MXPA00008554A

MXPA00008554A - Glass fiber-reinforced laminates, electronic circuit boards and methods for assembling a fabric

Info

Publication number: MXPA00008554A
Authority: MX
Inventors: Xiang Wu; Bruce E Novich
Original assignee: Ppg Ind Ohio Inc
Priority date: 1998-03-03
Filing date: 2000-09-01
Publication date: 2001-03-01
Also published as: JP2002505216A; TW436422B; HUP0101382A2; BR9908520A; AU2788999A; WO1999044959A1; IL137977A0; PL342654A1; ID26528A; CN1291963A; NO20004272D0; NO20004272L; HUP0101382A3; MXPA00008517A; KR20010041518A; CA2320746A1; TR200002520T2; EP1060144A1

Abstract

The present invention provides fiberglass strands coated with solid, inorganic, non-hydratable lubricating particles, useful for reinforcing composites as laminated electronic supports.

Description

GLASS FIBER TORONES COATED WITH INORGANIC LUBRICANT AND PRODUCTS THAT INCLUDE THEM Cross reference to related applications This patent application is a partial continuation of the United States serial number 09 / 034,525 by B. Novich et al. Entitled "Fiberglass strands coated with inorganic lubricant and products including them" filed on March 3, 1998. This patent application is related to the United States patent application serial number of B. Novich et al. entitled "Methods to inhibit the abrasive wear of fiberglass strands", which is a so-licitud partial continuation of the application of United States serial number 09 / 034,078 filed "on March 3, 1998; United States patent application serial number of B. Novich et al. entitled" Coated fiberglass strands with inorganic solid particles with thermal conductors and products that include them ", which is a partial continuation of the application of United States serial number 09/0 34,663 filed on March 3, 1998; US patent application serial number of _B. Novich et al. Entitled "Impregnated fiberglass strands and products including them", which is a partial continuation application of the United States application serial number 09 / 034,077 filed March 3, 1998; US 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 the United States application serial number 09 /034,056 filed on March 3, 1998; and the United States patent application serial number of B. Novich et al. entitled "Fiberglass reinforced laminates, electronic circuit boards and methods for assembling a fabric", which is a partial continuation application of the United States application number of series 09 / 130,270 filed on August 6, 1998, each of which has been filed simultaneously with the present application. FIELD OF THE INVENTION This invention relates generally to coated fiberglass strands for reinforcing composites and, more specifically, to fiberglass strands coated with non-hydratable inorganic solid lubricating particles useful for weaving fabric to reinforce laminated printed circuit boards. .

BACKGROUND OF THE INVENTION Typically, glass fiber surfaces are coated with a size composition in the forming process to protect the fibers against abrasion during the next treatment. For example, starch and oil based sizing compositions are used to protect the fibers against abrasion between filaments and equipment during weaving, which may contribute to fiber breakage. Other organic lubricants, such as alkyl imidazoline derivatives and substituted amide polyethylene imines, have been added to sizing compositions to reduce abrasion. However, such organic lubricants can deteriorate during the subsequent treatment or produce undesirable side reactions with other sizing components and matrix material and, as is the case for woven fabric for printed circuit board applications, it is often necessary to Remove by heat cleaning before lamination to improve compatibility with the polymeric matrix material. An inert lubricant is desirable to inhibit abrasion of glass fibers that does not deteriorate appreciably during processing and is compatible with polymeric matrix materials. However, the use of inorganic materials has mainly focused on fillers to modify the general physical characteristics of the compounds instead of improving the abrasion resistance characteristics of the reinforcing fibers. For example, to dissipate thermal energy, U.S. Patent No. 4,869,954 discloses a thermal conductive material in the form of a sheet formed of a urethane binder, curing agent and thermal conductive fillers such as aluminum oxide, aluminum nitride, nitride of boron, magnesium oxide and zinc oxide and various metals (see column 2, lines 62-65 and column 4, lines 3-10). One or more layers of a support material, such as fiberglass cloth, may be included in the thermally conductive material. To improve the penetration of resin between the glass reinforcing fibers during the formation of a composite, U.S. Patent No. 3,312,569 discloses alumina particles that adhere to the surfaces of the glass fibers, and the application Japanese Patent 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 solid inorganic particles such as colloidal silica, calcium carbonate, kaolin and talcum. However, the Mohs hardness values of alumina and silica are greater than about 9 and about 11, respectively, which can cause abrasion of the softer glass fibers. 1 See R. east (ed.), Handbook of Chemistry and Physics, CRC Press (1975), page F-22, and H. Katz and others, (ed.), Handbook of Fillers and Plastics, (1987), page 28, which are incorporated herein by reference.

U.S. Patent No. 5,541,238 discloses a fiber for reinforcing thermoplastic or thermosetting composites which is coated by vapor deposition or plasma process with a single layer of an ultrafine material such as inorganic oxides, nitrides, carbides, borides , metals and their combinations with an average particle diameter of 0.005-1 miera. Limited space and environmental considerations mean that the use of vapor deposition processes or plasma under a fiberglass production bush is impossible. Soviet Union patent number 859400 discloses an impregnating composition for making glass fiber cloth laminates, the composition containing an alcohol 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 which are impregnated. and cover with a thermosetting cement or binder system. The binder may include particles of friction as black car-bon, graphite, metal oxides, barium sulfate, aluminum silicate, rubber particles crushed, ground organic resins, nut oil polymerized cashew, clay, silica or cryolite ( see column 2, lines 55-66). Lubricating coatings are needed to inhibit abrasion and breakage of glass fibers that are thermally stable, non-corrosive and non-reactive in the presence of high humidity, reactive acids and alkalis and are compatible with a wide variety of polymeric matrix materials.

