RU2211814C2 - Impregnated yarns of glass fibers and cloth on their base - Google Patents

Abstract

FIELD: fiber yarns with coating. SUBSTANCE: yarns of fibers with coating include, at least, one fiber having layer of dried residue compatible with polymers of coating composition, at least, on a part of surface, at least, of one fiber. Coating composition compatible with polymers includes: (a) multitude of discrete and stable in size particles produced from materials selected from group consisting of organic materials, polymer materials, composite materials and their mixtures ensuring production of hollows between one fiber and, at least, one adjacent fiber, with particles having overage size of about 0.1 to about 5 mcm; (b) at least, one lubricating material; (c) at least, one polymer film-forming material, and (d) at least, one finishing agent. Invention also covers cloth including, at least, one of such yarns of fibers. EFFECT: reduced wear and brittleness of fibers in friction, provided good wettability and impregnability of coating with matrix material. 59 cl, 8 dwg, 5 tbl, 4 ex

Description

Cross references to related applications
This patent application is partly continuing the US patent application serial No. 09/170566 by B. Novich et al., Entitled "Impregnated strands of glass fibers and products including them", registered October 13, 1998, which in turn is partly continuing U.S. Patent Application Serial No. 09/034077 by B. Novich et al., entitled "Impregnated Strands of Fiberglass and Including Products thereof", filed March 3, 1998, which is currently canceled.

 This application is related to the US patent application Serial No. 09/170579, B. Novich et al., Entitled "Methods for Decelerating Friction-induced Wear of Strands of Fiberglass", filed October 13, 1998, which in turn is partially continuing US patent application Serial No. 09/034078 by V. Novich et al., entitled "Methods for Decelerating Friction-induced Wear of Fiberglass Strands", filed March 3, 1998, now canceled; US Patent Application Serial No. 09/170781, by B. Novich et al., entitled "Strands of Glass Fiber Coated with Heat-Conducting Inorganic Solid Particles and Including These Strands of Product", filed October 13, 1998, which in turn is partly continuing U.S. Patent Application Serial No. 09/034663, B. Novich et al., entitled "Strands of Glass Fiber Coated with Heat-Conducting Inorganic Solid Particles and Including These Strands of Product", filed March 3, 1998, which has now been canceled; US Patent Application Serial No. 09/170780, by B. Novich et al., entitled “Strands of Glass Fiber Coated with Inorganic Lubricant and Including These Strands of Product,” registered October 13, 1998, which in turn is in part a continuation of the application US patent serial 09/034525, B. Novich et al., entitled "Strands of glass fibers coated with inorganic lubricant and including these strands of the product", registered March 3, 1998, is now revoked; U.S. Patent Application Serial No. 09/170565, B. Novich et al., entitled "Strands of Glass Fiber Coated with Inorganic Particles and Including These Strands of Product", filed October 13, 1998, which in turn is partly continuing the application for US patent serial 09/034056, B. Novich et al., entitled "Strands of glass fibers coated with inorganic particles and including these strands of the product", registered March 3, 1998, is now revoked; US Serial Application No. 09/170578, B. Novich et al., entitled “Fiberglass-Reinforced Laminates, Electronic Boards, and Fabric Assembly Methods,” October 13, 1998, which is partly continuing the US serial application. 09/130270, B. Novich et al., Entitled "Fiberglass Reinforced Laminates, Electronic Boards, and Fabric Assembly Methods," registered August 6, 1998, which in turn is partly a continuation of the US patent application serial No. 09/034525, B. Novich et al., Entitled "Strands of fiberglass, by rytye inorganic lubricant containing these strands of products, "filed March 3, 1998, now repealed.

 This patent application claims the provisional patent application US 60/133076, registered May 7, 1999, and 60/146337, registered July 30, 1999

Technical field
The present invention relates mainly to coated strands of glass fibers for reinforcing composites, and more particularly to strands of glass fibers coated with particles forming voids between adjacent strands of glass fiber.

State of the art
When performing thermosetting (thermosetting) materials molding operations, the properties of good “wetness” (penetration of the polymer matrix material through the mat or fabric) and good “penetration” (penetration of the polymer matrix material through individual bundles or strands of mat or fabric fibers) are desirable. Conversely, the properties of good dispersibility are of prime importance when performing typical molding operations for thermoplastic materials.

 Japanese patent application 9-208268 describes a fabric having filaments formed by glass fibers coated immediately after spinning with starch or synthetic resin, and constituting 0.001-20.0 wt.% Particles of inorganic solids such as colloidal silica, calcium carbonate, kaolin and talc, with an average particle size of 5 to 200 nanometers (0.05 to 2 micrometers), to improve the impregnation of polymers. In paragraph 13 of the detailed description of the aforementioned invention, it is indicated that if such coatings have more than 20 wt.% Inorganic solid particles, then they cannot be used for coating glass fibers. Before forming the laminate, heat or water degreasing is necessary to remove such a coating from the glass fibers.

 US patent 3,312,569 describes the adherence of alumina particles to the surface of glass fibers, which improves the penetration of the polymer between the reinforcing glass fibers during the preparation of the composite. However, the Mos hardness values for alumina are higher than about 9 (see R. Weast (Ed.), Handbook of Chemistry and Physics, CRC Press, 1975, page F-22, which is incorporated herein by reference) which can lead to abrasion of softer fiberglass.

 USSR patent 859400 describes an impregnating composition for the manufacture of fiberglass laminates, the composition containing an alcohol solution of phenol-formaldehyde polymer, graphite, molybdenum disulfide, polyvinyl butyral and a surfactant. Volatile alcohol solvents are not desirable for fiberglass applications.

 To modify the characteristics associated with the ability of the reinforcing material to be impregnated and / or to reduce the overall density of the composite material made from it, hollow filler particles can be used. For example, US Pat. No. 5,412,003 describes the impregnation of glass fibers with a polymer composition comprising an unsaturated ester, a polymerizable monomer, a thermoplastic polymer, a polymerization initiator, and hollow glass microspheres (Column 2, lines 6-14). The casting mass and molded products obtained from such impregnated fibers are light weight (column 2, lines 26-30). U.S. Pat. 4, lines 39-43 and column 3, lines 15-30). Preferably, these fillers are used for reinforcing materials in the form of an aqueous suspension, without sizing compositions (column 3, lines 63-68 and column 4, lines 1-3). US Pat. No. 5,866,253 describes the inclusion of heat-expanding hollow particles in strands of fibers. When expanding, these particles form "micro bubbles", as a result of which the cross section of strands of fibers intended for use in composite materials increases. Expanded particles usually have a diameter of from about 40 to about 50 micrometers, which is larger than the diameter of the fibers of the strand (column 3, lines 5-10). The diameter of the strands of fibers, including expanded particles, is usually four times increased compared to strands of fibers without expanded particles, and the density of the strands is significantly reduced (column 4, lines 12-18). The increased diameter of the strands allows the use of fewer strands in the preparation of composites, which ensures a lower density of the finished product (column 1, lines 39-43).

In the event that composites or laminates are obtained from strands of fibers woven into a fabric, in addition to providing good wetting properties and good impregnation of the fibers, it is also desirable that the coating on the surfaces of the fiber strands protect the fibers from abrasion during technological operations and ensure good suitability for the process weaving, in particular on pneumatic looms, and was also compatible with the polymer material of the matrix, which includes strands of fibers. Many sizing components commonly used for strands of fibers to be woven can adversely affect the adhesion between the glass fibers and the laminate of the matrix. For example, starch, which is usually used as a sizing component for textile fibers, is generally not compatible with the matrix material, which is a layered polymer. To prevent incompatibilities between the glass fibers and the matrix material, the coating or sizing composition is typically removed from the fabric prior to lamination, by thermal decomposition of the sizing components (called thermal cleaning or degreasing) or by washing the fabric with water (also called degreasing). The usual method of thermal cleaning for thermal decomposition of sizing components involves heating the fabric at 380 ^o C for 60-80 hours. The thermally cleaned fabric is then re-coated with a silicone sizing compound (sizing) to improve adhesion between the glass fiber strands and the matrix material. However, such degreasing methods do not always successfully remove incompatible materials, and in addition, they can contaminate the tissue with decomposition products.

 Japanese Patent Application 8-119-682 describes a primary sizing composition comprising a water-soluble epoxy resin that can be easily removed by rinsing with water (page 3, paragraph 2), which improves the removal of sizing compositions or their degreasing for use in composites. Preferably, the primary sizing comprises an epoxy resin having aggregated and formed particles with diameters from 0.5 to 50 micrometers and a pH between 5.5 and 7.5 (page 4, paragraph 1). Preferably, the epoxy resin is a colloid with particles ranging in size from 1 to 5 micrometers (page 6, paragraph 1). It is believed that the particles help to prevent the spreading or flowing of the epoxy resin during drying.

 U.S. Pat.

 Other patents describe methods for producing a composite material by incorporating polymer resin particles into fiber strands and then heating or compressing the strands to form a composite. US Pat. No. 4,615,933 describes the saturation of glass fabrics or strands of glass fibers with aqueous dispersions of polytetrafluoroethylene or other fluoropolymer particles to produce strands having about 50-70 wt.% Fibers and about 30-50 wt.% Polytetrafluoroethylene. Then the strands are pressed to obtain composites. US patents 5364657 and 5370911 describe the incorporation of polymer particles into fiber strands by either contacting the wet strands with an air stream containing dry polymer particles (Column 2, lines 60-68 and Column 3, lines 1-8 of patent 5364657), or by providing electrostatic adhesion of polymer particles to fiber strands (column 3, lines 13-37 of patent 5370911). Then the fiber strands are heated so that the particles stick together, forming a continuous polymer coating of more than 10 wt. % of coated fiber strands. Other additives, such as formulations or emulsifiers, are generally undesirable for use in such coatings (column 4, lines 50-51 of patent 5370911 and column 2, lines 18-21 of patent 5364657). However, fiber strands having high levels of polymer coating on their surfaces are often difficult to weave on pneumatic looms.

 There is a need for coatings that reduce wear due to friction (abrasive wear) and brittleness of glass fibers, compatible with a wide variety of polymer matrix materials and providing good wettability and impregnation of the matrix material. In addition, it is particularly desirable that these coatings be compatible with modern pneumatic weaving equipment in order to increase its productivity.

SUMMARY OF THE INVENTION
One aspect of the present invention is a strand of coated fibers comprising at least one fiber having a dried coat layer of a polymer-compatible coating composition on at least a portion of the surface of the at least one fiber, the polymer-compatible coating composition comprising: ( a) a lot of discrete, stable particle size obtained from materials selected from the group consisting of organic materials, polymeric materials, composite materials and mixtures thereof, framing the creation of voids between the at least one fiber and at least one adjacent fiber, the particles have an average size of from about 0.1 to about 5 micrometers; (b) at least one lubricant; (c) at least one polymeric film-forming material; (d) at least one sizing composition (sizing); as well as fabric comprising at least one such strand of fibers.

 Another aspect of the present invention is a strand of coated fibers comprising at least one glass fiber having a dried residue of an aqueous coating composition compatible with polymers on at least a portion of the surface of at least one fiber, the aqueous coating composition compatible with polymers, includes: (a) many discrete polymeric organic particles, providing voids between at least one fiberglass and at least one adjacent fiberglass, and h the particle, have an average size of about 5 micrometers; (b) a lubricant selected from the group consisting of oils, waxes, greases, and mixtures thereof; (c) a polymeric material forming a film selected from the group consisting of thermosetting polymeric materials, thermoplastic polymeric materials, natural polymeric materials and mixtures thereof; (d) a sizing; as well as fabric comprising at least one such strand of fibers.

 Another aspect of the present invention is a strand of coated fibers comprising at least one glass fiber having a dried residue of an aqueous coating composition compatible with polymers on at least a portion of the surface of at least one fiber, the aqueous coating composition being compatible with polymers includes; (a) a plurality of discrete particles, including: (i) at least one particle obtained from an acrylic copolymer, which is a copolymer of styrene and acrylic resin; (ii) at least one particle obtained from an inorganic solid lubricant selected from the group consisting of boron nitride, graphite and metal dichalcogenides, the particles having an average size of up to about 5 micrometers and include from about 35 to about 55 wt.% compatible with the polymer coating composition, based on the total weight of solids; (b) a lubricant selected from the group consisting of cetyl palmitate, cetyl laurate, octadecyl laurate, octadecyl myristate, octadecyl palmitate, octadecyl stearate and paraffin, the lubricant comprising from about 20 to about 40 wt. % polymer-compatible coating composition, based on the total weight of solids; (c) a thermoplastic polymer material forming a film selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polyacrylic acid, as well as their copolymers and mixtures thereof, wherein the thermoplastic polymer material forming a film comprises from about 5 to about 30 wt. .% compatible with polymers coating compositions, calculated on the total weight of dry matter; (d) a sizing; as well as fabric comprising at least one such strand of fibers.

 And another aspect of the present invention is a fabric comprising a plurality of strands of fibers including at least one fiber, wherein at least a portion of the fabric has a polymer-compatible coating composition comprising: (a) a plurality of discrete, stable particle sizes obtained from materials selected from the group consisting of organic materials, polymeric materials, composite materials and mixtures thereof, creating voids between at least one fiber and at least about adjacent adjacent fiber, the particles having an average size of from about 0.1 to about 5 micrometers; (b) at least one lubricant; (c) at least one polymeric film-forming material; (d) at least one sizing.

