in various ways, for example by washing the fabric or, more commonly, heat-treating the fabric in a manner known in the art. As a result of the cleaning operation, there is no adequate interface between the polymer matrix material used to impregnate the fabric and the clean surface of fiberglass, so that a coupling agent must be applied to the fiberglass surface. This operation is sometimes called finishing by experts in the field. Coupling agents most commonly used in finishing operations are silanes including, but not limited to, those described in E. P. Plueddemann, Silano Coupling Agents (1982), pages 146-147, which is incorporated herein by reference. See also Loewenstein, pages 249-256 (3rd ed., 1993). After treatment with the silane, the fabric is impregnated with a compatible polymeric matrix material, compressed between a set of dosing rollers and dried to form a semi-cured prepreg as explained 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 sizing and / or finishing steps can be eliminated. Then one or more prepregs incorporating conventional fiberglass composite technology can be combined with one or more prepregs incorporating the present invention to form an electronic support as explained above, and in particular a multilayer laminate or sheet electronic circuits. For more information on the manufacture of electronic circuit boards, see 1 Electronic Materials Handbpoj ™, ASM International (1989), pages 113-115; R. Tummala (ed.), Microelectronics Packaging Manual, (1989), pages 858-861 and 895-909; M. W. Jawitz, Printed Circuit_ Board Handbook (1997), pages 9.1-9.42; and C.

F. Coob, Jr. (ed.), Printed Circuits Handbook, (3rd ed. 1988), pages 6.1-6.7, which are incorporated herein by reference. The compounds and laminates forming the electronic supports of the present invention can be used to form the packaging used in the electronics industry, and more particularly in the first, second and / or third tier packaging, such as that described in Tummala, pages 25-43, which is incorporated herein by reference. In addition, the present invention can also be used for other levels of packaging. The present invention also includes a method for reinforcing a polymeric matrix material to form a compound. The method includes: (1) applying to the fiberglass strand reinforcement material the above size, secondary coating composition and / or tertiary coating including solid inorganic particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns, and preferably at least about 5 microns, and a Mohs hardness that is less than the Mohs hardness of the glass fibers; (2) drying the coating to form a substantially uniform coating on 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 polymeric composite reinforced in the manner explained in detail above. While not limiting the present invention, 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 fiberglass strand, including the steps of: (1) applying to a glass fiber strand the above size, the secondary coating composition or tertiary coating including inorganic solid particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns, and preferably at least about 5 microns, and a Mohs hardness that is lower to Mohs hardness of glass fibers; (2) drying the coating to form a substantially uniform coating on the glass fibers of the fiberglass strand, in such a way that adhesion is inhibited between adjacent glass fibers of the strand. The present invention will now be illustrated by the following specific non-limiting examples. EXAMPLE 1 Each of the components was mixed in the amounts set forth in Table 1 to form aqueous sizing compositions K to N according to the present invention. Each aqueous composition of sizing preparation was prepared in a similar manner to that explained. Less than about 1 weight percent acetic acid based on total weight was included in each composition. Each of the aqueous sizing compositions of Table 1 was coated on E 2G-18 glass fiber strands. Each of the forming sizing compositions had about 10 weight percent solids.

Table 1 Aqueous polyurethane emulsion based on thermoplastic polyester having 65 percent solids, charge of anionic particles, particle size of about 2 microns, a pH of 7.5 and a viscosity of 400 centipoise (Brookfield LVF) at 25 ° C. 21 Aqueous polyurethane dispersion based on thermoplastic polyester having a solids content of 62 percent, pH of about 10, and average particle size in the range of about 0.8 to about 2.5 microns. 22 ORPAC BORON NITRIDE RELEASECOAT-CONC particles of boron nitride in aqueous dispersion that can be purchased in the ZYP Coatings market, Inc., of Oak Ridge, Tennessee. Composite samples of each of the above coated glass fiber samples and the comparative sample were molded by extrusion at 270 ° C for 48 seconds at approximately 7 MPa (975 pounds per square inch) to produce plates of 254 x 254 x 3.175 millimeters (10 x 10 x 0.125 inches). Each specimen was evaluated with respect to: tensile strength, tensile elongation and tensile modulus according to ASTM method D-638M; Flexural strength and flexural modulus according to ASTM D-790 method; and Notched Izod Impact Resistance and Not Notched according to ASTM Method D-256 to the glass content specified below. Table 2 presents the results of tests performed on compounds formed using a conventional nylon 6,6 matrix resin. Table 2 As shown in Table 2, fiberglass strands coated with boron nitride particles (KN samples) according to the present invention exhibit better properties of tensile strength and notched Izod impact and similar elongation to the traction and modulus, bending strength and modulus and Izod impact properties without notch compared to a comparative sample with similar components that did not contain boron nitride in the nylon 6,6 reinforcement. When evaluated using nylon 6 resin under similar conditions, improvements in tensile strength and notched Izod impact properties were not observed. EXAMPLE 2 Each of the components was mixed in the amounts set forth in Table 3 to form aqueous size preparation compositions P to S according to the present invention. Each aqueous composition of sizing preparation was prepared in a manner similar to that explained above. Less than about 1 weight percent acetic acid based on total weight was included in each composition. Each of the aqueous sizing compositions of Table 3 was coated on glass fiber strands E G-31. Each of the forming sizing compositions had about 10 weight percent solids.