SUMMARY OF THE INVENTION The present invention provides a re-roughened fiber strand including at least one glass fiber having a primary layer of a dried residue of an aqueous sizing composition applied to at least a portion of a surface of the at least one single fiberglass, including the aqueous sizing composition: (a) lamellar, non-hydratable, inorganic solid lubricating particles, having a hardness value not exceeding a hardness value of the at least one glass fiber and (b) a polymeric material, the aqueous sizing composition being essentially free of glass materials. Another aspect of the present invention is a coated fiber strand including at least one glass fiber having a primary layer of a dried residue of an aqueous sizing composition applied to at least a portion of a surface of the at least one fiber of glass, including the hexagonal structure boron nitride sizing composition, thermoplastic polyester, polyvinyl pyrrolidone and an epoxy functional organ silane coupling agent. Another aspect of the present invention is a coated fiber strand including at least one glass fiber having a primary layer of a dried residue of an aqueous sizing composition applied to at least a portion of a surface of the at least one fiber of glass, including the aqueous sizing composition: (a) lamellar, non-hydratable, inorganic solid lubricating particles, having a hardness value that does not exceed a hardness value of the glass fiber and (b) a fiber coupling agent of vi-drio, the aqueous sizing composition being essentially free of glass materials. Another aspect of the present invention is a coated fiber strand including at least one glass fiber having a primary layer of a dried residue of a size composition applied to at least a portion of a surface of the at least one fiber. of glass, and a secondary layer of an aqueous secondary coating composition including inorganic solid non-hydratable lubricating particles applied on at least a portion of the dried residue of the sizing composition. Another aspect of the present invention is a coated fiber strand including at least one glass fiber having a primary layer of a size composition applied to at least a portion of a surface of the at least one glass fiber, and a secondary layer of a secondary coating composition placed on at least a portion of the primary layer, the secondary coating composition including hydrophilic solid inorganic lubricating particles that absorb and retain water in the interstices of the hydrophilic particles. Another aspect of the present invention is a coated fiber strand including at least one glass fiber having a primary layer of a dried residue of a size composition applied to at least a portion of a surface of the at least one fiber. glass, a secondary layer of a secondary coating composition including a polymeric material placed on at least a portion of the primary layer, and a tertiary layer including solid inorganic powder lubricating particles placed on at least a portion of the secondary layer. Another aspect of the present invention is a coated fiber strand including at least one glass fiber having a primary layer of a dried residue of an aqueous sizing composition applied to at least a portion of a surface of the at least one fiberglass, including the aqueous sizing composition: (a) metallic inorganic solid lubricating particles having a hardness value not exceeding a hardness value of the at least one glass fiber, including solid inorganic lubricating particles At least one particle selected from the group consisting of indium, thallium, tin, copper, zinc, gold and silver, and (b) a polymeric film-forming material. Another aspect of the present invention is a reinforced polymeric composite comprising: (a) a coated fiber strand including at least one glass fiber having a primary layer of a dried residue of an aqueous size composition applied to at least a portion of a surface of the at least one glass fiber, including the aqueous sizing composition: (1) lamellar, non-hydratable, inorganic solid lubricating particles, having a hardness value not exceeding a hardness value of the at least one fiber of glass; and (2) a polymeric material, the aqueous sizing composition being essentially free of glass materials; and (b) a polymeric matrix material. Another aspect of the present invention is a fabric including a coated fiber strand including at least one glass fiber having a primary layer of a dried residue of an aqueous size composition. applied to at least a portion of a surface of the at least one glass fiber, including the aqueous sizing composition: (a) lamellar, non-hydratable, inorganic solid lubricating particles having a hardness value not exceeding one hardness of the at least one fiberglass and (b) a polymeric polymeric material. Another aspect of the present invention is an electronic support including: (a) a fabric including a coated fiber strand including at least one glass fiber having a main layer of a coating composition including lamellar, non-hydratable, inorganic solid lubricating particles , applied to at least a portion of a surface of the at least one glass fiber and (b) a layer of a polymeric matrix material applied on at least one 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 at least one glass fiber having a main layer of one coating composition including lamellar, non-hydratable, inorganic solid lubricating particles, applied to at least a portion of a surface of the at least one glass fiber and (ii) a layer of a polymeric matrix material applied over at least a portion of the cloth; and (b) an electrical conductive layer positioned adjacent 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 at least one partially coated fiber strand including at least one glass fiber having a primary layer of a coating composition including lamellar inorganic solid lubricating particles, non-hydratable, applied to at least a portion of a surface of the at least one glass fiber and (ii) a layer of a polymeric matrix material applied over at least one 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 that includes a fabric that includes at least one partially coated fiber strand that includes at least one fiber of glass having a main layer of a coating composition including lamellar, non-hydratable, inorganic solid lubricating particles applied to at least a portion of a surface of the at least one glass fiber; and a layer of a polymeric 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. Another aspect of the present invention is a method for bleaching a polymeric compound, including the steps of (a) applying a particle layer, at least one of the particles being selected from the group consisting of boron nitride, zinc sulphide, montmorillonite and their blends to at least a portion of a surface of at least one glass fiber of a fiberglass strand to form a fiberglass strand at least partially coated; (b) combining the fiberglass strand with a polymeric matrix material; and (c) forming a reinforced polymer composite from the fiberglass strand and polymer matrix material, wherein the whiteness index value of the reinforced polymeric composite is less than a whiteness index value of a composite formed from the polymeric matrix material.

The description of the drawings is provided 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. 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 break 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 srt according to the present invention. And Figures 7 and 8 are cross-sectional views of alternative embodiments of an electronic srt 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 fiber breakage, but can provide good rolling resistance, good technical stability, good hydrolytic stability, low corrosion and reactivity in the 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 prior to lamination. Another considerable advantage of the coated fiberglass strands of the present invention is the good processability in weaving and knitting. Little fluff and halos, few broken filaments, low strand tension, high foldability and little insertion time are features that can be provided by the coated fiberglass strands of the present invention to facilitate weaving and knitting and to provide coherently a fabric with few surface flaws 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 at least one glass fiber 12, according to the present invention, is depicted in Figure 1. Preferably the strand 10 includes a plurality of glass fibers 12. In the sense used herein, the term "strand" means one or more individual fibers. The term "fiber" means an individual filament. The glass fibers 12 can be formed of any type of fibrillable glass composition known to those skilled in the art, including those prepared from fibrillable glass compositions such as "E glass", "A glass", "C glass". , "glass D", "glass R", "glass S", and glass derivatives E. In the sense in which it is used in the pre-senté memory, "glass derivatives E" means glass compositions that include minor amounts of fluorine and / or boron and preferably are free of fluorine and / or free of boron. Also, in the sense in which it is used herein, small means less than about 1 percent by weight of fluorine and less than about 5 percent by weight 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 or 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. Yes, 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 of the 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 fibrizable 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 alcohol). poly) Non-glass fibers which are considered useful in the present invention and methods for preparing and treating such fibers are extensively 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, the fibers 12 of the fiber strand 10 of the present invention are coated 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", "sizing" 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 inorganic solid lubricating particles 18. In the sense in which it is used in the pre-senté memory, "solid lubricant" means that the particles 18 have a characteristic crystalline habit which causes them to tear into thin flat plates which easily slide over one another and thus produce a anti-scratch lubricating effect between the surface of the glass fiber and an adjacent solid surface, of which at least one is in motion. (See R. Lewis, Mr. Hawley's Condensed Chemical Dictionary, (12th ed., 1993), page 712, which is incorporated herein by reference). The friction is the resistance to sliding of one solid over another. (See F.