Brief Description of the Drawings
The preceding brief description of the present invention, as well as the following detailed description of preferred embodiments thereof, will be better understood when taken in conjunction with the accompanying drawings.

 FIG. 1 is a perspective view of a strand of coated fibers having a primary layer of dried residue of a coating composition in accordance with the present invention.

 FIG. 2 is a perspective view of a strand of coated fibers having a primary layer of a dried residue of a sizing composition, and on top of it is a secondary layer of a secondary coating composition in accordance with the present invention.

 FIG. 3 is a perspective view of a strand of coated fibers having a primary layer of dried residue of a sizing composition, a secondary layer of a secondary coating composition, and over them a tertiary layer in accordance with the present invention.

 Figure 4 is a top view of a composite in accordance with the present invention.

 Figure 5 is a top view of the fabric in accordance with the present invention.

 FIG. 6 is a cross-sectional view of the base for electronic circuit boards in accordance with the present invention.

 Figures 7 and 8 are cross-sectional views of alternative embodiments of electronic structural material in accordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION
The strands of fibers of the present invention have a unique coating, which not only reduces abrasive wear and breakage of fibers during technological operations, but also provides good wetting, wetting and dispersing qualities in the preparation of composites. Other desirable characteristics exhibited by strands of coated fibers of the present invention are good layered strength, good heat resistance, good hydrolytic stability, low corrosion and low reactivity in high humidity conditions in the presence of reactive acids and alkalis, and compatibility with a number of polymeric materials matrices, which can eliminate the need to remove the coating, in particular by heat cleaning, before lamination.

 Another significant advantage of the strands of coated fibers of the present invention is their good suitability for technological operations during weaving and knitting. Low levels of fluffing, low amount of broken fibers, low strand tension, high volatility and short turn-on time are characteristics provided by the coated glass fiber strands of the present invention, which improve weaving and knitting, and therefore provide fabric with fewer surface defects, suitable for use in printed circuit boards.

 Significant advantages of composite materials made from fiber strands of the present invention include good flexural strength, good bond strength between the layers, and good hydrolytic stability, i.e. resistance to movement of water along the interface of the fiber and the matrix. In addition, the bases for electronic boards and printed circuit boards made from fiber strands in accordance with the present invention have good drillability and resistance to metal movement (also called cathode-anode filament, or CAF). In particular, printed circuit boards made from the fiber strands of the present invention provide low tool wear during drilling and good location accuracy of drilled holes.

 1, where the same numbers denote the same elements, a coated fiber strand 10 including a plurality of fibers 12 of the present invention is shown. As used herein, the term “strand” means a plurality of individual fibers. The term "fiber" means an individual thread. Although the scope of the invention is not limited to this, the fibers 12 typically have an average nominal diameter of from about 3 to about 35 micrometers. Preferably, the average nominal fiber diameter of the present invention is about 5 micrometers or more. For thin-thread applications, the average nominal fiber diameter is preferably from about 5 to about 7 micrometers.

Fibers 12 can be obtained from any type of fiber-forming materials known to those skilled in the art, including inorganic fiber-forming materials, organic fiber-forming materials, and mixtures and combinations thereof. Inorganic and organic materials can be of either artificial or natural origin. Those skilled in the art will recognize that fiber-forming inorganic and organic materials can also be polymeric materials. As used herein, the term "polymeric material" means a material formed by macromolecules consisting of long chains of atoms that are interconnected and which can intertwine in solution or in solid state ^{2 2} (James Mark et al., Inorganic Polymers, Prentice Hall Polymer Science and Engineering Series, 1992, on page 1, incorporated herein by reference). The term “fiber-forming”, as used herein, means a material from which a conventional continuous filament, fiber, strand or thread can be formed.

 Preferably, the fibers 12 are made from inorganic fiber-forming glass materials. Fiber-forming glass materials suitable for use in the present invention include, without limitation, the scope of the invention, materials obtained from fiber-forming glass compositions, such as "E-glass", "A-glass", "C-glass", "D-glass "," R-glass "," S-glass "and derivatives of E-glass. As used herein, the term “E-glass derivatives” means glass compositions comprising small amounts of fluorine and / or boron, and preferably not containing fluorine and / or boron. In addition, in this description, the expression "small amounts" means an amount of less than about 1 wt. % fluorine and less than about 5 wt.% boron. Examples of other fiber-forming glass materials suitable for use in the present invention are basalt and mineral wool. Preferred glass fibers are obtained from E-glass and from derivatives of E-glass. Such compositions are well known to those skilled in the art, and further discussion in the present description is not necessary. The glass fibers of the present invention can be obtained by any suitable method known in the art for glass fibers. For example, glass fibers can be obtained by molding fibers directly from molten glass or by molding from molten glass beads. In the case of the operation of forming fibers directly from glass, the raw materials are combined, melted and homogenized in an oven for melting glass. The molten glass moves from the furnace to the piggy bank and to the device for producing fibers, where they are converted into continuous glass fibers. In the case of the operation of forming fibers from molten glass beads, pieces of glass or glass beads having the desired finished glass composition are preformed and fed into dies, where they are melted and converted into continuous glass fibers. If pre-boiling is used, then the glass beads are first fed to the pre-boiling device, melted, then the molten glass is fed to the fiber production device, where the glass is converted into continuous fibers. In the present invention, glass fibers are preferably obtained by molding directly from glass. For more information on glass compositions and methods for producing glass fibers, see K. Loewenstein publications. The Manufacturing Technology of Glass Fiber, 3d Ed. , 1993, pages 30-44, 47-103 and 115-165, US Patents 4,542,106 and 5,789,329, and IPC-EG-140 "Specification for Finished Fabric Woven from 'E' Glass for Printed Boards," on page 1, The Institute for Interconnecting and Packaging Electronic Circuits, June 1997, which are incorporated herein by reference.

 Non-limiting examples of suitable non-glass fiber-forming inorganic materials include ceramic materials derived from silicon carbide, coal, graphite, mullite, alumina, and piezoelectric ceramic materials. Non-limiting examples of suitable organic fiber-forming materials include cotton, cellulose, natural rubber, linen, ramie, hemp, sisal and wool. Non-limiting examples of suitable organic polymeric fiber-forming materials include materials derived from polyamides (such as nylon and aramids), thermoplastic polyesters (such as polyethylene terephthalate and polybutylene terephthalate), acrylics (such as polyacrylonitriles), polyolefins, polyurethanes and vinyl polymers (such like polyvinyl alcohol). Non-glass fiber-forming materials suitable for use in the present invention, as well as methods for producing and processing such fibers, are described in detail in Encuclopedia of Polymer Science and Technology, v.6, 1967, pages 505-712, which is incorporated herein by reference links. It is understood that mixtures or copolymers of any of the above materials and combinations of fibers obtained from any of the above materials can also be used for the present invention, if desired.

 The present invention will hereinafter be described mainly in the context of fiberglass strands, although it will be understood by those skilled in the art that strand 10 may include fibers 12 obtained from any fiber-forming material known in the art and described above.

 Continuing with reference to FIG. 1, in a preferred embodiment of the invention, at least one, and preferably all of the fibers 12 of the strand 10 of the fibers of the present invention have a residue composition layer 14 on at least part 17 of surface 16 of fibers 12, to protect surfaces 16 fibers from abrasion during technological operations and to reduce the fragility of the fibers. Preferably, layer 14 is present on the entire outer surface 16 or on the periphery of the fibers 12.

 The coating compositions of the present invention are preferably aqueous coating compositions, and more preferably aqueous, polymer compatible coating compositions. Although not preferred for safety reasons, coating compositions may also contain volatile organic solvents such as alcohol or acetone, if necessary, but preferably they do not contain such solvents. In addition, the coating compositions of the present invention can be used as compositions for primary sizing and / or compositions for secondary sizing or for secondary coating.

 In the present application, in the description of a preferred embodiment of the invention, the terms “sizing”, “sizing” or “sizing” refer to coating compositions applied to the fibers. The terms “primary sizing” or “primary sizing” refer to coating compositions that are applied to the fibers immediately upon receipt of the fibers. The terms "secondary sizing", "secondary sizing" or "secondary coating" refer to coating compositions that are applied to the fibers after application of the primary sizing. This coating can be applied to the fibers before the fibers are incorporated into the fabric, or it can be applied to the fibers after the fibers are incorporated into the fabric, for example, by coating the fabric. In an alternative embodiment of the invention, the terms “sizing”, “sizing” or “sizing” additionally refer to coating compositions (also known as “finishing sizing”) applied to the fibers after at least part, and usually all the usual polymer incompatible sizing composition is removed by heat or chemical treatment, i.e., the finishing sizing is applied to uncoated glass fibers incorporated into the fabric.

 As used herein, the term “compatible with polymers” means that the coating composition applied to the glass fibers is compatible with the polymer matrix material into which the glass fibers will be included, so that this coating composition (or selected coating components) does not need to be removed before being incorporated into the matrix material (for example, removal by heat cleaning), and also contributes to good impregnation and good wetting of the matrix material during technological operations, resulting in a composite material Having desirable physical properties and hydrolytic stability.

 The coating composition of the present invention includes one or more, and preferably a plurality of particles 18, which, when deposited on at least one fiber 23 of the plurality of fibers 12, adhere to the outer surface 16 of at least one fiber 23 and form one or more voids 21 between adjacent fiberglass 23, 25 strands 10. These voids 21 correspond mainly to the average size 19 of the particles 18 located between adjacent fibers.

Particles 18 of the present invention are preferably discrete particles. In the present description, the term "discrete" means that the particles do not show a tendency to merge or merge with the formation of films under the conditions of technological operations, but instead, as a rule, they retain their individual shape. In addition, the particles preferably have a stable size. In the present description, the term "particles of stable size" means that the particles, as a rule, retain their average size and shape under the conditions of technological operations, for example, when exposed to forces arising between adjacent fibers during weaving, spinning and other technological operations, which allows maintain the desired void sizes between adjacent fibers 23, 25. In other words, the particles are preferably not crushed, not dissolved and essentially not deformed in the coating composition, that is, particles are not formed, the maximum size of which is smaller than the selected average particle size under ordinary conditions of technological processing of fiberglass, such as exposure at temperatures reaching about 25 ^o C, and preferably up to about 100 ^o C, even more preferably up to about 140 ^o C. In addition, the particles 18 should not significantly increase in size or grow in the conditions of the technological processing of glass, and in particular, in terms of technological composite processing when the processing temperatures can exceed 150 ^o C. in the present description, The phrase "do not substantially increase in size" with respect to the particles indicates that the particles should not expand or increase in size by more than about 3 times as compared to their initial size during processing. Preferably, the coating compositions of the present invention are substantially free of heat expanding hollow particles. As used herein, the term “heat expanding hollow particles” refers to hollow particles filled or containing a foaming agent that, at temperatures sufficient to convert the foaming agent into a volatile form, expand or substantially increase in size. As used herein, the term “substantially free of” means that the sizing composition contains less than 20 wt.% Of heat-expanding hollow particles based on the total weight of solids, more preferably less than about 5 wt.% And most preferably less than 0.001 wt.%. In addition, in the present description, the term "stable size" includes both crystalline and non-crystalline materials.

 In addition, although this is not necessary, it is preferable that the particles 18 are non-wax. The term "non-wax" means that the materials from which the particles are obtained are not wax-like. As used herein, the term “wax-like” refers to materials consisting primarily of hydrocarbons with unbranched hydrocarbon chains, with an average chain length of from about 25 to about 100 carbon atoms (LH Sperling. Introduction of Physical Polymer Science, John Wiley and Sons, Inc, 1986 , pages 2-5, incorporated by reference. W. Pushaw et al. Use of Micronized Waxes and Wax Dispersions in Waterborne Systems, Polymers, Paint, Colors Journal, v. 189, 4412, January 1999, pages 18-21, incorporated herein by reference).

 Preferably, the particles 18 of the present invention are discrete, dimensionally stable, non-wax particles.

 Particles 18 may have any desired shape or configuration. Non-limiting examples of suitable particle forms include spherical shapes (such as spheres, beads, or hollow spheres), cubic, plate, or needle shapes (elongated or threadlike). In addition, the particles 18 may have a hollow, porous or void-free internal structure. In addition, the particles 18 may have a combination of these structures, for example, a hollow center with porous or solid walls. 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.