Table 3 23 Aqueous polyurethane emulsion based on thermoplastic polyester having 65 percent solids, anionic charge, particle size of approximately 2 microns, a pH of 7.5 and a viscosity of 400 centipoise (Brookfield LVF) at 25CC. 24 Aqueous polyurethane dispersion based on thermoplastic polyester having a solids content of 62 percent, pH of about 10, and average particle size in the range of about 0.8 to about 2.5 microns. PolarTherm® PT 160 particles of bore nitride powder marketed by Advanced Ceramics Corporation of Lakewood, Ohio. 26 VANTALC 2003 talcum powder particles sold by R. I. Vanderbilt Company, Inc., of Norwalk. Connec- ticut. Compound samples of each of the above coated glass fiber samples and the comparative sample of Table 1 above were molded by extrusion to produce plates of 400 x 400 x 2.5 millimeters (16 x 16 x 0.100 inches) in the conditions stated in example 1 above. Each specimen was evaluated with respect to: tensile strength, tensile elongation, tensile modulus, Izod notched impact strength and no notch as explained in example 1 above to the glass content specified below. Color tests were performed on compounds with a thickness of 3.175 millimeters (1/8 inch) and a diameter of 76.2 millimeters (3 inches) using a Hunter Colorimeter Model D25-PC2A. To evaluate the handling characteristics of the material, cone flow tests were performed on fiber-glass chips. The cone was 45.72 cm (18 inches) long and a hole 43.18 cm (17 inches) in diameter at the top and a hole 5.08 cm (2 inches) at the bottom. The cone was vibrated and the flow time of 9.06 kg (20 pounds) of sample material was recorded through the cone. The PD-104 test evaluates the filament resistance of the chopped fiberglass sample. 60 grams of sample, 140 grams of an abrasive material (crushed walnut husk particles number 6/10 sold by Hammon Products Company) and an antistatic drying sheet of the conventional foam type in a 4 liter stainless steel cylinder were enclosed and was vibrated using a Red Devil model 5400E3 paint shaker for six minutes. The vibrated material was screened using US standard test sieves # 5 and # 6. The percentage by weight of fluff material collected on the sieves as a percentage of the original sample is indicated below. Table 4 presents the results of tests performed on compounds formed using P-S samples and the comparative sample using nylon 6.6 matrix resin. Table 4 As shown in Table 4, fiberglass strands coated with boron nitride particles (PS samples) according to the present invention exhibit better whiteness and yellowness and similar properties of tensile strength, elongation and modulus, resistance to flexure and modulus, and Izod impact notched and notched compared to a comparative sample with similar components that did not contain boron nitride in the nylon 6,6 reinforcement. EXAMPLE 3 Each of the components was mixed in the amounts set forth in Table 5 to form aqueous size preparation compositions T and U according to the present invention. Each aqueous composition of sizing preparation was prepared in a manner similar to that explained above. Less than about 1 weight percent acetic acid based on total weight was included in each composition. Table 5 presents the results of the whiteness and yellowness tests performed on compounds formed using the samples T, U and the comparative sample using nylon matrix resin 6.6. Color tests were performed on compounds with a thickness of 3.175 millimeters (1/8 inch) and a diameter of 76.2 millimeters (3 inches) using a Hunter Model colorimeter D25-PC2A. Table 5 27 Aqueous polyurethane emulsion based on thermoplastic polyester having 65 percent solids, anionic particle charge, particle size of approximately 2 microns, a pH of 7.5 and a viscosity of 400 centipoise (Brookfield LVF) at 25 ° C. b Aqueous polyurethane dispersion based on thermoplastic polyester having a solids content of 62 percent, pH of about 10, and average particle size in the range of about 0.8 to about 2.5 microns. 2 ORPAC BORON NITRIDE RELEASECOAT-CONC particles of boron nitride in aqueous dispersion that can be purchased from ZYP Coatings, Inc., of Oak Ridge, Tennessee. As shown in Table 5, samples T and U, each coated with a size composition containing boron nitride particles according to the present invention, had lower whiteness indexes in nylon 6, 6 than a comparative sample of a formulation. similar that did not include boron nitride. EXAMPLE 4 The components were mixed in the amounts set forth in Table 6 to form aqueous sizing compositions A-D according to the present invention in a manner similar to that explained above. Less than 1 weight percent acetic acid was included in each composition.