Clauss, Solid Lubricants and Self-Lubricating Solids, (1972), page 1, which is incorporated herein by reference). The glass fibers are subjected to abrasive wear by contact with asperities of the adjacent 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. . "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 removal of glass fibers by frictional contact with particles, edges or entities (asperities) of materials. which are hard enough to cause damage to the glass fibers. See K. Ludema, Friction, Wear, Lubrication, (1996), page. 129, which is incorporated herein by reference. In the formation, for example, the glass fibers contact solid objects, such as a metallic collection shoe and a transverse or spiral path before being wound up in a formation package. In knitting operations, such as weaving or knitting, the fiberglass strand contacts solid objects, such as portions of the fiber assembly apparatus (loom or knitting device) that can abrade the fiber surfaces 16 of glass in contact 12. Examples of the portions of a loom that contact the glass fibers include the air jets and the shuttles. The surface roughness of said solid objects having a hardness value greater than that of the glass fibers, can produce abrasive wear of the glass fibers. For example, many portions of the torsion frame, loom and weaving device are formed from metallic materials, such as steel, having a Mohs hardness of up to about 8.52. The abrasive wear of the fiberglass strands produced by the contact with as-slots of said solid objects produces breakage of the strand during the treatment and surface defects in the products, such as woven cloth and compounds, which increase the waste and the cost of manufacturing. To minimize abrasive wear, the fibers of the strands of the present invention are coated at least partially, and preferably completely, with solid, inorganic, non-hydratable lubricating particles, which have a hardness value that does not exceed, ie, is less than or equal to a hardness value of the glass fiber (s). The hardness values of the inorganic, non-hydratable solid lubricating particles, and the glass fibers can be determined by any conventional method of measuring hardness, such as Vickers or Brinell hardness, but is preferably determined according to the original Mohs hardness scale. which indicates the re- Handbook of Chemistry and Physics, page F-22. resistance to scratching the surface of a material. The Mohs hardness value of glass fibers generally ranges between about 4.5 and about 6.5, and is preferably about 6. (See 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 non-hydratable, inorganic solid lubricating particles is preferably in the range of about 0.5 to about 6. The Mohs hardness values of several non-limiting examples of non-hydratable inorganic solid lubricants suitable for use herein invention are set forth in Table A below.