Particles 18 can be obtained from materials selected from the group consisting of polymer and non-polymer inorganic materials, polymer and non-polymer organic materials, composite materials and mixtures thereof. As used herein, the term “polymeric inorganic material” means a polymeric material having a main chain repeat element based on an element or elements other than carbon. See JE Mark et al., Page 5, incorporated herein by reference, for more information. Organic polymeric materials include synthetic polymeric materials, semi-synthetic polymeric materials and natural polymeric materials. The term "organic material" in the present description refers to all carbon compounds, except for binary compounds such as carbon oxides, carbides, carbon disulfide, etc .; such ternary compounds as metal cyanides, metal carbonyls, phosgene, carbonyl sulfide, etc. and metal carbonates such as calcium carbonate and sodium carbonate. See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, 12 ^th Ed., 1993, pages 761-762, which is incorporated herein by reference. In most cases, organic materials include carbon-containing compounds in which carbon is usually attached to itself and to hydrogen, and often also to other elements, with the exception of carbon-containing ionic compounds. See publication of M. Silberberg, Chemistry, The Molecular Nature of Matter and Change, 1996, on page 586, which is incorporated herein by reference. The term "inorganic material", as a rule, includes all materials that are not carbon compounds, with the exception of carbon oxides and carbon disulfide. See publication R. Lewis, Sr. , Hawley's Condensed Chemical Dictionary, 12 ^th Ed., 1993, at page 636, which is incorporated herein by reference. Used in this description, the term "inorganic materials" means any materials that are not organic materials. As used herein, the term “composite material” means a combination of one or more different materials. For more information on the particles useful for this invention, see G. Wypych, Handbook of Fillers, 2 ^nd Ed., 1999, pages 15-202, which is incorporated herein by reference.

 Non-polymeric inorganic materials suitable for producing particles 18 of the present invention include inorganic materials selected from the group consisting of metals, oxides, carbides, nitrides, borides, sulfides, silicates, carbonates, sulfates and hydroxides. A non-limiting example of a suitable inorganic nitride from which particles 18 are obtained is boron nitride, which is the preferred inorganic material from which particles 18 used in the present invention are obtained. A non-limiting example of a suitable inorganic oxide is zinc oxide. Suitable inorganic sulfides include molybdenum disulfide, tantalum disulfide, tungsten disulfide and zinc sulfide. Suitable inorganic silicates include aluminosilicates and magnesium silicates such as vermiculite. Suitable metals include molybdenum, platinum, palladium, nickel, aluminum, copper, gold, iron, silver, as well as their alloys and mixtures.

Although not necessary, particles 18 can be obtained from solid lubricants. Used in the present description, the term "solid lubricant" means any solid substance placed between two surfaces to protect them from damage during relative movement and / or to reduce friction and wear. In one embodiment, the solid lubricants are inorganic solid lubricants. Used in the present description, the term "inorganic solid lubricant" means that solid lubricants have a characteristic crystallization form, as a result of which they turn into thin flat plates that easily glide on each other's surface, resulting in the effect of antifriction lubrication between the surface of the fiberglass and the surface of the adjacent solid, and at least one of these elements is in motion. See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, 12 ^th Ed., 1993, page 712, which is incorporated herein by reference. Friction is the sliding resistance of one solid substance to another. See F. Clauss, Solid Lubricants and Self-Lubricating Solids, 1972, page 1, which is incorporated herein by reference.

In one embodiment of the present invention, solid lubricants have a layered structure. Solid lubricants having a layered structure are composed of layers of atoms arranged in the form of hexagons, with strong bonds within this layer and weak van der Waals bonds between the layers, resulting in a low shear force between these layers. A non-limiting example of a layered structure is a hexagonal crystal structure. See K. Ludema, Friction, Wear, Lubrication, 1996, on page 125, Solid Lubricants and Self-Lubricating Solids, on pages 19-22, 42-54, 75-77, 80-81, 82, 90-102 , 113-120 and 128, and W. Campbell "Solid Lubricants", Boundary Lubrication; An Appraisal of World Literature, ASME Research Committee on Lubrication, 1969,
pages 202-203, which are incorporated herein by reference. Inorganic solid particles having a layered felt structure are also suitable for the present invention.

 Non-limiting examples of suitable layered solid lubricants suitable for producing particles 18 of the present invention include boron nitride, graphite, metal dichalcogenides, mica, talc, gypsum, kaolinite, calcite, cadmium iodide, silver sulfide, and mixtures thereof . Preferred inorganic solid lubricants include boron nitride, graphite, metal dichalcogenides and mixtures thereof. Suitable metal dichalcogenides include molybdenum disulphide, molybdenum disulide, tantalum disulphide, tantalum disulide, tungsten disulphide, tungsten diselide and mixtures thereof.

 A non-limiting example of an inorganic solid lubricant suitable for use in the coating compositions of the present invention having a hexagonal crystal structure is boron nitride. Particles derived from boron nitride, zinc sulfide and montmorillonite also provide good whiteness of composites with polymer matrix materials such as nylon 6,6.

Non-limiting examples of boron nitride particles suitable for use in the present invention are boron nitride powder particles of PolarTherm ^® 100 Series (PT 120, PT 140, PT 160 and PT 180), 300 Series (PT 350) and 600 Series (PT 620, PT 630, PT 640 and PT 670) manufactured by Advanced Ceramics Corporation of Lakewood, Ohio. See the publication "PolarTherm ^® Thermally Conductive Fillers for Polymeric Materials", a technical bulletin from Advanced Ceramics Corporation of Lakewood, Ohio, 1996, which is incorporated herein by reference. These particles have a thermal conductivity of about 250-300 W / (m • K) at 25 ^{° C.} , a dielectric constant of about 3.9, and a volume resistivity of about 10 ¹⁵ Ω • cm. The 100 Series powder particles have an average particle size of from about 5 to about 14 micrometers, the 300 Series powder particles have an average particle size of from about 100 to about 150 micrometers, and the 600 Series powder particles have an average particle size of from about 16 to about 200 micrometers.

In another embodiment of the present invention, particles 18 are made from inorganic solid lubricants that are not hydratable. As used herein, the term “non-hydratable” means that solid inorganic lubricant particles do not react with water molecules to form hydrates and do not contain hydration water or crystallization water. A "hydrate" is obtained by the reaction of water molecules with a substance in which the H-OH bond is unsplit. See publications R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, 12 ^th Ed. , 1993, pages 609-610 and T. Perros, Chemistry, 1967, pages 186-187, which are incorporated herein by reference. Hydrates contain coordinated water, which coordinates the cations in the hydrated material and cannot be removed without destroying the structure, and / or structural water, which occupies voids in the structure, which increases electrostatic energy without disturbing the charge balance. See R. Evans, An Introduction to Crystal Chemistry, 1948, on page 246, which is incorporated herein by reference. Preferably, the coating composition is substantially free of hydratable inorganic solid lubricants. As used herein, the term “substantially free of” means that the coating composition comprises less than about 20 wt.% Particles of hydratable inorganic solid lubricants based on the total dry matter, more preferably less than about 5 wt. % and most preferably less than about 0.001 wt.%
Although not preferred, the coating compositions of the present invention may contain particles derived from hydratable or hydrated inorganic solid lubricants, in addition to the non-hydratable inorganic solid lubricants described above. Non-limiting examples of such hydratable inorganic solid lubricants are clay mineral phyllosilicates, including mica (such as Muscovite), talc, montmorillonite, kaolinite and gypsum.

 Particles 18 can be obtained from non-polymer organic materials. Examples of non-polymeric organic materials suitable for the present invention include, but are not limited to, stearates (such as zinc stearate and aluminum stearate), carbon black, and stearamide.

Particles 18 can be obtained from inorganic polymeric materials. Non-limiting examples of inorganic polymeric materials include polyphosphazenes, polysilanes, polysiloxane, polygermans, polymer sulfur, polymer selenium, silicones, and mixtures thereof. A specific, non-limiting example of particles derived from an inorganic polymer material suitable for use in the present invention is Tospearl ^{5 5} (See RJ Perry. Applications for Cross-Linked Siloxane Particles, Chemtech, February 1999, pages 39- 44.), which is particles derived from crosslinked siloxanes, and is manufactured by Toshiba Silicones Company, Ltd., from Japan.

 Suitable synthetic organic polymeric materials from which the particles can be obtained include, but are not limited to, thermoset materials and thermoplastic materials. Suitable thermosetting materials include thermosetting polyesters, vinyl polyesters, epoxies, phenolic plastics, aminos, thermosetting polyurethanes, and mixtures thereof. A specific, non-limiting example of a preferred synthetic polymer particle obtained from an epoxy material is an epoxy microgel particle.

Suitable thermoplastic materials include thermoplastic polyesters, polycarbonates, polyolefins, acrylic polymers, polyamides, thermoplastic polyurethanes, vinyl polymers, and mixtures thereof. Preferred thermoplastic polyesters include, but are not limited to, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Preferred polyolefins include, but are not limited to, polyethylene, polypropylene, and polyisobutylene. Preferred acrylic polymers include styrene-acrylic copolymers and polymers containing methacrylate. Non-limiting examples of synthetic polymer particles obtained from an acrylic copolymer are ROPAQUE ^® HP-1055 ^{6 6} (see product properties sheet entitled: ROPAQUE ^® HP-1055, Hollow Sphere Pigment for Paper and Paperboard Coatings ", October 1994, from Rohm and Haas Company, Philadelphia, PA, on page 1, incorporated herein by reference), which is an opaque, non-film forming, styrene acrylic polymer synthetic pigment with a particle size of 1.0 micrometer, with a dry content substances of 26.5 wt.% and with a volume of voids of 55% , ROPAQUE ^® OP-96 ^{7 7} (see product technical bulletin entitled "Architectural Coatings -" ROPAQUE ^® OP-96, The All Purpose Pigment ", April 1997, from Rohm and Haas Company, Philadelphia, PA, at page 1, incorporated herein by reference), which is a dispersion of an opaque, non-film forming, styrene acrylic polymer synthetic pigment with a particle size of 0.55 micrometers and a solids content of 30.5 wt.%, and ROPAQUE ^® OP -62-L0 ^{8 8} (ibid.), Which is a dispersion of an opaque, non-forming film, styrene acrylic polymer synthetic o pigment with a particle size of 0.40 micrometers and with a solids content of about 36.5 wt.%, each of which is manufactured by Rohm and Haas Company, from Philadelphia, PA.

 Suitable semi-synthetic organic polymeric materials from which particles 18 can be obtained include, but are not limited to, cellulosic materials such as methyl cellulose and cellulose acetate, and modified starches such as acetate starch ether and ethoxylated starch ether.

 Suitable natural polymeric materials from which particles 18 can be obtained include, but are not limited to, polysaccharides such as starch; polypeptides such as casein; and natural hydrocarbons such as natural rubber and gutta-percha.

(каждый из которых описан выше).In one embodiment of the present invention, polymer particles 18 are made from hydrophobic polymer materials to reduce or limit moisture absorption by coated strands. Non-limiting examples of hydrophobic polymeric materials that are considered suitable for use in the present invention include, but are not limited to, polyethylene, polypropylene, polystyrene, and polymethyl methacrylate. Non-limiting examples of polystyrene copolymers include pigments

(each of which is described above).

In another embodiment of the present invention, the polymer particles 18 are obtained from polymeric materials having a glass transition temperature (T _g ) and / or a melting point higher than about 25 ^{° C.} , and preferably higher than about 50 ^° C.

 Composite particles 18 suitable for use in the present invention include particles obtained by cladding, encapsulating or coating particles derived from a primary material with one or more secondary materials. For example, an inorganic particle made from an inorganic material, such as silicon carbide or aluminum nitride, can be coated with silica, carbonate or nanoclay to obtain a suitable composite particle. In another example, it is possible to react an organosilicon sizing having alkyl side chains with the surface of an inorganic particle derived from an inorganic oxide to produce a suitable composite particle having a softer surface. Other examples include cladding, encapsulating, or coating particles derived from organic or polymeric materials with inorganic materials or various organic or polymeric materials. A specific example of such non-limiting composite particles of the present invention is DUALITE, a synthetic calcium carbonate coated polymer particle manufactured by Pierce and Sevens Corporation of Buffalo, NY.

(каждый из которых описан выше). Другие не ограничивающие объем настоящего изобретения примеры полимерных полых частиц, подходящих для использования в настоящем изобретении, см. в публикации H. Katz et al. (Ed.), 1987, на страницах 437-452, которая включена в настоящее описание в качестве ссылки.In yet another embodiment of the present invention, the particles 18 may be hollow particles obtained from materials selected from the group consisting of inorganic materials, organic materials, polymeric materials, composite materials, and mixtures thereof. Non-limiting examples of materials from which hollow particles can be obtained are described above. Non-limiting examples of polymer hollow particles suitable for use in the present invention are pigments

(each of which is described above). Other non-limiting examples of polymer hollow particles suitable for use in the present invention, see H. Katz et al. (Ed.), 1987, pages 437-452, which is incorporated herein by reference.