Table 6 RD-847A polyester resin that can be purchased from the Borden Chemicals market in Columbus, Ohio. 31 DESMOPHEN 2000 polyethylene diol adipate available from the Bayer market in Pittsburgh, Pennsylvania. 32 EPI-REZ® 3522-W-66 available on the market from Shell Chemical Co. , from Houston, Texas. 33 PVP K-30 polyvinyl pyrrolidone available from the ISP Chemicals market in Wayne, New Jersey. A-187 gamma-glycidoxypropyltrimethoxysilane obtainable commercially from OSi Specialties, Inc., of Portland, New York. 35 A-174 gamma-methacryloxypropyltrimethoxysilane which is available commercially from OSi Specialties, Inc., of Tarrytown, New York. 3G A-1100 amino functional organ coupling agent that can be purchased from the OSI Specialties, Inc., of Tarrytown, New York. 37 PLURONIC ™ F-108 polyoxypropylene-polyoxyethylene copolymer available commercially from BASF Corporation of Parsippany, New Jersey. 38 IGEPAL CA-630 ethoxylated octylphenoxyethanol that can be purchased from the GAF Corporation market in Wayne, New Jersey. 39 VERSAMID 140 Polyamide available from General Mills Chemicals, Inc. 40 MACOL NP-6 nonylphenol surfactant available from the BASF market in Parsippany, New Jersey. 41 EMERY® 6760 lubricant available from the Henkel Corporation market in Kankakee, Illinois.