Table A Solid lubricant material Mohs hardness (original scale) Boron nitride approximately 23 Graphite approximately 0,5-l4 Molybdenum disulfide approximately l5 Aluminum approximately 2,5d Copper approximately 2,5-37 Gold approximately 2,5-38 Silver approximately 2,5-49 K. Ludema, Friction, Wear, Lubrication, (1996), page 27, which is incorporated herein by reference. 4 Handbook of Chemistry and Physics, page ^ F-22. 5 R. Lewis, Mr., Hawley's ^ Condensed Chemical Dictionary, (12th ed., 1993), page 793, which is incorporated herein by reference. 6 Friction, Wear, Lubrication, page 27. 7 Handbook of Chemistry and Physics, page F-22. 8 Handbook of Chemistry and Physics, page F-22. 9 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 hardness on their surface that is different from the hardness of the internal portions of the particle below its surface. More specifically, the surface of the particle can be modified in any 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, so that the 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, although without limiting the present invention, the inorganic particles, such as silicon carbide and aluminum nitride, can be provided with a silica, carbonate or nanoclay coating. In addition, the silane coupling agents with alkyl side chains can be reacted with the surface of many oxide particles to obtain a "softer" surface. In a preferred embodiment, the non-hydratable inorganic solid lubricating particles have a lamellar structure. The particles that have a lamellar or hexagonal crystalline structure are composed of sheets or plates of atoms in a hexagonal arrangement, with strong union within the lamina and weak van der Waals junction between sheets, providing low resistance to shear 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 is incorporated herein by reference. Inorganic solid non-hydratable lubricating particles that stain a lamellar fullerene structure (soccer ball) are also useful in the present invention. Non-limiting examples of suitable non-hydratable inorganic solid lubricating particles with lamellar structure include boron nitride, graphite, metal dicalcogenides, cadmium iodide, silver sulfide and mixtures thereof. Preferred non-hydratable inorganic solid lubricating particles include boron nitride, metal dicalcogenides, cadmium iodide, silver sulfide and mixtures thereof. Suitable metal dicalcogenides include molybdenum disulfide, molybdenum diselenide, tantalum disulfide, tantalum di-selenide, tungsten disulfide, tungsten diselenide, and mixtures thereof. Boron nitride particles having a hexagonal crystal structure are highly preferred for use in the aqueous sizing composition. Non-limiting examples of boron nitride particles suitable for use in the present invention are PolarTher ® Series 100 boron nitride powder particles (PT 120, PT 140, PT 140 and PT 180), Series 300 (PT 350) and Series 600 (PT 620, PT 630, PT 640 and PT 670) available from the Advanced Ceramics Corporation market in Lakewood, Ohio. "PolarTherm® Thermally Conductive Fillers for Palymeric 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 particle size of the order of from about 16 to more than about 200 microns. The average particle size 19 (equivalent spherical diameter) of the inorganic solid particles is generally less than about 1000 microns, preferably is in the range of from about 0.001 to about 100 microns, and more preferably from about 0.1 to about 25 microns . The shape or shape of the solid particles 18 may be generally spherical (such as beads or microbeads), cubic, laminar or acicular (elongated or fibrous), as desired. For more information on suitable particle characteristics, see H. Katz et al. (Ed.), Handbook of Fillers and Plastics, (1987), pages 9-10, which is incorporated herein by reference). The non-hydratable inorganic 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 weight percent) may be included in the sizing composition, if desired. The amount of non-hydratable inorganic solid lubricating particles 18 in the aqueous sizing composition may be in the range of from about 0.001 to about 99 weight percent based on the total weight, preferably from about 1 to about 50 weight percent, and more preferably of about 25 weight percent. A non-limiting example of a preferred dispersion of about 25 weight percent boron nitride particles in water is ORPAC BORON NI-TRIDE RELEASECOAT-CONC which is commercially available from ZYP Coatings, Inc. of Oak Ridge, Tennessee See "ORPAC BO-RON NITRIDE RELEASECOAT-CONC", technical bulletin of ZYP Coatings, Inc., which is incorporated herein by reference. According to the supplier, the boron nitride particles of this product have an average particle size of less than about 3 microns. This dispersion has approximately 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 that can be obtained in the ZYP Coatings market include BORON NITRIDE LUBRICOAT® paint, BRAZE STOP and WELD RELÉASE products. In an alternative preferred embodiment, the sizing composition may include non-hydratable inorganic solid metal lubricating particles selected from the group consisting of indium, thallium, tin, copper, zinc, gold, silver and mixtures thereof. In an alternative preferred embodiment, the non-hydratable inorganic solid lubricating particles 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 solid lubricants. inorganic metals explained above. The thermal conductivity of a solid material can be determined by any method known to those skilled in the art, such as the hot plate 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 non-hydratable inorganic solid lubricating particles are electrical insulators or have high electrical resistivity, that is, they have an electrical resistivity of greater than about 1000 microohm-cm, such as, for example, boron nitride. In the sense in which it is used herein, "non-hydratable" means that solid inorganic lubricant particles do not react with water molecules to form hydrates and do not 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, Mr. Hawley's Condensed Chemical Dictionary, (12th ed., 1993), pages 609-610, and T. Perros, Chemistry, (1967), pages 186-187, which are incorporated herein by reference. In chemical formulas of hydrates, the addition of water molecules is conventionally indicated with a centered point, for example, 3MgO-4Si02 • H20 (talc), A1203 • 2Si02-2H20 (kaolinite). Structurally, the hydratable inorganic materials include at least one hydroxyl group within a layer of a crystal lattice (but not including hydroxyl groups in the surface planes of a unitary structure or materials that absorb water in their surface planes or by capillary action. ), for example, as shown in the kaolinite structure given in Figure 3.8, page 34, by J. Mitchell, Fundamentáis of Soil Behavior (L976), and as shown in the minerals structure of layer 1: 1 and 2: 1 in figures 18 and 19, respectively. By H. Van Olphen, Clay Colloid Chemistry, (2nd ed., 1977), page 62, which are incorporated herein by reference. A "layer" of crystal lattice is a combination of sheets, which is a combination of planes of atoms. Minerals in Soil Environments, Soil Science Sci. Of America (1977), pages 196-199, which is incorporated herein by reference. The assembly of a layer and interlayer material (as cations) is called a unitary structure. 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 interstices in the structure to increase the electrostatic energy without disturbing the load balance. R. Evans, An In-troduction 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 (CaSo4 • 2H20). Preferably, the sizing composition is essentially free of hydratable solid inorganic lubricating particles or silica or calcium carbonate particles, ie, includes less than about 20 weight percent hydratable inorganic lubricating particles, abrasive silica particles or calcium carbonate based to total solids, more preferably less than about 5 weight percent, and most preferably less than 0.001 weight percent. The non-hydratable inorganic solid lubricant includes 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 weight percent. percent in weight. In a preferred embodiment, the sizing composition may contain from about 0.001 to 5% boron nitride based on the total solids. In addition to the non-hydratable solid inorganic lubricant, the aqueous sizing composition preferably includes one or more polymeric materials, such as thermoset materials, thermoplastics, starches and mixtures thereof. Preferably, the polymeric materials form a generally continuous film when applied to the surface 16 of the glass fibers. In general, the amount of polymeric material may be in the range of from about 1 to about 99 weight percent of the aqueous sizing composition based on total solids, preferably from about 20 to about 99 weight percent, and more preferably from about 60 to about 99 weight percent. The thermoset polymeric materials are preferred polymeric materials for use in the aqueous sizing composition for coating fiberglass strands of the pre-sent 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 specific embodiment of the invention are brominated difunctional epoxy resins. See 1 Electronic Materials Handbook1 ASM International (1989), pages 534-537, which are incorporated herein by reference. Useful thermosetting materials include thermoset polyesters, epoxy materials, vinyl esters, phenolics, animoplastics, thermosetting polyurethanes, and mixtures thereof. Suitable thermoset polyesters include STYPOL polyesters marketed by Cook Composites and Polymers of Port Washington, Wisconsin, and NEOXIL polyesters marketed by DSM B.V from 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 sold 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 the VERSAMID products marketed by General Mills Chemicals, Inc. Useful thermoplastic polyurethanes include WITCOBOND® W-290H available commercially from Witco Chemical Corp., of Chicago, Illinois, and RUCOTHANE polyurethane latex. ® 2011L that can be purchased at 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 an alternative preferred embodiment suitable for laminates for printed circuit boards, the polymeric materials of the aqueous sizing composition include a blend 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 ilawley '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 coupling agents such as organosilane coupling agents, transition metal coupling agents, phosphonate coupling agents, coupling agents. of aluminum, 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. 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, for example by polar forces, of Wetting or dissolution Examples of hydrolysable groups include: OH 0 R ~ -0R1, -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 gli-ool, wherein R 1 is C 1 -C 3 alkyl; R 2 is H or C 1 -C 4 alkyl; R3 and R4 are independently selected from H, C? -C4 alkyl or Ce-Cs 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 organ coupling agents include gamma-aminopropyl trialkoxysilanes, gamma-isocyanatopropyltriethoxysilane, vinyl trialkoxysilanes, Licidoxypropyltrialkoxysilanes 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 coupling agent 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 and metal chelate type known to those skilled in the art can be used here. The amount of coupling agent may 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), to ethoxylated L-alkyl phenols (such as IGEPAL CA-630 octylphene-ethanol ethoxylate which is available commercially from GAF Corporation of Wayne, New Jersey), polyoxyethylene octylphenyl glycol ethers, ethylene oxide derivatives of esters of sorbitol, polyoxyethylated vegetable oils (such as ALKA-MULS ES-719, which can be purchased from the Rhone Poulenc market) and nonylphenol surfactants (such as MACOL NP-6 which can be purchased from the BASF market in Parsippany, New Sweater) . Generally, the amount of emulsifying agent can range from about 1 to about 30 weight percent of the aqueous sizing composition in base 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 commercially 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 can range from about 1 to about 5 weight percent of the sizing composition based on the s-1. Total losses. 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 materials r < AG that sells OSi Specialties, Inc., of Danbury, Connecticut and MAZU DF-136 that 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 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 printed circuit boards, a primary layer of a dry residue of an aqueous sizing composition including boron nitride powder is applied to the glass fibers of the coated fiber strands of the present invention. PolarTherm® 160 and / or BORON NITRIDE RELEASECOAT dispersion, EPON 826 epoxy film-forming material, polyvinyl pyrrolidone PVP K-30, epoxy-functional functional silane coupling agent A-187, polyoxyethylated vegetable oil ALKAMULS EL-719, ethoxylated octylphenoxyethanol IGEPAL CA-630 , polyethylene glycol monolaurate ester KESSCO PEG 600 available commercially from the Stephan Company of Chicago, Illinois, and EMERY® 6717 partially amidated polyethylene imine. In a more preferred embodiment for knitting fabric, glass fibers of the coated fiber strands of the present invention a primary layer of a dried residue of an aqueous sizing composition has been applied which n-clude PolarTherm® boron nitride powder and / or BORON NITRIDE RELEASECOAT dispersion, RD-847A polyester, polyvinyl pyrrolidone PVP K-30, DESMOPHEN 2000 polyester, acrylic silane coupling agents A-174 and organ coupling agents epoxy functional silane A-187, polyoxypropylene-polyoxyethylene copolymer PLURONIC F-108, nonylphenol surfactant MACOL NP-6, VERSAMID 140 and epoxidized silicone emulsion LE-9300. The aqueous sizing compositions of the present invention can be prepared by another suitable method such as conventional mixing 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. It is possible to premix non-hydratable inorganic lubricants in powder with water or to add to the polymeric material before mixing with the other components of the sizing. The primary size coat can be applied in many ways, for example by contacting the filaments with a roller or belt applicator, spraying or other means. The sizing fibers are preferably dried 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 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 1 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 previously explained for a time sufficient to at least partially dry or cure the secondary coating composition. The method and apparatus for applying the secondary coating composition to the strand is determined in part by the configuration of the strand material. The strand 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 described 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 alternative 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 that can 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 