Particles 18 may be present in the form of a dispersion, suspension or emulsion in water. Other solvents such as mineral oil or alcohol (preferably in an amount of less than 5 wt.%) Can also be included in the dispersion, suspension or emulsion, if desired. A non-limiting example of a preferred dispersion of particles derived from inorganic material is ORPAC BORON NITRIDE RELEASECOAT-CONC, which is a dispersion of about 25 wt.% Boron nitride particles in water, manufactured by ZYP Coatings, Inc., from Oak Ridge, Tennessee . See "ORPAC BORON NITRIDE RELEASECOAT-CONC", ZYP Coatings, Inc. Technical Bulletin included in the present description by reference. The boron nitride particles in this product have an average particle size of less than about 3 micrometers and include about 1% magnesium aluminosilicate to bind the boron nitride particles to the dispersion substrate. Other products suitable for this invention manufactured by ZYP Coatings include BORON NITRIDE LUBRICOAT ^® , as well as BRAZE STOP and WELD RELEASE products. Specific non-limiting examples of emulsions and dispersions of synthetic polymer particles derived from acrylic polymers and copolymers include the following products: Rhoplex ^® GL-623 ⁹ , ⁹ (see product properties sheet entitled: Rhoplex ^® GL-623, Self-Crosslinking Acrylic Binder of Industrial Nonwovens ", March 1997, from Rohin and Haas Company, Philadelphia, PA, incorporated herein by reference), which is an emulsion of a fully acrylic dense polymer, with a solids content of 45 wt.% And with glass transition temperature of about 98 ^o C; EM ULSION E-2321 ^{10 10} (see product property sheet entitled: "Building Products Industrial Coatings - Emulsion E-2321", 1990, from Rohm and Haas Company, Philadelphia, PA, incorporated by reference herein) which is an emulsion of solid methacrylate polymer, with a solids content of 45 wt.% and with a glass transition temperature of about 105 ^o C; ROPAQUE ^® OR-96 (described above), supplied in the form of a dispersion with a particle size of 0.55 micrometers and with a solids content 30.5 wt.%; ROPAQUE ^® OP-62-LO (described above), also representing a dispersion of an opaque, non-forming synthetic pigment with a particle size of 0.40 micrometers and with a solids content of about 36.5 wt.%; and ROPAQUE ^® HP-1055 (described above) may be supplied as a dispersion with a solids content of about 26.5 wt.%, all of which are available from Rohm and Haas Company, of Philadelphia, PA.

 Particles 18 are selected so that they have an average particle size 19 sufficient to create the desired distance between adjacent fibers. For example, the average size of 19 particles 18 included in the sizing composition applied to the fibers 12 to be woven on pneumatic looms is preferably chosen to provide a sufficient distance between adjacent fibers, allowing the strands 10 of the fibers to be pneumatically moved through the loom. The term "pneumatic loom" as used herein, refers to a type of loom in which weft is inserted into the throat of a loom using a strong jet of compressed air coming from one or more air-jet nozzles. In another example, the average size of 19 particles 18 included in the sizing composition applied to the fibers 12 to be impregnated with the polymer matrix material is chosen so as to create a sufficient distance between adjacent fibers, providing good wettability and impregnation of the strand 10.

 In a specific non-limiting embodiment, the average particle size 19 is at least about 0.1 micrometers, preferably at least about 0.5 micrometers, and is in the range of about 0.1 to about 5 micrometers. preferably in the range of from about 0.5 to about 2.0 micrometers. In this embodiment, the particles 18 have an average size of 19, which is generally smaller than the average diameter of the fibers 12 on which the coating composition is applied. It was found that in a twisted yarn made of strands of 10 fibers having a layer 14 of the remainder of the composition for primary sizing, including particles 18 with an average particle size of 19, above, there are sufficient distances between adjacent fibers 23, 25, which makes it suitable for weaving on a pneumatic loom (ie for pneumatic movement through a loom), while maintaining the integrity of the strand 10 of the fiber and ensuring acceptable characteristics of "wet" and "impregnation" during impregnation with a polymer mat Rial matrix.

 In another specific embodiment of the invention, not limiting the scope of the present invention, the average size of 19 particles 18 is at least about 3 micrometers, preferably at least about 5 micrometers, and is in the range from about 3 to about 1000 micrometers, preferably in the range from about 5 to about 1000 micrometers, and more preferably in the range of from about 10 to about 25 micrometers. Preferably, each of the particles 18 has a minimum size of at least 3 micrometers, and more preferably at least about 5 micrometers. In this embodiment, it is also preferable that the average particle size 19 of the particles 18 basically corresponds to the average nominal diameter of the glass fibers. It has been established that fabric made from strands coated with particles of the above sizes shows good “wet” and “wet” characteristics during impregnation with the matrix polymer material.

 Those skilled in the art will understand that mixtures of one or more particles 18 having different particle sizes 19 can be included in the sizing composition in accordance with the present invention to impart desired properties and processing characteristics to strands 10 of fibers and articles subsequently made from them. More specifically, particles of different sizes can be combined in the required quantities so as to ensure the production of fibers having good suitability for pneumatic movement through a weaving machine, as well as fabrics having good impregnation and wetting characteristics.

 Glass fiber undergoes abrasion when it comes into contact with the rough surfaces of adjacent glass fibers and / or other solid objects or materials with which the glass fibers come into contact during their preparation and subsequent technological operations, such as weaving or spinning. The term "abrasive wear", as used in the present description, refers to the scraping or cutting of pieces of glass fiber surface or the breakage of glass fibers due to friction in contact with particles, edges or objects made of materials that are sufficiently hard to damage the glass fibers. See K. Ludema, page 129, which is incorporated herein by reference. Abrasive wear of fiberglass strands leads to breakage of the strands during technological operations and to the formation of surface defects in products such as woven materials and composites, which increases the cost and cost of manufacture.

 In order to minimize abrasive wear, in one embodiment of the present invention, the particles 18 have a hardness index not exceeding, i.e. equal to or less than the hardness index of fiberglass (fiberglass). The hardness values of particles and glass fibers can be determined by any conventional hardness measurement method, such as Vickers or Brinell hardness, but they are preferably determined according to the original Mos hardness scale, which indicates the relative resistance to scratches on the surface of the material. Mohs of glass fibers typically range from about 4.5 to about 6.5, and are preferably about 6. See R. Weast (Ed.), Handbook of Chemistry and Physics, CRC Press, 1975, page F -22, which is incorporated herein by reference. In this embodiment of the invention, the Mos hardness indices of the particles 18 are preferably in the range of about 0.5 to about 6. The Mos hardness indices of several non-limiting examples of particles derived from inorganic materials suitable for use in the present invention are given in table A below.

 In another embodiment of the present invention, the particles 18 are thermally conductive, i.e., have a thermal conductivity higher than about 30 W / (m • K), such as, for example, particles derived from boron nitride, graphite and the metallic inorganic solid lubricants described above. The thermal conductivity of a solid material can be determined by any method known to those skilled in the art, such as a hot plate protected method, in accordance with ASTM C-177-85 (incorporated herein by reference) at a temperature about 300 K.

 In yet another embodiment of the present invention, the particles 18 are electrically insulating, or have a high electrical resistivity, i.e., have an electrical resistance higher than about 1000 μΩ · cm, for example, such as those derived from boron nitride.

Particles 18 may comprise from about 1 to about 80 wt.% Of the coating composition based on the total weight of solids, preferably from about 1 to about 60 wt. % In one embodiment, the coating composition contains from about 20 to about 60 wt.% Particles 18 based on the total weight of solids, preferably from about 35 to about 55 wt.% And more preferably from about 30 to about 50 wt. %
Those skilled in the art will recognize that the discrete particles 18 of the coating composition may include any combination or mixture of particles 18 described above. More specifically, particles 18 may include additional discrete particles obtained from any of the materials described above used to produce particles 18 in an amount less than the number of particles 18. These additional particles differ from other particles 18 in a polymer-compatible coating composition, t .e. additional particles (1) are chemically different from other particles; or (2) they are chemically the same, but differ in configuration or properties. Additional particles may comprise up to half the number of particles 18, preferably up to about 15% of the number of particles 18.

In addition to particles, the coating composition preferably includes one or more polymeric film-forming materials, such as organic, inorganic and natural polymeric materials. Suitable organic polymeric materials include, but are not limited to, synthetic polymeric materials, semi-synthetic polymeric materials, natural polymeric materials, and mixtures thereof. Synthetic polymeric materials include, but are not limited to, thermoplastic materials and thermoset materials. Preferably, the polymer film-forming materials form a substantially continuous film after being applied to the surface 16 of the glass fibers. Typically, the amount of polymer film-forming materials can be from about 1 to about 60 wt.% By weight of the coating composition, based on the total weight of solids, preferably from about 5 to about 50 wt.%, And more preferably from about 10 to about 30 wt.%
In one embodiment of the invention, thermosetting polymer film-forming materials are preferred polymer film-forming materials for use in a composition for coating glass fiber strands. Such materials are compatible with thermosetting matrix materials used as printed circuit board laminates, such as FR-4 epoxies, which are multifunctional epoxies, and in one embodiment of the invention, bi-functional brominated epoxies are used. See Electronics Materials Handbook ^TM , ASM International, 1989, pages 534-537, which is incorporated herein by reference.

 Suitable thermosetting materials include thermosetting polyesters, epoxies, vinyl esters, phenolic plastics, aminos, thermosetting polyurethanes, and mixtures thereof. Suitable thermosetting esters include STYPOL polyesters manufactured by Cook Composites and Polymers of Port Washington, Wisconsin, and NEOXIL polyesters manufactured by DSM B.V. from Como, Italy.

A non-limiting example of a thermosetting polymer material is epoxy. Suitable epoxy materials for this invention contain in their molecule at least one epoxy or oxirane group, such as polyglycidyl ethers of polyhydric alcohols or thiols. Examples of suitable epoxy film-forming polymers include epoxy resins EPON ^® 826 EPON ^® 880 and manufactured by Shell Chemical Company, of Houston's, Texas.

 Suitable thermoplastic polymeric materials for this invention include vinyl polymers, thermoplastic polyesters, polyolefins, polyamides (e.g., aliphatic polyamides or aromatic polyamides, such as aramid), thermoplastic polyurethanes, acrylic polymers (such as polyacrylic acid) and mixtures thereof.

 In another embodiment of the present invention, the preferred polymer film-forming material is a vinyl polymer. Vinyl polymers suitable for the present invention include, but are not limited to, polyvinyl pyrrolidones such as PVP K-15, PVP K-30, PVP K-60, and PVP K-90, all of which are available from ISP Chemicals from Wayne, New Jersey. Other suitable vinyl polymers include Resin 2828 Resin and 1037 vinyl acetate emulsion copolymers manufactured by National Starch and Chemical from Bridgewater, New Jersey, other polyvinyl acetates such as those made by Fuller (N.V. Fuller) and Air Products and Chemicals Company, from Allentown, PA, as well as polyvinyl alcohols, also manufactured by Air Products and Chemicals Company.

Thermoplastic polyesters suitable for use in the present invention include DESMOPHEN 2000, and DESMOPHEN 2001KS, both of which are supplied by Bayer, from Pittsburgh, PA. Preferred polyesters include the RD-847A polyester polymer manufactured by Borden Chemicals from Colombo, Ohio and the DYNAKOLL SI 100 polymer manufactured by Eka Chemicals AB, Sweden. Suitable polyamides include VERSAMID products manufactured by General Mills, Inc. Suitable thermoplastic polyurethanes include WITCOBOND ^® W-290H, manufactured by Witco Chemical Corp., Chicago, Illinois, and polyurethane latex RUCOTHANE ^® 2011L, manufactured by Ruco Polymer Corp., of Hicksville, New York.

 The aqueous sizing composition of the present invention may include a mixture of one or more thermosetting polymeric materials with one or more thermoplastic polymeric materials. In one embodiment of the present invention, particularly suitable for printed circuit board laminates, the polymeric materials of the aqueous sizing composition include a blend of RD-847A polyester polymer, PVP K-30 polyvinylpyrrolidone, DESMOPHEN 2000 polyester and VERSAMID polyamide. In an alternative embodiment of the invention suitable for laminates for the manufacture of printed circuit boards, the polymeric materials of the aqueous sizing composition include polyvinylpyrrolidone PVP K-30, optionally together with EPON 826 epoxy.

 Semi-synthetic polymeric materials suitable for use as polymeric film formers include, but are not limited to, cellulosic materials such as hydroxypropyl cellulose, and modified starches such as KOLLOTEX 1250 (low viscosity and low amylose potato starch esterified with ethylene oxide) AVEBE from the Netherlands.

 Natural polymeric materials suitable for use as polymeric film-forming agents include, but are not limited to, starches obtained from potatoes, corn, wheat, waxy maize, sago, rice, sorghum, and mixtures thereof.

 It should be borne in mind that, depending on the nature of starch, starch can perform the functions of both particles 18 and / or film former. More specifically, some starches dissolve completely in a solvent, in particular in water, and act as a film former, while other starches do not completely dissolve, retain a granular structure and act as particles 18. Although starches (both natural and semi-synthetic) can used in accordance with the present invention, the sizing composition of the present invention is preferably substantially free of starchy materials. As used herein, the expression “substantially free of starchy materials” means that the coating composition includes these materials in an amount of less than 20 wt.% Based on the total solids content of the coating composition, preferably less than 5 wt.% And more preferably not contains starchy materials. Primary sizing compositions containing starches that are applied to fiber strands to be included in printed circuit board laminates are generally not compatible with polymers and should be removed before incorporation into the polymer matrix material. As indicated above, the coating compositions of the present invention are preferably compatible with polymers and do not require removal. More preferably, the coating compositions of the present invention are compatible with the matrix materials used for the manufacture of printed circuit boards (described below), and most preferably they are compatible with epoxy resins.