TO? POLYOX WSR-301 polyoxyethylene polymer available from the Union Carbide market in Danbury, Connecticut. 43 PolarTherm® PT 160 boron nitride powder particles marketed by Advanced Ceramics Corporation of Lakewood, Ohio. 44 ORPAC BORON NITRIDE RELEASECOAT-CONC boron nitride particles in aqueous dispersion available from the market of ZYP Coatings, Inc., Oak Ridge, Tennessee. The aqueous sizing compositions A-D and comparative sample number 1 were coated on glass fiber strands E. Each of the sizing compositions had approximately 2.5 weight percent solids. Each fiberglass-coated strand was twisted to form a yarn and wound on coils in a similar manner using conventional torsion equipment. Several physical properties were evaluated, such as ignition loss (LOI), air jet compatibility (aerodynamic re-resistance), friction force and broken filaments of the samples AD strands, comparative sample number 1 and a comparative sample No. 245. The average ignition loss (percent by weight solids of the formation sizing composition divided by the total weight of the glass and dried sizing composition) of three tests of each sample is set forth in Table 7. evaluated the drag force or tension of each yarn by feeding the yarn at a controlled feed rate of 274 meters (300 yards) per minute through a reference line tension meter, which applied tension to the yarn, and a Ruti air nozzle two millimeters in diameter at an air pressure of 310 kPa (45 pounds per square inch). 4: '1383 fiberglass yarn product available on the market PPG Industries, Inc. The friction force of the samples and comparative samples was also evaluated by applying a tension of approximately 30 grams to each sample of yarn when the sample was dragged at a speed of 274 meters (300 yards) per minute through a pair of conventional strain gauges having a stationary chrome pole of approximately 5 centimeters (2 inches) in diameter mounted therebetween to displace the thread approximately 5 centimeters of a straight line path between the devices measuring the voltage. The difference in force in grams is shown in table 7 below. The friction force test aims to simulate the friction forces to which the yarn is subjected during weaving operations. The broken filaments of each sample and comparative sample were also evaluated using an abrasion meter. Two hundred grams of tension was applied to each test sample when each test sample was drawn at a rate of 0.46 meters (18 inches) per minute for five minutes through an abrasion tester. Two test passages of each sample and comparative sample were evaluated and the average number of broken filaments is indicated in table 7 below. The abrasimeter consisted of two parallel rows of steel combs, each row being placed approximately one inch away. Each sample of test yarn was passed between two adjacent combs of the first row of combs, then passed between two adjacent combs of the second row of combs, but moved a distance of 1.27 cm (one-half inch) between the rows of combs. The combs were moved back and forth a length of 10.16 cm (four inches) in a direction parallel to the direction of travel of the yarn at a speed of 240 cycles per minute. The results of the aero dynamic strength, the frictional force and the broken filaments under abrasion for the samples A-D and the comparative samples are shown in table 7 below. Table 7 As shown in Table 7, samples A and B, which are coated with size compositions containing boron nitride according to the present invention, had few broken filaments, low frictional force and higher drag values compared to the comparative samples. Samples C and D also had higher aerodynamic drag values than the comparative samples. The aerodynamic drag test is a relative test designed to simulate the weft insertion process of an air jet loom in which the yarn is transported through the loom by air jet propulsion. The yarns that are more easily filamented by the air jet provide greater surface area for air jet propulsion, which can facilitate the advance of the yarn through the loom and increase productivity. The aerodynamic drag values of the samples A-D (samples prepared according to the present invention) are higher than those of the comparative samples, which indicates excellent compatibility with the air jet. EXAMPLE_5 Each of the components was mixed in the amounts set forth in Table 8 to form aqueous size preparation compositions E, F, G and H according to the present invention and the comparative sample in a manner similar to that explained above. Less than about 1 weight percent acetic acid based on total weight was included in each composition. Each of the aqueous sizing compositions of Table 8 was coated on glass fiber strands E G-75. Each of the formation sizing compositions had between about 6 and about 25 weight percent solids. Table 8 4 EPON 826 that can be purchased at the Shell Chemical market in Houston, Texas. 47 PVP K-30 polyvinyl pyrrolidone available from the ISP Chemicals market in Wayne, New Jersey. 48 ALKAMULS EL-719 polyoxyethylated vegetable oil available from the Rhone-Poulenc market. 49 IGEPAL CA-630 ethoxylated octylphenoxyethanol that can be purchased from the GAF Corporation market in Wayne, New Jersey. 50 KESSCO PEG 600 polyethylene glycol monolaurate ester available from the Stephan Company market in Chicago, Illinois. 51 A-187 gamma-glycidoxypropyltrimethoxysilane available commercially from OSi Specialties, Inc., of Tarrytown, New York. 52 EMERY® 6717 partially amidated polyethylene imine available from the Henkel Corporation market in Kankakee, Illinois. 53 Protolube HD high density polyethylene emulsion available from the Sybron Chemicals market in Birmingham, New Jersey. 54 PolarTherm® PT 160 particles of boron nitride powder marketed by Advanced Ceramics Corporation of Lakewood, Ohio. 55 ORPAC BORON NITRIDE RELEASECOAT-CONC boron nitride particles in aqueous dispersion that can be purchased from ZYP Coatings, Inc., of Oak Ridge, Tennessee. Each coated fiberglass strand was twisted to form yarn and coiled in coils in a similar manner using conventional torsion equipment. The threads of samples F and H exhibited minimal sizing fall during twisting, and the threads of samples E and G exhibited severe sizing drop during torsion. The aerodynamic drag of the EH samples and the comparative sample was evaluated in a manner similar to that of Example 4 above, except that the aerodynamic drag values were determined for two coil samples at the pressures indicated in Table 9. The average number of broken filaments per 1200 meters of wire at 200 meters per minute using a Shirley Model No. 84 041L broken filament detector, which can be purchased from SDL International Inc., of England. These values represent the average of the measurements made on four coils of each thread. The broken filament values are taken from sections taken from a complete coil, 136 grams (3/10 pound) and 272 grams (6/10 pound) of thread unwound from the coil. The tension of the wicket of each yarn was also evaluated. The results of the test are shown in Table 9 below. The number of broken filaments measured according to the tension method of the gate is determined by unwinding a sample of yarn from a coil at 200 meters / minute, passing the yarn through a series of 8 parallel ceramic tines and passing the thread through the Shirley broken filament detector cited above to count the number of broken filaments.