inorganic lubricating particles. hydratable and / or non-hydratable 216 as explained in detail above. Preferably, the inorganic lubricant particles in the secondary coating composition are non-hydratable lamellar inorganic lubricating particles as 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 the total solids and preferably from about 20 to about 90 weight percent. The solids of the aqueous secondary coating composition is generally in the range of about 5 to about 50 weight percent In an alternative embodiment, the inorganic solid lubricating particles of the secondary coating composition include hydrophilic solid inorganic lubricating particles which absorb and They retain water in the interstices of the hydrophilic particles.The hydrophilic inorganic solid lubricating particles can absorb water or swell when they come into contact with water or participate in a chemical reaction with water to form, for example, a similar viscous solution. to blocking gel or inhibits the additional 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 on sticky sizing or other sticky secondary coating materials. The amount of hydrophilic inorganic lubricating particles in the secondary coating composition can range from about 1 to about 99 weight percent based on the 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 of the coated fiber strand 310, i.e., such fiber strand 312 it would have a primary primer layer 314, 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 powdered non-hydratable, lamellar, inorganic lubricating particles, such as PolarTherm boron nitride particles. ® explained above. Preferably, the powder coating is applied by passing the strand to which a liquid secondary coating composition has been applied through a fluidized bed or spray dispersion to adhere the powder particles to the sticky secondary coating composition. Alternatively, the strands can be mounted on a fabric 810 before applying the layer 812 of the tertiary coating as shown in Figure 8. The weight percentage of non-hydratable lamellar, inorganic lubricating particles, powder, adhered to the fiber strand Coated 310 may range from about 0, about 30 weight percent of the total weight of the dried strand. The tertiary powder coating may also include one or more polymeric materials as explained 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 cut strand, braided strand, wick and / or fabric, such as woven, non-woven, knitted and mats. The coated fiber strands 10, 210, 310 and the 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, such 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 telecommunication cables, and various other compounds. In a preferred method shown in Figure 5, the coated fiber strands 510 made in accordance with 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 strands 514 can be twisted before the secondary coating by any conventional torsion technique known to those skilled in the art, for example using torsion frames to impart a torsion of about 0.5 to about 3 turns to the strand. 2.54 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 (of about the 15 weft threads per inch) of the strand (ie weft 516. Suitable woven reinforcement fabric 512 can be formed using any conventional loom known to those skilled in the art, such as a shuttle loom, air jet loom or rapier loom A preferred loom is a Tsudakoma loom that can be purchased in the Tsudakoma market of Japan The construction of the weave may be a regular taffeta weave or mesh (shown in Figure 5), although any other weaving style known to those skilled in the art may be used, such as a spreadable weave or satin weave With reference now to Figure 6, the fabric 612 can be used to form a composite or laminate 614 by coating and / or mpregnation with a film-forming thermoplastic or thermoset polymeric matrix material 616. The composite or mine 614 is suitable for use as an electronic support. In the sense in which it is used in the present specification"electronic support" means a structure that mechanically supports and / or electrically interconnects elements including, but not limited to, active electronic components, passive electronic components, printed circuits, integrated circuits, semiconductor devices and other hardware associated with such elements that include, although without limitation, connectors, female plugs, retention clips and heat sinks. The 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, animoplastic , thermostable 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 co-positions 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 matrix material, and dried to form an electronic support 718 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 multi-layer 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 conducting conductor (s) of the single-layer or multi-layer electronic support using techniques known in the art for constructing 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 , although without limitation, 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 layer of multilayer electronic circuits constructed by laminating one or more layers of electronic (described above) with one or more coating laminates (described above). ) and / or one or more prepregs (described above) If desired, additional electrical conductive layers can be incorporated into the electronic support, for example along a portion of an exposed side of the electronic circuit board muiticapa. if necessary, additional circuits can be formed from the electric 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 circuits as external, additional holes are formed, as explained above, partially or completely through the plate for mitir the electrical interconnection between the layers in 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 polymeric matrix material used by the composite manufacturers and the fabric must be cleaned to remove essentially all of the organic material from the surface of the polymer. 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 suitable interface between the polymeric matrix material used to impregnate the fabric and the clean surface of glass fiber, so that a coupling agent must be applied to the glass fiber 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 in the present specification 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 glass fiber 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 electronic circuit board . For more information on the manufacture of electronic circuit boards, see 1 Electronic Materials Handbook ™, 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 a fiberglass strand reinforcement material the above sizing, secondary and / or tertiary coating composition including particles of one or more non-hydratable inorganic solid-s lubricants; (2) drying the coating to form a substantially uniform coating on the reinforcement material; (3) combining the reinforcing material with the polymeric matrix material; and (4) at least partially curing the polymeric matrix material to obtain a polymeric composite reinforced in the manner described above in detail. 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. Boron nitride particles, zinc sulphide and / or montmorillonite can also be used to obtain good whitening in compounds with polymer matrix materials, such as nylon 6,6. A method for bleaching a polymeric compound according to the present invention includes (a) applying a layer of particles selected from the group consisting of boron nitride, zinc sulphide, montmorillonite and mixtures thereof to a surface of at least one glass fiber of a fiberglass strand to form a coated fiberglass strand as explained above in detail; (b) combining the fiberglass strand with a polymeric matrix material as explained above; and (c) forming a reinforced polymer composite from the glass fiber strand and polymer matrix material as explained above, wherein the whiteness index value of the reinforced polymer composite is less than the whiteness value of a compound formed from or consisting of the polymeric matrix material. The whiteness index values of the compounds can be determined using a conventional colorimeter, such as a Hunter colorimeter. As explained above, the reinforcing material can be combined with the polymeric matrix material, for example by dispersing it in the matrix material The present invention will now be illustrated by the following non-limiting examples: EXAMPLE 1 components in the amounts set forth in Table 1 to form aqueous compositions of AD formation size 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 1 10 RD-847A polyester resin that can be purchased from the Borden Chemicals market in Columbus, Ohio. 11 DESMOPHEN 2000 polyethylene diol adipate that can be purchased at the Bayer market in Pittsburgh, Pennsylvania. 12 EPI-REZ® 3522-W-66 available from the Shell Chemical Co. market in Houston, Texas. 13 PVP K-30 polyvinyl pyrrolidone available from the ISP Chemicals market in Wayne, New Jersey. 14 A-187 gamma-glycidoxypropyltrimethoxysilane which is available commercially from OSi Specialties, Inc., of Tarrytown, New York. A-174 gamma-methacryloxypropyltrimethoxysilane available commercially from OSi Specialties, Inc., of Tarrytown, New York. 16 A-1100 amino functional organ silane coupling agent available commercially from OSi Specialties, Inc., of Tarrytown, New York. 17 PLURONIC ™ F-108 polyoxypropylene-polyoxyethylene copolymer available commercially from BASF Corporation of Parsippany, New Jersey. IGEPAL CA-630 ethoxylated octylphenoxyethanol that can be purchased from the GAF Corporation market in Wayne, New Jersey. 19 VERSAMID 140 polyamide available on the market of General Mills Chemicals, Inc. 20 MACOL NP-6 nonylphenol surfactant available from the BASF market in Parsippany, New Jersey. 21 EMERY® 6760 lubricant available from the Henkel Corporation market in Kankakee, Illinois. 22 POLYOX WSR-301 polyoxyethylene polymer available from the Union Carbide market in Danbury, Connecticut. 23 PolarTherm® PT 160 boron nitride powder particles marketed by Advanced Ceramics Corporation of Lakewood, Ohio. 24 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 thread 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 drag), friction force and broken filaments of the samples AD strands, the comparative sample number 1 and a comparative sample number 225 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 shown in Table 2. The strength of aerodynamic drag or tension of each yarn 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 an air nozzle Ruti two millimeters in diameter at an air pressure of 310 kPa (45 pounds per square inch). 33 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 that have a stationary chrome pole about 5 centimeters (2 inches) in diameter mounted in between to move the wire about 5 centimeters of a straight-line path between the devices measuring the voltage. The difference in force in grams is shown in Table 2 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 speed 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 of the number of broken filaments is indicated in table 2 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 thread travel at a speed of 240 cycles per minute. The results of the aerodynamic drag force, the frictional force and the broken filaments under abrasion for the samples A-D and the comparative samples are shown in table 2 below. Table 2 As shown in Table 2, 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 fílamenizados by the air jet provide greater surface area for propulsion by air jet, which can facilitate the advance of the thread 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 2 Each of the components was mixed in the amounts set forth in Table 3 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 3 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 3 EPON 826 that can be purchased at the Shell Chemical market in Houston, Texas. 27 PVP K-30 polyvinyl pyrrolidone available from the ISP Chemicals market in Wayne, New Jersey. 28 ALKAMULS EL-719 polyoxyethylated vegetable oil that can be purchased at the Rhone-Poulenc market. 29 IGEPAL CA-630 ethoxylated octylphenoxyethanol that can be purchased from the GAF Corporation market in Wayne, New Jersey. KESSCO PEG 600 polyethylene glycol monolaurate ester available from the Stephan Company market in Chicago, Illinois. A-187 gamma-glycidoxypropyltrimethoxysilane which can be purchased from the OSi Specialties, Inc., of Tarrytown, New York. 32 EMERY® 6717 partially amidated polyethylene imine available from the Henkel Corporation market in Kankakee, Illinois. 33 Protolube HD high density polyethylene emulsion available from the Sybron Chemicals market in Birmingham, New Jersey. 34 PolarTherm® PT 160 particles of boron nitride powder marketed by Advanced Ceramics Corporation of Lakewood, Ohio. 35 ORPAC BORON NITRIDE RELEASECOAT-CONC boron nitride particles in aqueous dispersion available from the market of ZYP Coatings, Inc., 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 yarns of the EH samples and the comparative sample was evaluated in a manner similar to that of Example 1 above, except that the aerodynamic drag values were determined for two coil samples at the pressures indicated in Table 4. The average number of broken filaments per 1200 meters of yarn at 200 meters per minute using a Shirley Model No. 84 041L broken filament detector, which can be purchased from the SDL International Inc. market in 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 4 below. The number of broken filaments measured according to the gate tension method is determined by unwinding a wire sample from a coil at 200 meters / minute, passing the thread 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 4 Although the results of the test presented in Table 4 seem to indicate that the EH samples according to the present invention had abrasion resistance generally higher than the comparative sample, it is believed that these results are inconclusive since it is believed that a component The polyethylene emulsion of the comparative sample, which was not present in the EH samples, contributed to the abrasive properties of the yarn. EXAMPLE 3 Each of the components was mixed in the amounts set forth in Table 5 to form aqueous size preparation compositions K to N 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 5 was coated on E 2G-18 glass fiber strands. Each of the forming sizing compositions had about 10 weight percent solids. Table 5 36 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. 37 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. 38 ORPAC BORON NITRIDE RELEASECOAT-CONC boron nitride particles in aqueous dispersion available from the market of ZYP Coatings, Inc., 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 D-638M method; 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 6 presents the results of tests performed on compounds formed using a conventional nylon 6,6 matrix resin.