 Polymer film-forming materials may be water soluble, emulsifiable, dispersible and / or curable. As used herein, the term “water soluble” means that polymeric materials are capable of being substantially uniformly mixed and / or molecularly or ionically dispersed in water to form a true solution. See Hawley's publication on page 1075, incorporated herein by reference. The term “emulsifiable” means that the polymeric materials are capable of forming a substantially stable mixture or of being suspended in water in the presence of an emulsifier. See Hawley's publication on page 461, incorporated herein by reference. Non-limiting examples of emulsifiers are provided below. The term "dispersible" means that any of the components of the polymeric materials is capable of being distributed in water in the form of finely divided particles, for example, a material such as latex. See Hawley's publication on page 435, incorporated herein by reference. The uniformity of the dispersion can be enhanced by the addition of wetting, dispersing and emulsifying agents (surfactants), described below. The term “curable” means that polymeric materials and other components of the sizing composition are capable of being converted into a film or crosslinked with each other, which changes the physical properties of the polymeric materials. See Hawley's publication on page 331, incorporated herein by reference.

и моногидроксильный и/или С₂-С₃-циклический остаток 1,2- или 1,3-гликоля, где R¹ представляет собой C₁-С₃-алкил; R² представляет собой Н или С₁-С₄-алкил; R³ и R⁴ независимо выбирают из Н, С₁-С₄-алкила или С₆-С₈-арила; и R⁵ представляет собой С₄-С₇-алкилен. Примеры подходящих компатибилизирующих или функциональных групп включают эпоксильную, глицидоксильную группы, меркаптогруппу, цианогруппу, аллильную, алкильную группы, уретаногрупппу, галогеновую группу, изоцианатогруппу, уреидогруппу, имидазолинильную, винильную группы, акрилатогруппу, метакрилатогруппу, аминогруппу или полиаминогруппу.In addition to, or instead of, the polymeric film-forming materials described above, the coating composition preferably includes one or more glass fiber resins, such as organosilicon resins, transition metal resins, phosphonate resins, aluminum resins, Werner amino resins, and mixtures thereof. These sizing usually perform two functions. Each metal or silicon atom is attached to one or more groups of these resins, which can either react with the surface of the fiber and / or components of the polymer matrix, or combine with them. The term “combine” as used in the present description means that the groups are chemically attracted to the surface of the fiber and / or to the components of the coating composition, but do not bind to them, for example, under the influence of polar forces, wetting forces and solvation forces. In one of the non-limiting embodiments of the invention, each metal or silicon atom has one or more hydrolyzable sizing groups attached to it, which allows the sizing to react with the surface of the glass fibers, as well as one or more of its functional groups, which allows the sizing to react with the components polymer matrix. Examples of hydrolyzable groups include:

and a monohydroxy and / or C ₂ -C ₃ cyclic residue of 1,2- or 1,3-glycol, wherein R ¹ is C ₁ -C ₃ -alkyl; R ² represents H or C ₁ -C ₄ alkyl; R ³ and R ^{4 are} independently selected from H, C ₁ -C ₄ alkyl or C ₆ -C ₈ aryl; and R ⁵ is C ₄ -C ₇ alkylene. Examples of suitable compatibilizing or functional groups include an epoxy, glycidoxyl group, mercapto group, cyano group, allyl group, alkyl group, urethane group, halogen group, isocyanato group, ureido group, imidazolinyl group, vinyl group, acrylate group, methamino group, methacryl group.

 Functional silicone resins are preferred for use in the present invention. Examples of suitable functional silicone resins include gamma-aminopropyltrialkoxysilanes, gamma-isocyanatopropyltriethoxysilanes, vinyltrialkoxysilanes, glycidoxypropyltrialkoxysilanes and ureidopropyltrialkoxysilanes. Preferred functional silicone resins include gamma-glycidoxypropyltrimethoxysilane A-187, gamma-methacryloxy-propyltrimethoxysilane A-174, gamma-aminopropyltriethoxysilane A-1100, aminosilane A-1108 and gamma-ureidopropyltriethoxysilane Inc., from Tarrytown, New York). The organosilicon sizing can be at least partially hydrolyzed with water before applying it to the fibers, preferably in a stoichiometric ratio of about 1: 1, or, if desired, it can be applied in non-hydrolyzed form. The pH of the water can be changed by adding an acid or a base to initiate or accelerate the hydrolysis of the sizing, which is well known to specialists in this field of technology.

 Suitable transition metal based finishes include titanium, zirconium, yttrium and chrome finishes. Suitable titanate and zirconate resins are manufactured by Kenrich Petrochemical Company. Suitable chromium complexes are manufactured by E.I. duPont de Nemours, from Willington, Delaware. Amino-containing resins of the type of Werner resins are complex compounds in which a trivalent atom, such as a chromium atom, is coordinated with an organic acid having a functional amino group. Other metal chelates and coordination type resins known to those skilled in the art can also be used for this invention.

The amount of sizing can be in the range from about 1 to about 30 wt. % based on the total dry weight of the coating composition, preferably from about 1 to about 10 wt.%, and more preferably from about 2 to about 8 wt.%
The coating composition may also include one or more plasticizers or surfactants that impart the same charge to the surface of the fibers, causing the fibers to repel from each other, which reduces friction between the fibers, i.e. These substances act as lubricants. Although not required, it is preferred that the plasticizers are chemically different from other components of the coating composition. Such plasticizers include cationic, nonionic or anionic plasticizers and mixtures thereof, such as amine salts of fatty acids, alkylimidazoline derivatives such as CATION X manufactured by Rhone Poulenc of Princeton, New Jersey, acid solubilized fatty acid amides, fatty acid condensates and polyethyleneimine, and amide substituted polyethylene imines, such as EMERY ^® 6717, a partially amidated polyethyleneimine, manufactured by Henkel Corporation of Kankakee, Illinois. Although the coating composition may include up to about 60 wt.% Plasticizers, it is preferable that the coating composition include less than about 20 wt.% Plasticizers and more preferably less than about 5 wt.% Plasticizers. For more information on plasticizers, see AJ Hall, Textile Finishing, 2 ^nd Ed., 1957, pages 108-115, which is incorporated herein by reference.

 The coating composition may also include one or more lubricants that are chemically different from the polymeric materials and plasticizers described above, and which give the fiber the desired processing characteristics during weaving. Suitable lubricants can be selected from the group consisting of oils, waxes, greases and mixtures thereof. Non-limiting examples of wax materials suitable for use in this invention include water-soluble emulsifiable or dispersible wax materials such as vegetable, animal, mineral, synthetic or petroleum waxes, such as paraffin. Oils suitable for use in the present invention include both natural oils and semi-synthetic and synthetic oils. Typically, the amount of wax or other lubricant may be in the range from 0 to about 80 wt.% Based on the total dry weight of the sizing composition, preferably from about 1 to about 50 wt.%, More preferably from about 20 to about 40 wt.% And most preferably from about 25 to about 35 wt.%.

Preferred lubricants include waxes and
oils having polar characteristics, and more preferably include highly crystalline waxes having polar characteristics and having melting points higher than about 35 ^{° C.} and higher, preferably higher than about 45 ^° C. Such materials are considered to improve the wetting and wetting properties of polar polymers applied on fiber strands coated with sizing compositions containing such polar materials, compared to fiber strands coated with sizing compositions containing skins and oils that do not have polar characteristics. Preferred polar lubricants include esters resulting from the reaction of (1) monocarboxylic acid and (2) monohydric alcohol. Non-limiting examples of such fatty acid esters suitable for use in the present invention include cetyl palmitate, which is preferred (such as KESSCO 653 or STEPANTEX 653 manufactured by Stepan Company of Maywood, New Jersey), cetyl myristate (also manufactured by Stepan Company, called STEPANLUBE 654), cetillaurate, octadecyl laurate, octadecyl myristate, octadecyl palmitate and octadecyl stearate. Other fatty acid ester lubricants suitable for use in the present invention include trimethylolpropanetripelargonate, natural spermaceti and triglyceride oils, such as (but not limited to) soybean oil, linseed oil, epoxidized soybean oil, and epoxidized linseed oil.

Although not preferred, the coating composition may include one or more other lubricants, such as non-polar petroleum paraffins, instead of or in addition to the lubricants described above. Non-limiting non-polar petroleum paraffins include MICHEM ^R LUBE 296 microcrystalline paraffin, POLYMEKON ^® SPP-W microcrystalline paraffin and PETROLITE 75 microcrystalline paraffin manufactured by Michelman Inc., from Cincinnati, Ohio, and Petrolite Corporation, from Tulsa, Tomoma, Toma, Inc. .

 Although not necessary, if desired, the coating composition may also include a polymer-reactive diluent to further improve the lubrication of the coated fiber strands of the present invention and to provide good processability during weaving and knitting by reducing possible fluffing and the amount of broken filaments during such manufacturing operations, and at the same time maintain compatibility with polymers. The term “polymer reactive diluent,” as used herein, means that the diluent includes functional groups capable of chemically reacting with the same polymer with which the coating composition is compatible. The diluent may be any lubricant with one or more functional groups reacting with a polymer system, preferably with functional groups reacting with an epoxy system, and more preferably with functional groups reacting with an FR-4 epoxy system. Non-limiting examples of lubricants include lubricants with amino groups, alcohol groups, anhydride groups, acid groups, and epoxy groups. A non-limiting example of an amino group lubricant is a modified polyethyleneamine, such as EMERY 6717, which is a partially amidated polyethyleneimine manufactured by Henkel Corporation of Kankakee, Illinois. A non-limiting example of an alcohol group lubricant is polyethylene glycol, for example CARBOWAX 300, which is polyethylene glycol manufactured by Union Carbide of Danbury, Connecticut. A non-limiting example of an acid group lubricant are fatty acids, for example, stearic acid and stearic acid salts. Non-limiting examples of epoxy lubricants include epoxidized soybean oil and epoxidized linseed oil, for example FLEXOL LOE, which is epoxidized linseed oil, and FLEXOL EPO, which is epoxidized soybean oil, both manufactured by Union Carbide of Danbury, Connecticut and LE-9300 epoxidized silicone emulsion manufactured by Witco Corporation OSi Specialties, Inc. of Danbury, Connecticut. Although this does not limit the scope of the present invention, the sizing composition may include a polymer-reactive diluent described above in an amount of up to about 15% by weight based on the total dry weight of the sizing composition.

The coating composition may include one or more emulsifiers for emulsifying or dispersing components of the sizing composition, such as particles 18 and / or lubricants. Non-limiting examples of suitable emulsifiers or surfactants include polyoxyalkylene block copolymers (such as the copolymer of polyoxypropylene and polyoxyethylene PLURONIC ^TM F-108 manufactured by BASF Corporation, from Parsippany, New Jersey), ethoxylated alkyl phenols (such as ethoxylated octylphenol ethoxyphenols -630, manufactured by GAF Corporation of Wayne, New Jersey), polyoxyethylene octyl phenyl glycol esters, ethylene oxide derivatives of sorbitol esters (such as TMAZ 81 manufactured by BASF Corpo ration, from Parsippany, New Jersey), polyoxyethylene vegetable oils (such as ALKAMULS EL-719 manufactured by Rhone-Poulenc), ethoxylated alkyl phenols (such as MACOL OP-10, also manufactured by BASF) and nonylphenol surfactants (such like MACOL NP-6, also manufactured by BASF). Typically, the amount of emulsifier may be from about 1 to about 30 wt.% Based on the total amount of solids of the coating composition, preferably from about 1 to about 15 wt.%.

 Crosslinking materials, such as melamine formaldehyde, and plasticizers, such as phthalates, trimethyllates and adipates, can also be included in the coating composition. The amount of crosslinking agent or plasticizer may be from about 1 to about 5 wt.% Based on the total amount of solids of the coating composition.

 Other additives may be included in the coating composition, such as silicones, fungicides, bactericides and antifoam agents, typically in an amount of less than about 5% by weight. Organic and / or inorganic acids or bases may also be included in the coating composition in an amount sufficient to provide a pH of the coating composition of from about 2 to about 10. A non-limiting example of a suitable silicone emulsion is an epoxidized silicone emulsion LE-9300 manufactured by Witco Corporation OSi Specialties, Inc. of Danbury, Connecticut. An example of a suitable bactericide is the Biomet 66 antimicrobial compound manufactured by M&T Chemicals of Rahway, New Jersey. Suitable antifoam agents are SAG materials manufactured by OSi Specialties, Inc. , from Danbury, Connecticut, and MAZU DF-136, manufactured by BASF Company, from Parsippany, New Jersey. If desired, ammonium hydroxide may be added to the coating composition to stabilize the coating. Preferably, water, and more preferably deionized water, is included in the coating composition in an amount sufficient to facilitate uniform application of the composition to the strands. The mass percentage of solids in the coating composition, as a rule, is from about 1 to about 20 wt.%.

 The coating composition is preferably substantially free of glass materials. The expression “substantially free of glass materials”, as used herein, means that the sizing composition comprises less than 20 vol.% Glass matrix materials to produce glass composites, preferably less than about 5 vol.%, And more preferably does not contain glass materials. Examples of such glass matrix materials include black glass ceramic matrix material or aluminosilicate matrix materials well known to those skilled in the art.

In one of the embodiments of the present invention, intended for the manufacture of fabric for multilayer printed circuit boards, the fiberglass strands of the present invention have a primary layer of the dried residue of the aqueous composition for primary sizing, including styrene acrylic polymer synthetic pigments ROPAQUE ^® HP-1055 or ROPAQUE ^® OS-96, polyvinylpyrrolidone PVP K-30, acrylic-functional organosilicon resins A-174 and epoxy-functional organosilicon resins A-187, partially amidated polyethyleneimine EMERY ^® 67 17, cetyl palmitate STEPANTEX 653, ethylene oxide derivatives of sorbitol esters TMAZ 81, ethoxylated alkyl phenol MACOL OP-10 and antifoam MAZU DF-136.