Table 9 Although the results of the test presented in Table 9 seem to indicate that the EH samples according to the present invention had generally higher abrasion resistance than the comparative sample, it is believed that these results are inconclusive since it is believed that a component of Polyethylene emulsion of the comparative sample, which was not present in the EH samples, contributed to the abrasive properties of the yarn. EXAMPLE 6 Five layers of ADFLO-C ™ chopped fiberglass punched mat, available commercially from PPG Industries, Inc., were piled to form a mat having a surface weight of about 4614 grams per square meter ( 15 ounces per square foot). The thickness of each sample was approximately 25 millimeters (approximately 1 inch). Four 20.32 cm (8 inch) square samples of said mat were heated to a temperature of approximately 649 ° C (approximately 1200 ° F) to remove essentially all the sizing components from the samples. Two uncoated samples were used as comparative samples. The other two samples were immersed and saturated in a bath of an aqueous coating composition consisting of 1150 milliliters of BORON NITRIDE RELEASECOAT-CONC ORPAC (25 weight percent boron nitride particles in an aqueous dispersion) and 150 milliliters of 5 weight percent aqueous solution of A-187 gamma-glycidoxypropyltrimethoxysilane. The total solids of the aqueous coating composition were approximately 18, 5 weight percent. The amount of boron nitride particles applied to each mat sample was approximately 120 grams. The coated mat samples were dried in air overnight at a temperature of about 25 ° C and heated in an oven at about 150 ° C for about three hours. The thermal conductivity and thermal resistance in air of each set of samples were evaluated at temperatures of approximately 300K (approximately 70 ° F) according to ASTM method C-177, which is incorporated herein by reference. The values of the thermal conductivity and thermal resistance for each sample are shown in Table 10 below. Table 10 With reference to Table 10, the thermal conductivity at a temperature of about 300K of the test sample coated with boron nitride particles according to the present invention was greater than the thermal conductivity of the comparative sample that was not coated with nitride particles. of boron. EXAMPLE 7 Filament wound cylindrical compounds were prepared from samples of G-75 yarn coated with size G from Example 2 above and glass fiber yarn 1062 available commercially from PPG Industries, Inc. Cylinders were prepared removing eight ends of yarn from a yarn supply, coating the yarn with the matrix materials discussed below, and winding the filaments of the yarn to a cylindrical shape using a conventional filament winding apparatus. Each of the cylinders was 12.7 centimeters (5 inches) high, an internal diameter of 14.6 centimeters (5.75 inches) and a wall thickness of 0.635 centimeters (0.25 inches). The matrix materials were a mixture of 100 parts of EPON 880 epoxy resin (sold by Shell Chemical), 80 parts of AC-200J methyl tetrahydrophthalic anhydride (marketed by Anhydrides and Chemicals, Inc., of Newton, New Jersey). ), and 1 part of ARALDITE® DY 062 benzyl dimethyl amine accelerator (marketed by Ciba-Geigy). The filament winding cylinders were cured for two hours at 100 ° C and then for three hours at 150 ° C. The radial thermal diffusivity (thermal conductivity / (heat capacity x density)) of each test sample in air was determined by exposing one side of the cylindrical wall of the sample to a 6.4 kJ flashing lamp and detecting the temperature change in the opposite side of the wall using an infrared CCD camera at a speed of up to 2000 blocks per second. The thermal diffusivity values were also determined along a length of the yarn (circumferential) and along a length or height of the cylinder (axial). The results of the test are shown below in Table 11. Table 11 With reference to table 11, the thermal diffusivity values for the test sample (which was coated with a small amount of boron nitride) are lower than those of the comparative sample, which was not coated with boron nitride. The air voids in the filament winding cylinder and the small sample area verified are factors that may have influenced these results. It can be seen from the above description that the present invention provides fiberglass strands having an abrasion resistant coating that provide good thermal stability, low corrosion and reactivity in the presence of high humidity, reactive acids and alkalis and compatibility with a variety of polymeric matrix materials. These strands can be twisted or chopped, formed into a wick, chopped mat or continuous strand mat or woven into a fabric for use in a wide variety of applications, including reinforcements for composites such as printed circuit boards. Those skilled in the art will appreciate that changes could be made to the embodiments described above without departing from its broad novel concept. It is understood, therefore, that this invention is not limited to the particular embodiments described, but is intended to cover the modifications that fall within the spirit and scope of the invention, defined by the appended claims.