Table 6 As shown in Table 6, fiberglass strands coated with boron nitride particles (KN samples) according to the present invention exhibit better tensile and Izod impact properties with notch and similar tensile elongation and modulus, flexural strength and modulus and Izod impact properties without notch compared to a comparative sample with similar components that did not contain boron nitride in 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 4 Each of the components was mixed in the amounts set forth in Table 7 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 7 was coated on glass fiber strands E G-31. Each of the forming sizing compositions had about 10 weight percent solids. Table 7 39 Aqueous polyurethane emulsion based on thermoplastic polyester that has 65 percent solids, charge of anionic particles, particle size of approximately 2 microns, a pH of 7.5 and a viscosity of 400 centipoise (Brookfield LVF) at 25 ° C. 40 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. 41 PolarTherm® PT 160 boron nitride powder particles marketed by Advanced Ceramics Corporation of Lakewood, Ohio. 42 VANTALC 2003 talcum powder particles marketed by R. I. Vanderbilt Company, Inc., of Norwalk. Connecticut Composite samples of each of the above coated glass fiber samples and the comparative sample of Table 5 above were molded by extrusion to produce plates of 400 x 400 x 2.5 millimeters (16 x 16 x 0.100 inches) under the conditions exposed in the previous example 3. Each specimen was evaluated with respect to: tensile strength, tensile elongation, tensile modulus, Izod notched impact strength and no notch as explained in Example 3 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 samples of cut glass fiber. 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 of 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 sieved using US standard test sieves # 5 and # 6. The weight percentage of fluff material collected on the sieves as a percentage of the original sample is indicated below. Table 8 presents the results of tests performed on compounds formed using P-S samples and the comparative sample using nylon 6.6 matrix resin. Table 8 As shown in Table 8, 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 5 Each of the components was mixed in the amounts set forth in Table 9 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 9 presents the results of the whiteness and yellowness tests performed on compounds formed using 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 Colorimeter Model D25-PC2A.