In another preferred embodiment of the present invention for manufacturing a fabric for laminated printed circuit boards, glass fibers of the coated fiber strands of the present invention have applied to them a primary layer of a dried residue of an aqueous composition for the primary dressing consisting of hollow spheres of styrene acrylic copolymer ROPAQUE ^® HL-1055 or ROPAQUE ^® OS-96, PolarTherm ^® 160 boron nitride powder and / or ORPAC BORON NITRIDE RELEASECOAT-CONC boron nitride dispersion, polyvinylpyrrolidone PVP K-30, acrylic-functional organosilicon resins A-174 and epoxy-functional organosilicon resins A-187, partially amidated polyethyleneimine EMERY ^® 6717, cetyl palmitate STEPANTEX 653, ethylene oxide derivatives of sorbitol esters TMAZ 81, ethoxylated alkyl phenol MACOL OR-10 and antifoam MAZU D-136.

 Although not preferred, fiber strands can also be made in accordance with the present invention having the remainder of a coating composition similar to those described above but containing no particles 18. In particular, aqueous polymer compatible sizing compositions can be made in accordance with the present invention, comprising one or more film-forming polymeric materials, such as polyvinylpyrrolidone PVP K-30; one or more organosilicon resins, such as acrylic-functional organosilicon resins A-174 and epoxy-functional organosilicon resins A-187; and at least about 25 wt.% based on the total dry weight of the sizing composition of lubricants having polar characteristics, such as STEPANTEX 653 cetyl palmitate. It will also be understood by those skilled in the art that from fiber strands having a remainder of water compatible with polymers a sizing composition substantially free of particles 18 can be woven into fabric and made into a base for electronic boards and electronic boards (as described below) in accordance with the present invention.

 The coating compositions of the present invention can be obtained using suitable methods, such as conventional mixing, well known to specialists in this field of technology. Preferably, the components described above are diluted with water to have the desired solids content (in wt.%), And mixed. Particles 18 can be pre-mixed with water, emulsified or otherwise added to one or more components of the coating composition, before mixing with the remaining components of the coating.

 The sizing compositions of the present invention can be applied in many ways, for example, by contacting the filaments with a roller or tape applicator, by spraying, or by other methods. The sintered fibers are preferably dried at room temperature or at elevated temperatures. Drying removes excess moisture from the fibers, and if any, cures any curable components of the sizing composition. The temperature and drying time of the glass fibers depends on variables such as the percentage of solids in the sizing composition and the type of glass fiber.

The amount of coating composition present as a dry residue on the strands of fibers, preferably less than about 30 wt.%, More preferably less than about 10 wt.%, Most preferably less than about 5 wt. %, which is measured by determining the loss on ignition (LOI). In one embodiment, the LOI is less than 1 wt.%. The term "loss on ignition", as used here, refers to the percentage (by weight) of the dried coating composition present on the surface of the fiber strand, determined using equation 1:
LOI = 100 • [(W _dry -W _uncoated) W _suxoy]
in which W _dry indicates the weight of the fiber strand plus the remainder of the coating composition after drying in an oven at a temperature of about 104 ^{° C.} for about 60 minutes, and W _{without coating} indicates the weight of an uncoated fiber strand after removing the remainder of the coating composition by heating the fiber strand in an oven at about 621 ^{° C.} for about 20 minutes.

 After applying the primary sizing, the fibers are collected in strands having from 2 to about 15,000 fibers per strand, and preferably from about 100 to about 1,600 fibers per strand.

 The secondary layer of the composition for secondary sizing of the composition or the composition of the secondary coating can be applied to the primary layer in an amount effective to coat or impregnate part of the strands, for example, by dipping the coated strand in a bath containing the secondary coating composition, or by spraying the secondary coating composition onto coating the strand, or by contacting the coated strand with the applicator, as described above. The coated strand can be passed through a press to remove excess coating composition from the strand and / or dried, as described above, for a time sufficient to allow at least partial drying or curing of the secondary coating composition. The method and apparatus for applying the secondary coating composition to the strand is partially determined by the configuration of the strand material. The strand is preferably dried after application of the secondary coating composition in a manner well known to those skilled in the art.

 Suitable secondary coating compositions may include one or more film-forming materials, lubricants, and other additives, such as those described above. The secondary coating is preferably different from the composition for the primary sizing, i.e. it (1) contains at least one component chemically different from the components of this sizing composition; or (2) contains at least one component in an amount different from the amount of the same component in said sizing composition. Non-limiting examples of suitable secondary coating compositions comprising polyurethane are described in US Pat. Nos. 4,762,750 and 4,762,751, which are incorporated herein by reference.

 In FIG. 2, an alternative embodiment of the present invention is shown, fiberglass 212 having a coating of strands 210 of fibers can have a primary layer 214 of the dried residue of the composition for primary sizing, which may include any of the sizing components in the amounts indicated above. Examples of suitable sizing components are presented in Loewenstein, 3d Ed., 1993, pages 237-291 and in US Pat. Nos. 4,390,647 and 4,795,678, which are incorporated herein by reference. The secondary layer 215 of the secondary coating composition is applied to at least a portion of the outer surface, and preferably to the entire outer surface of the primary layer 214. The secondary coating composition includes one or more types of discrete particles 216, such as those described in detail above. The number of particles in the secondary coating composition may be from about 1 to about 99 wt.% Based on the total weight of solids, and preferably from about 20 to about 90 wt.%. The solids content in the aqueous composition of the secondary coating, as a rule, is from about 5 to about 50 wt.%.

 In an alternative embodiment of the invention, the particles of the secondary coating composition include hydrophilic inorganic solid particles that absorb and retain water in the voids of the hydrophilic particles. Hydrophilic inorganic solids can absorb water or swell when they come in contact with water or participate in a chemical reaction with water, forming, for example, a viscous gel-like solution that blocks or inhibits the further flow of water into the voids of a telecommunication cable covered with fiberglass strands used for reinforcement. The word "absorb", as used here, means that water penetrates into the internal structure or into the voids of the hydrophilic material and is essentially retained in them. See the Hawley's Condensed Chemical Dictionary, on page 3, incorporated herein by reference. “Swell” means that the hydrophilic particles increase in size or volume. See Webster's New Collegiate Dictionary, 1977, on page 1178, incorporated herein by reference. Preferably, the hydrophilic particles swell after contact with water at least one and a half times in relation to its original dry weight, and more preferably about 2-6 times compared to the original weight. Non-limiting examples of hydrophilic inorganic particles of swellable solid lubricants include smectites such as vermiculite and montmorillonite, absorbent zeolites, and inorganic absorbent gels. Preferably, these hydrophilic particles are applied in powder form to a sticky sizing or other sticky secondary coating materials. The amount of hydrophilic inorganic particles in this embodiment of the secondary coating composition may be from about 1 to about 99 wt.% Based on the total weight of solids, and preferably from about 20 to about 90 wt.%.

 In an alternative embodiment of the invention shown in FIG. 3, the tertiary layer 320 of the tertiary coating composition can be applied to at least a portion of the surface, and preferably to the entire surface of the secondary layer 315, i.e. such a strand 312 of fibers will have a primary layer of primary sizing 314, a secondary layer 315 of the composition of the secondary coating and the tertiary, outer layer 320 of the tertiary coating. The tertiary coating preferably differs from the composition for primary sizing and from the composition of the secondary coating, i.e., the tertiary coating composition (1) contains at least one component chemically different from the components of the composition for primary sizing and the composition of the secondary coating; or (2) contains at least one component in an amount different from the amount of the same component in the composition for primary sizing or in the composition of the secondary coating.

In this embodiment, the secondary coating composition includes one or more of the polymeric materials described above, such as polyurethane, and the tertiary powder coating composition includes solid particles such as PolarTherm ^® boron nitride particles and hollow particles such as ROPAQUE ^® pigments described above . It is preferred that the powder coating is applied by passing the strands coated with the liquid secondary coating composition through a fluidized bed or spray device so that the powder particles adhere to the sticky secondary coating composition. Alternatively, fabric 810 may be made from strands before applying a tertiary coating layer 812, as shown in FIG. The content of powdery solid particles adhering to the coated strand 310 of fibers may be from about 0.1 to about 30 wt.% Based on the total weight of the dried strand.

 The tertiary powder coating may also include one or more of the polymeric materials described 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 dry powders.

 The strands 10, 210, 310 of coated fibers described above can be used as a continuous strand or further processed into various products, such as chopped strands, twisted yarn, rovings and / or fabrics, such as woven materials, non-woven materials, knitted and woven products (mats). In addition, coated strands of fibers used as warp and weft threads can be untwisted (also called zero torsion) or twisted before weaving, and the fabric can include various combinations of both twisted and non-twisted weft and warp threads.

 Although it was mainly discussed above the application of the coating compositions of the present invention directly to the glass fibers after the fibers are prepared, followed by incorporation of these fibers into the fabric, it will be understood by those skilled in the art that the present invention also includes an embodiment in which the coating composition of the present invention is applied on fabric after its manufacture, using various methods known in the art. Depending on the fabrication technology, the coating composition of the present invention can be applied directly to the glass fibers in the fabric or to another coating already on the glass fibers and / or the fabric. For example, glass fibers can be coated with a conventional starch-oil sizing after the fibers are obtained, and then weaved from them. The fabric is then treated to remove the starchy oil slick before applying the coating composition of the present invention. Such removal of the sizing can be carried out using methods well known to specialists in this field of technology, such as heat treatment or washing the fabric. In this case, the coating composition is applied directly to the surface of the fabric fibers. If at least a portion of the sizing composition originally applied to the glass fibers after their preparation has not been removed, then in this case the coating composition of the present invention is applied to the remaining portion of the sizing composition, and not directly to the surface of the fibers.

 In another embodiment of the invention, the selected components of the coating composition of the present invention can be applied to the glass fibers immediately after their preparation, and the remaining components of the coating composition can be applied to the fabric after its manufacture. Just as described above, some of the selected components or all selected components can be removed from the glass fibers before coating these fibers and fabric with the remaining components. As a result, these other components either directly cover the surface of the fabric fibers, or they cover those selected components that have not been removed from the surface of the fibers.

 Coated strands of 10, 210, 310 fibers and the products obtained from them can be used in a wide variety of applications, but they are preferably used as reinforcing elements 410 for reinforcing the polymer materials of the matrices 412 to obtain a composite 414, such as shown in FIG. 4, which will be described in detail below. Such applications include, but are not limited to, PCB laminates, reinforcing materials for telecommunication cables, and various other composites.

 One of the advantages of the coated strands of the present invention is that they are compatible with typical polymers used as polymer matrix materials used to make the bases for electronic circuit boards and printed circuit boards, and are suitable for weaving on pneumatic looms commonly used for fabrication of reinforced fabrics for such applications. Conventional sizing compositions applied to fibers to be woven on pneumatic looms include components (such as starches and oils) that are generally not compatible with systems of such polymers. It has been found that the technological characteristics associated with weaving are strands of glass fibers coated with the remainder of the primary sizing composition comprising particles 18 of the present invention are approximately the same as those of fiber strands coated with conventional starch / oil based sizing compositions and are compatible with epoxy resins FR-4. Although the authors do not associate this with any particular theory, they hypothesize that particles 18 of the present invention act in the same way as the starch component of conventional starch / oil based sizing compositions during fiber processing and weaving on air tools, providing fiber separation and aerodynamic drag required for weaving operations on pneumatic machines, while at the same time ensuring compatibility with the epoxy system, which is not typical for conventional s starch / oil compositions finishing agents. More specifically, the particles 18 impart to the coating dry powder properties similar to those of dry starch coating lubricants.

 Another advantage of the coated strands of the present invention is that the particles create voids between the strand fibers, which improve the passage of matrix material between them, thereby accelerating and / or making the wetness and permeability of the strand fibers more uniform. It turned out that the number of particles can exceed 20 wt.% Based on the total solids content in the coating composition applied to the fibers, while still retaining their ability to adhere well to the fibers, giving the strands the necessary qualities associated with their ease of use, at least comparable to the qualities of uncoated strands comprising particles.

 In another embodiment of the invention shown in FIG. 5, the strands 510 of coated fibers in accordance with the present invention can be used as warp and / or weft threads 514, 516 in the reinforcement of knitted or woven fabric 512, preferably to produce a laminate for printed circuit boards (shown in Fig. 6-8). Although not required, warp yarns 514 can be twisted before use by any method known to those skilled in the art, for example, using a twisting machine, to give yarns from about 0.5 to 3 turns per inch (about 0.2- 1.2 turns / cm). Reinforced fabric 512 may include from about 5 to about 100 warp threads 514 per centimeter, preferably has from about 6 to about 50 warp threads per centimeter. The structure of the woven material can be a simple plain woven fabric or mesh (as shown in FIG. 5), although any other fabric structures (types of weaving) that are well known to those skilled in the art, such as twill weave or satin weave, can be used.