Claims (68)

Rei indications

1. A coated fiber strand including a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the strand being impregnated at least partially with a dried residue of an aqueous size composition including solid particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns and a hardness not exceeding the hardness of the plurality of glass fibers.

2. The coated fiber strand according to claim 1, wherein the average nominal diameter of the fibers of the plurality of glass fibers is greater than 9 microns.

3. The coated fiber strand according to claim 1, wherein the minimum average particle size of the solid particles is of the order of 3 microns to less than about 1000 microns.

4. The coated fiber strand according to claim 1, wherein the minimum average particle size of the solid particles is at least about 5 microns.

5. The coated fiber strand according to claim 4, wherein the minimum average particle size of the solid particles is of the order of about 5 microns to less than about 1000 microns.

6. The coated fiber strand according to claim 1, wherein the hardness value of the solid particles is less than or equal to the hardness value of the glass fibers.

7. The coated fiber strand according to claim 1, wherein the solid particles have a hardness value Mohs of the order of from about 1 to about 6.

8. The coated fiber strand according to claim 1, wherein each of the solid particles has a shape independently selected from the group consisting of spherical, cubic, laminar and acicular.

9. The coated fiber strand according to claim 1, wherein the solid particles are formed from inorganic materials, organic materials and mixtures thereof.

10. The coated fiber strand according to the claim 9, where the solid particles are formed from at least one inorganic material selected from the group consisting of ceramic materials and metallic materials.

11. The coated fiber strand according to the claim 10, where the solid particles are formed from at least one ceramic material selected from the group consisting of metal nitrides, metal oxides, metal carbides, metal sulphides, metal borides, metal silicates, metal carbonates and their mixtures.

12. The coated fiber strand according to claim 11, wherein the solid particles are formed from a metal nitride which is boron nitride of hexagonal crystal structure.

13. The coated fiber strand according to claim 11, wherein the solid particles are formed from a metal oxide which is zinc oxide.

14. The coated fiber strand according to claim 11, wherein the solid particles are formed from at least one metal sulfide selected from the group consisting of molybdenum disulfide, tantalum disulfide, tungsten disulfide, zinc sulphide and mixtures thereof. .

15. The coated fiber strand according to claim 11, wherein the solid particles are formed from at least one metal silicate selected from the group consisting of aluminum silicates, magnesium silicates and mixtures thereof.

16. The coated fiber strand according to claim 11, wherein the solid particles are formed from at least one metallic material selected from the group consisting of graphite, molybdenum, platinum, palladium, nickel, aluminum, copper, gold, iron, silver and its mixtures

17. The coated fiber strand according to claim 9, wherein the solid particles are formed from at least one organic polymer material selected from the group consisting of thermoset materials, thermoplastics, starches and mixtures thereof.

18. The coated fiber strand according to claim 17, wherein the solid particles are formed from at least one thermoset material selected from the group consisting of thermoset polyesters, vinyl esters, epoxy materials, phenolics, aminoplasts, thermoset polyurethanes and their mixtures

19. The coated fiber strand according to claim 17, wherein the solid particles are formed from at least one thermoplastic material selected from the group consisting of vinyl polymers, thermoplastic polyesters, polyolefins, polyamides, thermoplastic polyurethanes, acrylic polymers and their mixtures

20. The coated fiber strand according to claim 1, wherein the aqueous sizing composition is essentially free of hydratable inorganic solid particles.

21. The coated fiber strand according to claim 1, wherein the solid particles include more than 20 to about 99 weight percent of the size composition based on the total solids.

22. The coated fiber strand according to the claim 21, wherein the solid particles include at least about 25 weight percent of the sizing composition based on the total solids.

23. The coated fiber strand according to the claim 22, where the solid particles include more than about 50 weight percent of the sizing composition based on the total solids.

24. The coated fiber strand according to claim 1, wherein the sizing composition further includes at least one polymeric film-forming material selected from the group consisting of thermoset materials, thermoplastics, starches and mixtures thereof.

25. The coated fiber strand according to claim 1, wherein the sizing composition further includes a glass fiber coupling agent.