Table 9 43 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 25 ° C. 44 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. 5 ORPAC BORON NITRIDE RELEASECOAT-CONC boron nitride particles in aqueous dispersion available from the market of ZYP Coatings, Inc., Oak Ridge, Tennessee. As shown in Table 9, 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 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 square 20.32 cm (8 inch) 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 ORPAC BORON NITRIDE RELEASE-COAT-CONC (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 about 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 area of verified sample are factors that may have influenced these results. It can be seen from the foregoing description that the present invention provides fiberglass strands with 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, such as 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

Revictions

1. A coated fiber strand including at least one glass fiber having a primary layer of a dried residue of an aqueous sizing composition applied to at least a portion of a surface of the at least one glass fiber, including the aqueous composition of sizing: (a) non-hydratable lamellar inorganic solid lubricating particles having a hardness value not exceeding a hardness value of the at least one glass fiber; and (b) a polymeric material, the aqueous sizing composition being essentially free of glass materials.

2. The coated fiber strand according to the claim 1, wherein the coated fiber strand includes a plurality of glass fibers.

3. The coated fiber strand according to claim 1, wherein the solid inorganic lubricant particles include at least one particle selected from the group consisting of graphite, boron nitride, metal dicalcogenides, cadmium iodide, silver sulfide and mixtures thereof.

4. The coated fiber strand according to the claim 3, wherein the solid inorganic lubricant particles include at least one particle selected from the group consisting of boron nitride, metal dicalcogenides, cadmium iodide, silver sulfide and mixtures thereof.

5. The coated fiber strand according to the claim 4, wherein solid inorganic lubricant particles include boron nitride particles of hexagonal crystal structure.

6. The coated fiber strand according to claim 3, wherein the solid inorganic lubricant particles include at least one metal dicalcogenide selected from the group consisting of molybdenum disulfide, molybdenum disodide, tantalum disulfide, tantalum disodium, tungsten disulfide, tungsten and its mixtures.

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

8. The coated fiber strand according to claim 1, wherein the hardness value of the solid inorganic lubricant particles is less than or equal to the hardness value of the at least one glass fiber.

9. The coated fiber strand according to claim 1, wherein the solid inorganic lubricant particles have a hardness value Mohs in the range of about 1 to about 6.

10. The coated fiber strand according to claim 1, wherein the average size of the inorganic lubricating particles is less than about 1000 microns.

11. The coated fiber strand according to claim 1, wherein the solid inorganic lubricating particles are thermal conductors.

12. The coated fiber strand according to claim 1, wherein the solid inorganic lubricating particles are electrical insulators.

13. The coated fiber strand according to claim 1, wherein the solid inorganic lubricant particles include from about 0.001 to about 99 weight percent of the size composition based on the total solids.

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

15. The coated fiber strand according to the claim 14, wherein the polymeric material includes at least one thermoset material selected from the group consisting of thermoset polyesters, vinyl esters, epoxy, phenolic, aminoplast, thermosetting polyurethanes and mixtures thereof.

16. The coated fiber strand according to the claim 15, where the thermosetting material is an epoxy material.

17. The coated fiber strand according to the claim 16, wherein the polymeric material includes at least one thermoplastic material selected from the group consisting of vinyl polymers, thermoplastic polyesters; polyolefins, polyamides, thermoplastic polyurethanes, acrylic polymers and their mixtures.

18. The coated fiber strand according to the claim 17, where the thermoplastic material is a polyester.

19. The coated fiber strand according to claim 17, wherein the thermoplastic material is a polyvinyl pyrrolidone.

20. The coated fiber strand according to claim 1, wherein the sizing composition includes less than 20 volume percent glass materials.

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

22. 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.

23. The coated fiber strand according to claim 22, wherein the at least one glass fiber is a glass fiber E.

24. The coated fiber strand according to claim 22, wherein the at least one glass fiber is a fiber of glass derivatives E.

25. A coated fiber strand including at least one glass fiber having a primary layer of a dried residue of an aqueous sizing composition applied to at least a portion of a surface of the at least one glass fiber, including the composition hexagonal structure boron nitride sizing fluid, thermoplastic polyester, polyvinyl pyrrolidone and an epoxy-functional si-lignum coupling agent.