 A suitable reinforced woven fabric 512 can be obtained using any conventional weaving machines well known to those skilled in the art, such as a shuttle weaving machine, a pneumatic weaving machine or a rapier weaving machine, but it is preferably obtained using a pneumatic weaving machine (described above). Pneumatic looms manufactured by Tsudakoma from Japan are preferred in the form of models 103, 1031, 1033 or ZAX; Sulzer Ruti, models L-5000, L-5100 or L-5200, manufactured by Sulzer Brothers LTD, from Zurich, Switzerland; and Toyoda, model JAT610.

 The fabric of the present invention is preferably made in the form of a structure that is suitable for the laminate used for the base of electronic boards or printed circuit boards, such as described in the publication "Fabrics Around the World", which is a technical bulletin from Clark-Schwebel, Inc. , from Anderson, South Carolina (1995), which is incorporated herein by reference. For example, a non-limiting example of a fabric structure using E225 E-glass fiberglass yarns is structure (type) 2116, in which the fabric has 118 warp and 114 weft 5 cm; warp and weft threads are used 7 22 1 • 0 (Е225 1/0); the fabric has a nominal thickness of about 0.094 mm; and the weight of the fabric (or base weight) is about 103.8 grams per square meter. A non-limiting example of a fabric structure using G75 E-glass fiberglass yarns is structure (type) 7628, in which the fabric has 87 warp yarns and 61 5 cm weft yarns; warp and weft threads are used 9 68 1 • 0 (G75 1/0); the fabric has a nominal thickness of about 0.173 mm; and the weight of the fabric is about 203.4 grams per square meter. A non-limiting example of a fabric structure using D450 E-glass fiberglass yarns is a structure (type) 1080 in which the fabric has 118 warp yarns and 93 weft yarns of 5 cm; warp and weft threads are used 9 11 1 • 0 (D450 1/0); the fabric has a nominal thickness of about 0.053 mm; and the weight of the fabric is about 46.8 grams per square meter. A non-limiting example of a fabric structure using E900 glass fiber D900 yarns is structure (type) 106, in which the fabric has 110 warp and 110 weft 5 cm; warp and weft threads are used 5 5.5 1 • 0 (D900 1/0); the fabric has a nominal thickness of about 0.033 mm; and the weight of the fabric is about 24.4 grams per square meter. Another non-limiting example of a fabric structure using E900 glass fiber D900 yarns is structure (type) 108, in which the fabric has 118 warp yarns and 93 5 cm weft yarns; warp and weft threads are used 5 5.5 1 • 2 (D900 1/2); the fabric has a nominal thickness of about 0.061 mm; and the weight of the fabric is about 47.5 grams per square meter. A non-limiting example of a fabric structure using E225 glass fiber and D450 E-glass filaments is structure (type) 2113, in which the fabric has 118 warp and 110 weft per 5 cm; warp yarns 7 22 • 0 (Е225 1/0) and weft yarns 5 11 1 • 0 (D450 1/0) are used; the fabric has a nominal thickness of about 0.079 mm; and the weight of the fabric is about 78.0 grams per square meter. A non-limiting example of a fabric structure using glass fibers G50 and G75 of E-glass is structure (type) 7535, in which the fabric has 87 warp and 57 weft 5 cm; warp threads 9 68 • 0 (G75 1/0) and weft threads 9 99 1 • 0 (G50 1/0) are used; the fabric has a nominal thickness of about 0.21 mm; and the weight of the fabric is about 232.3 grams per square meter. These and other suitable fabric structures (types) are given in IPC-EG-140 "Specification for Finished Fabric Woven from 'E' Glass for Printed Boards", a publication of The Institute for Interconnecting and Packaging Electronic Circuits, June 1997, which is included in the present description by reference. Although twisted yarns are used in the fabric structures described above, it is understood that these and other fabric structures using zero torsion yarns or rovings, together with or instead of twisted yarns, can be made in accordance with the present invention. It is also understood that some or all warp yarns in a fabric may have fibers coated with a first polymer-compatible sizing composition, and some or all weft yarns in a fabric may have fibers coated with a second polymer-compatible coating that is different from the first composition, i.e. . the second composition (1) contains at least one component chemically different from the components of the first sizing composition; or (2) contains at least one component in an amount different from the amount of the same component contained in the first sizing composition.

 It should be borne in mind that laminates can also be unidirectional laminates in which most fibers, filaments or strands in each layer are oriented in the same direction.

 In FIG. 6 shows that fabric 612 can be used to produce a composite or laminate 614 by coating and / or impregnating it with a polymer film-forming thermoplastic or thermosetting matrix material 616. Composite or laminate 614 is suitable for use as a base for electronic circuit boards. The term "base for electronic circuit boards," as used herein, means a structure that mechanically supports and / or electrically interconnects elements, including, but not limited to, active electronic components, passive electronic components, printed circuit boards, integrated circuits , semiconductor devices and other hardware elements associated with the above elements, including, but not limited to, connectors, sockets, clamps, and heat sinks.

Matrix materials suitable for use in the present invention include thermosetting materials, such as thermosetting polyesters, vinyl polyesters, epoxides (containing at least one epoxy or oxirane group, such as polyglycidyl ethers of polyhydric alcohols or thiols), phenoplasts , aminos, thermosetting polyurethanes, their derivatives and their mixtures. Preferred matrix materials for producing laminates for printed circuit boards are epoxy resins FR-4, polyimides and liquid crystalline polymers, the compositions of which are well known to those skilled in the art. If more detailed information on such compositions is required, see Electronic Materials Handbook ^TM ASM International, 1989, pages 534-537.

 Non-limiting examples of suitable thermostatic matrix materials include polyolefins, polyamides, thermoplastic polyurethanes and thermoplastic polyesters, vinyl polymers and mixtures thereof. Other examples of suitable thermoplastic materials include polyimides, polyethersulfones, polyphenyl sulfones, polyether ketones, polyphenylene oxides, polyphenylene sulfides, polyacetals, polyvinyl chlorides and polycarbonates.

 Other components that can be included in the composite, along with polymer matrix materials and reinforcing materials, include dyes or pigments, lubricants or processing aids, UV stabilizers, antioxidants, and various fillers.

 The fabric 612 can be coated or soaked by immersing the fabric 612 in a bath with a polymer matrix material 616, for example, as described in R. Tummala (Ed.), Microelectronics Packaging Handbook, 1989, pages 895-896, which is included in the present description by reference. In most cases, reinforcing materials in the form of chopped or continuous strands of fibers can be dispersed in the matrix material manually or using any suitable automatic feeding or mixing devices that fairly evenly distribute the reinforcing material throughout the polymer matrix material. For example, the reinforcing material can be dispersed in the polymer matrix material by dry mixing all the components simultaneously or sequentially.

 From the material 616 of the polymer matrix and strands, it is possible to obtain a composite or laminate 614 using various methods, the choice of which depends on factors such as the type of polymer matrix material used. For example, in the case of a thermosetting matrix material, a composite can be obtained by extrusion or injection molding, a method of producing a uniaxially oriented laminate, by winding yarns, laying layers manually, laying layers by spray impregnation, or by sheet forming or volume molding followed by pressing or injection molding. Thermosetting polymer matrix materials can be cured by incorporating crosslinking agents into the matrix material and / or, for example, by heat treatment. Suitable crosslinking agents suitable for crosslinking polymer matrix materials are described above. The temperature and curing time of the thermosetting polymer matrix material depend on factors such as the type of polymer matrix material used, the presence of other additives in the matrix system, the thickness of the composite, etc.

 Regarding thermoplastic matrix materials, suitable methods for producing composites include direct molding or extrusion mixing, followed by injection molding. Methods and devices for producing composites by the above methods are described in publication I. Rubin, Handbook of Plastic Materials and Technology, 1990, pages 955-1062, 1179-1215 and 1225-1271, which is incorporated herein by reference.

 In the specific embodiment of FIG. 7, the composite or laminate 710 includes a fabric 712 impregnated with a compatible matrix material 714. Then, the impregnated fabric can be squeezed out by passing between the metering rollers so that a measured amount of matrix material remains on it, and then dried to obtain a base for electronic circuit boards in the form of a semi-cured substrate or prepreg (prefabricated laminate). The conductive layer 720 can be positioned along part of the side of the prepreg 722, as described below in the present description, after which the prepreg is cured, having received the basis for electronic boards 718 with an electrically conductive layer. In another embodiment of the present invention, and most typically in the field of electronic circuit boards, two or more prepregs are combined with one or more conductive layers, laminated together and cured by a method well known to those skilled in the art, resulting in a multilayer base for electronic circuit boards. As an example, but not limited to the following, stacked prepregs can be laminated by pressing a stack of prepregs, for example, between polished steel plates, at elevated temperatures and elevated pressures, for a predetermined amount of time to cure the polymer matrix and obtain a laminate of the desired thickness . A portion of one or more prepregs may be provided with an electrically conductive layer, either before or after lamination and curing, so that the resulting base for electronic circuit boards is a laminate having at least one electrically conductive layer along a portion of the exposed surface (hereinafter referred to as “foil laminate” ").

 Then, circuits can be made from the electrical conductive layer (s) of the single-layer or multi-layer base for electronic circuit boards using methods well known to those skilled in the art, followed by the preparation of the bases for a printed circuit board or printed circuit (hereinafter referred to as "electronic boards") . If desired, holes can be made in the bases for the electronic boards (also called "through holes") to provide electrical connections between the circuits and / or components on opposite sides of the base for the electronic boards, by any convenient method known in the art, including but not limited to, mechanical drilling and laser drilling. More specifically, after making the holes, a layer of electrically conductive material is applied to the walls of these holes, or the hole is filled with electrically conductive material to provide the necessary electrical connection and / or heat transfer.

The electrical conductive layer 720 can be obtained by any method well known to specialists in this field of technology. By way of example, but not limiting the scope of the present invention, the electrical conductive layer can be obtained by laminating a thin sheet of metal or metal foil on at least a portion of the side of the semi-cured or cured prepreg or laminate. Alternatively, a conductive layer can be obtained by applying a layer of metallic material to at least a portion
sides of a semi-cured or cured prepreg or laminate using well-known methods, including, but not limited to, electroplating, chemical reduction coating or spraying. Metallic materials suitable for use as an electrically conductive layer include, but are not limited to, copper (which is preferred), silver, aluminum, gold, tin, tin and lead alloys, palladium, and combinations thereof.

 In another embodiment of the present invention, the base for electronic circuit boards can be made in the form of a multilayer electronic circuit board constructed by co-laminating one or more electronic circuit boards (described above) and one or more foil laminates (described above) and / or one or more prepregs (described above). Optionally, additional electrically conductive layers can be included in the base for electronic boards, for example, along a portion of the open side of a multilayer electronic board. In addition, if necessary, additional circuits can be formed from the electrically conductive layers, as described above. It should be borne in mind that, depending on the relative arrangement of the layers of the multilayer electronic circuit board, the circuit board can have both internal and external circuits. Additional holes are drilled, as described above, partially through the board or completely through the board to provide an electrical connection between the layers at selected locations. It should be borne in mind that the resulting structure may have several holes passing through the entire structure, several holes passing partially through the structure, and several holes that are completely inside the structure.

The present invention also relates to the manufacture of multilayer materials and electronic circuit boards, which include at least one composite layer made in accordance with the methods described here, and at least one composite layer made by a method different from the method for manufacturing a composite described in this application, for example using conventional glass fiber composites technology. More specifically, as is well known to those skilled in the art, traditionally, yarns in continuous fiberglass strands used for weaving are treated with a starch-oil dressing, including partially or fully dextrinized starch or amylose, hydrogenated vegetable oil, cationic wetting agent, emulsifier and water, including, but not limited to, the components listed in Loewenstein, 3d Ed., 1993, pages 237-244, incorporated herein by reference. The warp threads are obtained from these strands, and then, before weaving, they are treated with a solution to protect the strands from abrasion during weaving, for example, with a solution of polyvinyl alcohol, as described in US Pat. No. 4,530,876, column 3, line 67, column 4 line 11, which is incorporated herein by reference. This operation is commonly referred to as "hatching." Polyvinyl alcohol, like starch oil, is generally not compatible with the polymer matrix material used by composite manufacturers, and the fabric must be cleaned to remove substantially all organic material from the surface of the glass fibers before impregnating the woven material. This can be done using various methods, for example, by washing the fabric or, more commonly, by heat treating the fabric in a manner well known to those skilled in the art. As a result of cleaning operations, there is no necessary pairing between the polymer matrix material used to impregnate the fabric and the cleaned surface of the glass fibers, therefore, a sizing composition must be applied to the surface of the glass fibers. This operation is sometimes referred to as finishing in the art. The most commonly used finishes in finishing operations are silanes, including but not limited to those listed in the publication of E. R. Plueddemann, Silane Coupling Agents, 1982, pages 146-147, which is incorporated herein by reference. See also Loewenstein, 3d Ed. , 1993, pages 249-256. After silane treatment, the fabric is impregnated with a compatible polymer matrix material, squeezed between the metering rollers and dried to obtain the semi-cured prepreg described above. It should be borne in mind that, depending on the type of sizing composition, cleaning operations and / or the matrix material used in the composite, the hatching and / or finishing stages can be excluded. One or more prepregs, including fiberglass composites made by conventional technology, can then be combined with one or more prepregs made in accordance with the present invention, resulting in the above-described basis for electronic boards, and in particular, a multilayer material or electronic board. For more information on electronic circuit board manufacturing, see ^TM Electronic Materials Handbook, ASM International, 1989, pages 113-115, R. Tummala (Ed.), Microelectronics Packaging Handbook, 1989, pages 858-861 and 895 -909, MW Jawitz, Printed Circuit Board Handbook, 1997, pages 9.1-9.42, and C.F. Coombs, Jr. (Ed.), Printed Circuits Handbook, 3d Ed., 1988, pages 6.1-6.7, which are incorporated herein by reference.