26. The coated fiber strand according to claim 1, wherein at least one of the at least one glass fiber is formed from a fibrillatable material selected from the group consisting of non-glass inorganic materials, natural ma- terials, organic polymeric materials. and its combinations.

27. The coated fiber strand according to claim 1, wherein the at least one glass fiber is selected from the group consisting of glass fibers E, glass fibers D, glass fibers S, glass fibers Q, fibers of glass derivatives E, and their combinations.

28. The coated fiber strand according to claim 27, wherein the at least one glass fiber is a glass fiber E.

29. The coated fiber strand according to claim 27, wherein the at least one glass fiber is a fiber of glass derivatives E.

30. A coated fiber strand including a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the strand being impregnated at least partially with (1) a primary layer of a dried residue of a size composition applied to at least a portion of the surfaces of the plurality of glass fibers and (2) a secondary layer of an aqueous secondary coating composition applied over at least a portion of the primary layer, the secondary coating composition including solid particles providing spaces interstitial between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns.

31. The coated fiber strand according to claim 30, wherein the minimum average particle size of the solid particles is at least about 5 microns.

32. The coated fiber strand according to claim 30, wherein the at least one glass fiber is selected from the group consisting of glass fibers E, glass fibers D, glass fibers S, glass fibers Q, fibers of glass derivatives E, and their combinations.

33. The coated fiber strand according to claim 32, wherein the at least one glass fiber is a glass fiber E.

34. The coated fiber strand according to claim 32, wherein the at least one glass fiber is a fiber of glass derivatives E.

35. A coated fiber strand including a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the strand being impregnated at least partially with (1) a primary layer of a dried residue of a size composition applied to at least a portion of the surfaces of the plurality of glass fibers and (2) a secondary layer of a dried residue of an aqueous secondary coating composition applied on at least a portion of the primary layer, including the secondary coating composition. hydrophilic solids which provide interstitial spaces between adjacent glass fibers of the strand, the hydrophilic solid particles having a minimum average particle size of at least 3 microns and which, after exposure to water, absorb and retain water in interstices within the particles solid hydrophilic.

36. The coated fiber strand according to claim 35, wherein the minimum average particle size of the solid particles is at least about 5 microns.

37. The coated fiber strand according to claim 35, wherein the at least one glass fiber is selected from the group consisting of glass fibers E, glass fibers D, glass fibers S, glass fibers Q, fibers of glass derivatives E, and their combinations.

38. The coated fiber strand according to claim 37, wherein the at least one glass fiber is a glass fiber E.

39. The coated fiber strand according to claim 37, wherein the at least one glass fiber is a fiber of glass derivatives E.

40. A coated fiber strand including a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the strand being impregnated at least partially with (1) a primary layer of a dried residue of a size composition applied to at least a portion of the surfaces of the plurality of glass fibers; (2) a secondary layer of a secondary coating composition applied on at least a portion of the primary layer, the secondary coating composition comprising a polymeric material; and a tertiary layer including solid powder particles applied on at least a portion of the secondary layer providing interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns.

41. The coated fiber strand according to claim 40, wherein the minimum average particle size of the solid particles is at least about 5 microns.

42. The coated fiber strand according to claim 40, wherein the at least one glass fiber is selected from the group consisting of glass fibers E, glass fibers D, glass fibers S, glass fibers Q, fibers of glass derivatives E, and their combinations.

43. The coated fiber strand according to claim 42, wherein the at least one glass fiber is a glass fiber E.

44. The coated fiber strand according to claim 42, wherein the at least one glass fiber is a fiber of glass derivatives E.

45. A reinforced polymer composite including: (a) a coated fiber strand including a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the strand being impregnated at least partially with a dried residue of an aqueous composition sizing including solid particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns and a hardness not exceeding the hardness of the plurality of glass fibers; and (b) a polymeric matrix material.

46. The coated fiber strand according to claim 45, wherein the minimum average particle size of the solid particles is at least about 5 microns.

47. The reinforced polymer composite according to claim 45, wherein the at least one glass fiber is selected from the group consisting of glass fibers E, glass fibers D, glass fibers S, glass fibers Q, fibers of glass derivatives E , and their combinations.