26. The coated fiber strand according to the claim 25, 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.

27. The coated fiber strand according to claim 26, wherein the at least one glass fiber is a glass fiber E.

28. The coated fiber strand according to the claim 26, where the at least one fiberglass is a fiber of glass derivatives E.

29. A coated fiber strand including at least one glass fiber having a primary layer of a dried residue of an aqueous sizing composition applied to at least a portion of a surface of the at least one glass fiber, including the aqueous composition of sizing: (a) non-hydratable lamellar inorganic solid lubricating particles, having a hardness not exceeding the hardness of the at least one glass fiber; and (b) a glass fiber coupling agent, the aqueous sizing composition being essentially free of glass materials.

30. The coated fiber strand according to claim 29, wherein the glass fiber coupling agent includes at least one agent selected from the group consisting of organosilane coupling agents, transition metal coupling agents, Werner coupling agents containing amino and its mixtures.

31. The coated fiber strand according to claim 29, 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.

32. The coated fiber strand according to claim 31, wherein the at least one glass fiber is a glass fiber E.

33. The coated fiber strand according to claim 31, wherein the at least one glass fiber is a fiber of glass derivatives E.

34. A coated fiber strand including at least one glass fiber having a primary layer of a dried residue of a size composition applied to at least a portion of a surface of the at least one glass fiber and a secondary layer of a composition secondary coating aqueous including non-hydratable solid inorganic lubricating particles applied on at least a portion of the dried residue of the sizing composition.

35. The coated fiber strand according to the claim 34, 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.

36. The coated fiber strand according to the claim 35, where the at least one fiberglass is a fiberglass E.

37. The coated fiber strand according to claim 35, wherein the at least one glass fiber is a fiber of glass derivatives E.

38. A coated fiber strand including at least one glass fiber having a primary layer of a size composition applied to at least a portion of a surface of the at least one glass fiber and a secondary layer of a secondary coating composition placed on at least a portion of the primary layer, including the secondary coating composition, hydrophilic inorganic solid lubricating particles that absorb and retain water in the interstices of the hydrophilic particles.

39. The fiber-coated strand according to the claim 38, 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.

40. The coated fiber strand according to the claim 39, where the at least one fiberglass is a fiberglass E.

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

42. A coated fiber strand including at least one glass fiber having a primary layer of a dried residue of a size composition applied to at least a portion of a surface of the at least one glass fiber, a secondary layer of a composition of secondary coating including a polymeric material placed on at least a portion of the primary layer, and a tertiary layer including solid inorganic powder lubricating particles placed on at least a portion of the secondary layer.

43. The coated fiber strand according to claim 42, 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.

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

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

46. A coated fiber strand including at least one glass fiber having a primary layer of a dried residue of an aqueous sizing composition applied to at least a portion of a surface of the at least one glass fiber, including the aqueous composition of sizing: (a) metallic inorganic solid lubricating particles having a hardness not exceeding the hardness of the at least one glass fiber, including the solid metallic inorganic lubricating particles, at least one particle selected from the group consisting of indium, thallium, tin, copper, zinc, gold and silver; and (b) a polymeric film-forming material.

47. The coated fiber strand according to claim 46, 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. The coated fiber strand according to the claim 47, where the at least one fiberglass is a fiberglass E.

49. The coated fiber strand according to claim 47, wherein the at least one glass fiber is a fiber of glass derivatives E.

50. A reinforced polymeric composite comprising: (a) a coated fiber strand including at least one glass fiber having a primary layer of a dried residue of an aqueous sizing composition applied to at least a portion of a surface of the at least one fiberglass, including the aqueous sizing composition: (1) solid, inorganic, non-hydratable, inorganic lubricating particles having a hardness not exceeding the hardness of the at least one fiberglass; and (2) a polymeric material, the aqueous sizing composition being essentially free of glass materials; and (b) a polymeric matrix material.

51. The reinforced polymeric composite according to claim 50, 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.

52. A fabric including a coated fiber strand including at least one glass fiber having a primary layer of a dried residue of an aqueous sizing composition applied to at least a portion of a surface of the at least one glass fiber, including the aqueous sizing composition: (a) lamellar, non-hydratable, inorganic solid lubricating particles having a hardness not exceeding the hardness of the at least one glass fiber; and (b) a polymeric film-forming material.

53. The fabric according to claim 52, 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

54. An electronic support including: (a) a fabric including a coated fiber strand including at least one glass fiber having a main layer of a coating composition including lamellar, non-hydratable, inorganic solid lubricating particles applied to at least one a portion of a surface of the at least one fiberglass; and (b) a layer of a polymeric matrix material applied on at least a portion of the fabric.

55. The electronic support according to claim 54, 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.

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

57. An electronic circuit board including: (a) an electronic support including: (i) a fabric including a coated fiber strand including at least one glass fiber having a main layer of a coating composition including solid lamellar inorganic lubricant particles , non-hydratable, applied to at least a portion of a surface of the at least one glass fiber; 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.

58. The electronic circuit board according to claim 57, 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.

59. The electronic circuit board according to claim 57, further comprising at least one hole extending through at least a portion of the circuit board.

60. The electronic circuit board according to claim 57, wherein the support is a first, second or third tier package.

61. An electronic support including: (a) a first composite layer comprising: (i) a fabric including at least one partially coated fiber strand including at least one glass fiber having a main layer of a coating composition including lubricating particles lamellar inorganic solids, non-hydratable, applied to at least a portion of a surface of the at least one fiberglass; 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.

62. The electronic support according to claim 61, 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 61, 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 that includes a strand of at least partially coated fiber that includes at least one fiberglass having a main layer of a coating composition including lamellar, non-hydratable, inorganic solid lubricating particles applied to at least a portion of a surface of the at least one glass fiber; 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 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.

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

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

68. A method for bleaching a polymeric compound, including the steps of: (a) applying a particle layer, at least one of the particles of the group consisting of boron nitride, zinc sulphide, montmorillonite and mixtures thereof being selected to at least one portion of a surface of at least one glass fiber of a fiberglass strand to form at least one partially coated fiberglass strand; (b) combining the fiberglass strand with a polymeric matrix material; and (c) forming a reinforced polymer composite from the fiberglass strand and polymeric matrix material, wherein the whiteness index value of the reinforced polymeric composite is less than the whiteness index value of a composite formed from the material of polymeric matrix.

69. The method according to claim 68, wherein the polymeric matrix material is nylon.