48. A fabric including a coated fiber strand including a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the strand being impregnated at least partially with a dried residue of an aqueous size composition including solid particles which provide interstitial spaces between adjacent glass fibers of the tor, the solid particles having a minimum average particle size of at least 3 microns and a hardness not exceeding the hardness of the plurality of glass fibers.

49. The coated fiber strand according to claim 48, wherein the minimum average particle size of the solid particles is at least about 5 microns.

50. The fabric according to claim 48, wherein the at least one glass fiber is selected from the group consisting of glass fibers E, glass fibers D, glass fibers S, glass fibers Q, fibers of glass derivatives E, and your combinations

51. An electronic support including: (a) a fabric including a coated fiber strand including a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the strand being impregnated at least partially with a dried residue of an aqueous sizing composition that includes solid particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns and a hardness not exceeding the hardness of the plurality of fibers of glass; and (b) a layer of a polymeric matrix material applied on at least a portion of the fabric.

52. The coated fiber strand according to claim 51, wherein the minimum average particle size of the solid particles is at least about 5 microns.

53. The electronic support according to. claim 51, wherein the at least one fiberglass is selected from the group consisting of glass fibers E, glass fibers D, glass fibers S, glass fibers Q, fibers of glass derivatives E, and combinations thereof.

54. The electronic support according to claim 51 wherein the support is a first, second or third tier package.

55. An electronic circuit board including: (a) an electronic support including: (i) a fabric including a coated fiber strand including a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, At least partially impregnated the strand with a dried residue of an aqueous sizing composition including solid particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns and a hardness not exceeding the hardness of the plurality of glass fibers; and (ii) a layer of a polymeric matrix material applied on at least a portion of the fabric; and (b) an electrical conductive layer positioned adjacent selected portions of selected sides of the electronic support.

56. The coated fiber strand according to claim 55, wherein the minimum average particle size of the solid particles is at least about 5 microns.

57. The electronic circuit board according to claim 55, wherein the at least one glass fiber is selected from the group consisting of glass fibers E, glass fibers D, glass fibers S, glass fibers Q, fibers of derivatives of glass E, and their combinations.

58. The electronic circuit board according to claim 55, further including at least one hole extending through at least a portion of the circuit board.

59. The electronic circuit board according to claim 55, wherein the support is a first, second or third tier package.

60. An electronic support including: (a) a first composite layer comprising: (i) a fabric including a coated fiber strand including a plurality of glass fibers with an average nominal diameter of the fibers greater than 5 microns, the base impregnated with at least partially with a dried residue of an aqueous sizing composition including solid particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a minimum average particle size of at least 3 microns and a hardness that does not exceeds the hardness of the plurality of glass fibers; and (ii) a layer of a polymeric matrix material applied on at least a portion of the fabric; and (b) a second composite layer different from the first composite layer.

61. The coated fiber strand according to claim 60, wherein the minimum average particle size of the solid particles is at least about 5 microns.

62. The electronic support according to claim 60, wherein the at least one glass fiber is selected from the group consisting of glass fibers E, glass fibers D, glass fibers S, glass fibers Q, fibers of glass derivatives E, and its combinations.

63. The electronic support according to claim 60, wherein the support is a first, second or third tier package.

64. An electronic circuit board including: (a) an electronic support including: (i) a first composite layer comprising: (1) a fabric including a coated fiber strand including a plurality of glass fibers with an average nominal diameter of fibers greater than 5 microns, the strand being impregnated at least partially with a dried residue of an aqueous sizing composition including solid particles that provide interstitial spaces between adjacent glass fibers of the strand, the solid particles having a mean particle size minimum of at least 3 microns and a hardness not exceeding the hardness of the plurality of glass fibers; and (2) a layer of a polymer matrix material applied on at least a portion of the fabric; and (ii) a second composite layer different from the first composite layer; and (b) an electrical conductive layer positioned adjacent selected portions of selected sides of the first and / or second composite layers.

65. The coated fiber strand according to claim 64, wherein the minimum average particle size of the solid particles is at least about 5 microns.

66. The electronic circuit board according to claim 64, wherein the at least one glass fiber is selected from the group consisting of glass fibers E, glass fibers D, glass fibers S, glass fibers Q, fibers of glass derivatives E, and their combinations.

67. The electronic circuit board according to claim 64, further comprising at least one hole extending through at least a portion of the circuit board.

68. The electronic circuit board according to claim 64, wherein the support is a first, second or third tier package.