 The composites and laminates used to make the bases for the electronic boards of the present invention can also be used to obtain structural modules used in the electronics industry, and more specifically, structural modules of the first, second and / or third levels, such as described in the publication R. Tummala , pages 25-43, incorporated herein by reference. In addition, the present invention can also be applied to structural modules of other levels.

 The present invention also includes a method of reinforcing a polymer matrix material to produce a composite. The method includes: (1) applying to the reinforcing material from fiberglass strands the above composition for primary dressing, secondary coating composition or tertiary coating, including particles, providing voids between adjacent fiberglass strands, (2) drying the coating to obtain a substantially uniform coating on the reinforcing material; (3) combining a reinforcing material with a polymer matrix material; and (4) at least partially curing the polymer matrix material, to obtain a reinforced polymer composite by the method described in detail above. Although this does not limit the scope of the present invention, the reinforcing material can be combined with the polymer matrix material, for example, by dispersing it in the matrix material.

 The present invention also includes a method of inhibiting adhesion between adjacent glass fibers of a glass fiber strand, comprising the steps of: (1) applying to the glass fiber strand the above composition for a primary sizing, a secondary coating composition or a tertiary coating comprising particles to create voids between adjacent glass fiber strands; (2) drying the coating to obtain a substantially uniform coating on the glass fibers of the glass fiber strand, whereby adhesion between adjacent glass fibers of the strand is inhibited.

 The present invention is further illustrated by the following specific examples, not limiting the scope of the present invention.

Example 1
The components in the amounts shown in table 1 were mixed to obtain aqueous compositions for the primary sizing of A, B and C in accordance with the present invention. Each of the aqueous compositions for primary sizing was prepared as described above. Less than 1 wt.% Acetic acid, based on the total weight, was included in each composition. Each of the aqueous sizing compositions of Table 1 was applied to the fibers forming the glass fiber strands of G-75 from E-glass.

 Each coated fiberglass strand was dried, twisted into strands and wound on bobbins in the same way using conventional twisting equipment. The threads coated with sizing compositions showed minimal shedding of the sizing during torsion.

The yarns coated with each of the sizing compositions (A, B and C) were used as weft yarns in the manufacture of style 7628 fabric using a Sulzer Ruti model 5200 pneumatic weaving machine. G-75 twisted fiberglass strands made of E-glass were used as warp yarns coated with another polymer-compatible sizing composition ^{41 41} (As the warp yarns, fiberglass yarn manufactured by PPG Industries, Inc. under the name G-75 fiberglass yarn coated with size 1383 of PPG Industries, Inc. was used). The fabrics were then pre-impregnated with an FR-4 epoxy resin having a glass transition temperature of about 140 ^{° C.} (called resin 4000-2, manufactured by Neico International Corporation, from Anaheim, CA). Sizing compositions were not removed from the tissues before pre-impregnation. Laminates were obtained by laying 8 layers of pre-impregnated material between two layers containing 1 ounce of copper (1 ounce = 29.6 cm ³ ), and laminating them together at a temperature of about 179 ^o C, a pressure of about 2.1 MPa, for about 150 minutes (total cycle time). The thickness of the laminates without copper ranged from about 0.11 to about 0.13 cm

The resulting laminates (indicated by the letters A, B and C, in accordance with the strands of the fibers from which they were made) were tested as described below in table 2. During testing, laminate B was tested at the same time as the laminate made from fiberglass yarns coated with a sizing composition of sample A (hereinafter referred to as the laminate of sample A1). Some time later, laminate C was tested at the same time as the second laminate made of fiberglass yarn coated with a sizing composition of sample C (hereinafter referred to as the laminate of sample A2)
The soldering test was carried out afloat as follows: a piece of 10.6 cm by 10.6 cm copper foil laminate floated on the surface of a eutectic bath with lead-tin solder at a temperature of about 288 ^° C until bubbles or delamination began . We recorded the time (in seconds) elapsed before the appearance of the first bubble or before the start of separation.

An immersion soldering test was carried out as follows: the laminate sample was cut, copper was removed from the sample by etching, the sharp edges of the sample were smoothed out by grinding, and the sample was placed in an autoclave with a temperature of about 121 ^° C and a pressure of about 0.1 MPa for about 60 minutes. After this time, the sample was removed from the autoclave, slightly dried, immersed in a eutectic bath with lead-tin solder at a temperature of about 288 ^o C and kept until the appearance of bubbles or separation. We recorded the time (in seconds) elapsed before the appearance of the first bubble or before the start of separation.

 The bending strength test was carried out in accordance with the specified IPC standard.

 Laminates A, B and C made using strands of fibers coated with sizing compositions A, B and C, respectively, had properties (shown in Table 2) that were acceptable for use as a basis for the manufacture of printed circuit boards.

Example 2
The components in the quantities shown in table 3 were mixed to obtain aqueous sizing compositions of samples D, E and F in accordance with the present invention. Less than 0.5 wt.% Acetic acid, based on the total weight, was included in each composition.

 Each of the aqueous sizing compositions of Table 3 was used to coat the glass fibers forming the G-75 glass fiber strands from E-glass. Each coated fiberglass strand was dried, twisted into a thread and wound on a bobbin in the same way using conventional twisting equipment.

The yarn of sample D was evaluated by comparing the yarn coated with this sample and the yarn coated with a sizing composition similar to Sample D, but without epoxidized linseed oil (hereinafter referred to as "comparative example 1"). This comparison included a visual inspection of the appearance of 7628-style fabric woven on a pneumatic loom. In the manufacture of this fabric, we used sample D for weft yarn, and G-75 twisted yarn made of fiberglass E-glass strands with fibers coated with another polymer compatible sizing composition ^{57 57} (glass fiber yarn was used as the warp yarn). manufactured by PPG Industries, Inc., under the name G-75 fiberglass yarn, coated with size 1383 of PPG Industries, Inc.). It was found that a fabric woven from a thread coated with a sample D showed less fluffing on the fabric, as well as less fluff collected at the points of contact with the machine, especially at the yarn stacker, compared to a fabric woven from a thread coated with a comparative sample 1 Fabrics were not made of threads, including fibers coated with samples E and F, due to the large amount of fluff collected on the machine at the beginning of weaving. The authors believe that this was the result of the LOI being lower than that required to prevent excessive fluffing. The present invention assumes that the above sizing compositions require a LOI of at least 0.40 to reduce fluff formation during weaving.

Example 3
Samples A, B, and C and Comparative Sample 2 ^{58 58} (The yarn was a fiberglass yarn manufactured by PPG Industries, Inc. under the name G-75 fiberglass yarn coated with a 695 starch-oil sizing from PPG Industries, Inc.) ( a thread coated with a starch-oil sizing) was evaluated for some physical properties, such as loss on ignition (LOI), suitability for a pneumatic loom (aerodynamic resistance) and friction force. The results are shown in table 4.

 Loss on ignition (wt.% Solids of the sizing composition, divided by the total weight of glass and dried sizing composition) for each sample are presented in table 4.

 Each thread was evaluated for aerodynamic drag, or tensile force, by supplying the thread at a controlled speed of 274 meters per minute, through a tension measuring device with a control line, with which the threads were applied with a tensile force, and also with a Ruti air nozzle with a diameter of 2 mm, at an air pressure of 138 kPa.

 The test samples and the sample of comparative example 2 were also evaluated for friction force, by applying a friction force of about 20 grams to the sample of each thread, while pulling the threads at a speed of 274 meters per minute through a pair of conventional devices for measuring friction, with a stationary mounted between them a chrome stand with a diameter of about 5 cm, designed to move the thread about 5 cm away from the straight path between the two friction measuring devices. The difference in friction force (in grams) is presented in Table 4 below. The friction force test is intended to simulate the friction forces that the thread undergoes during weaving operations.

 During the test, samples B and 2 were tested at the same time as the first part of the fiberglass strands coated with the sizing composition of sample A (hereinafter referred to as sample A3), and sample C was tested at the same time as the second part strands of glass fiber strands coated with a sizing composition of sample A (hereinafter referred to as sample A4). Samples A3, A4 and B contained about 2.8 wt.% Solids. Sample C contained about 3.1 wt.% Solids. Comparative sample 2 contained about 5.9 wt.% Solids.

 From table 4 it can be seen that the sizes of samples A, B and C have an aerodynamic drag comparable with that of comparative sample 2 (which is a starch-oil sizing). In addition, the lower friction force of samples A, B, and C indicates that such yarns are easier to remove from the weaving machine drive during weaving, compared to comparative example 1.

Example 4
The yarns of samples A, B and C and comparative example 2 were evaluated for aerodynamic drag, in the same way as in the above example 3, except that the aerodynamic drag values were determined for the sample wound on a bobbin at the pressure values shown in table 5. Each the thread was also evaluated for the average number of breaks per 1200 meters of thread at a speed of movement of the thread of 200 meters per minute, using a Shirley thread break detector model 84 041L manufactured by SDL International Inc. from England (shown in table 5 as test 1). The values of the number of breaks in the thread are given for pieces of thread taken from a full bobbin, from the same bobbin with which 227 grams of thread are unwound and from the same bobbin with which 4540 grams of thread are unwound. Then, each thread was evaluated for the number of breaks with increased friction and increased abrasion (shown in table 5 as test 2). In Test 2, a sample of yarn was unwound from a spool at a speed of 200 meters per minute, serpentine passed through a series of 8 ceramic pins on a tension uniformity control device (sometimes also called a comb thread tensioner) and passed through a Shirley thread break detector (described above) to determine number of torn threads. The distances between the pins on the thread tensioner varied, gaining different settings to create different levels of thread tension. The UTC-2003 model tensioner manufactured by Steel Heddle Co. was used in this particular test. from south carolina. The rate of breakage of the threads was expressed as the number of breaks per meter of thread.

 The results of these tests for samples A, B and C and comparative sample 2 are presented in the following table 5. In the same way as described above in example 3, samples B and 2 were tested at the same time as the first part of the fiberglass strands coated with the sizing composition of sample A (hereinafter referred to as sample A5), and some time later, sample C was tested at the same time as the second part of the fiberglass strands coated with the sizing composition of sample A (hereinafter referred to as sample A6).

 As can be seen from table 5, samples A, B and C have aerodynamic drag comparable to that of comparative sample 2 (starch-oil sizing).

 From the preceding description, it can be seen that the present invention provides glass fiber strands having an abrasion resistant coating giving good thermal stability, low corrosion and low reactivity in the presence of high humidity, reactive acids and alkalis, as well as compatibility with various polymer matrix materials. These strands can be twisted or chopped, made into rovings, chopped mat or continuous thread mat, or woven or knitted from them for use in a variety of applications, such as reinforcing elements for composites, such as composites for printed circuit boards.

 Those skilled in the art will appreciate that changes can be made to the above-described embodiments of the invention that will not go beyond the scope of the idea of this invention. Therefore, it is understood that the invention is not limited to the specific embodiments described herein, but encompasses modifications that do not go beyond the essence and scope of the present invention, which are defined by the appended claims.

Claims (59)

 1. A strand of coated fibers comprising at least one fiber having a dried layer layer of a polymer-compatible coating composition on at least a portion of at least one fiber, the polymer-compatible coating composition comprising: (a) a plurality of discrete, stable sizes particles obtained from materials selected from the group consisting of organic materials, polymeric materials, composite materials and mixtures thereof, creating voids between at least one fiber and at least it least one adjacent fiber, the particles have an average size of from about 0.1 to about 5 microns; (b) at least one lubricant; (c) at least one polymeric film-forming material; (d) at least one sizing.  2. The strand of fibers according to claim 1, in which at least one fiber is an inorganic fiber obtained from a glass material selected from the group consisting of E-glass, D-glass, S-glass, Q-glass, derivatives of E glass and their combinations.  3. The strand of fibers according to claim 1, wherein the polymer-compatible coating composition is a polymer-compatible primary sizing composition compatible with an epoxy resin.  4. The strand of fibers according to claim 1, in which the particles have a Mos hardness value that is less than this value for at least one fiber.  5. The strand of fibers according to claim 4, in which the particles have a Mos value of less than about 6.  6. The strand of fibers according to claim 1, wherein the polymer-compatible coating composition is a secondary coating composition.  7. The strand of fibers according to claim 1, in which the particles have an average size of from about 0.5 to about 2 microns.  8. The strand of fibers according to claim 1, in which the particles comprise from about 20 to about 60 wt. % of the polymer composition of the coating composition, calculated on the total weight of solids.  9. The strand of fibers according to claim 8, in which the particles comprise from about 35 to about 55 wt. % of the polymer composition of the coating composition, calculated on the total weight of solids.  10. The strand of fibers according to claim 1, in which at least one particle is a hollow particle.  11. The strand of fibers according to claim 10, in which the hollow particle is obtained from a copolymer of styrene and acrylic.  12. The strand of fibers according to claim 1, in which at least one particle comprises a polymeric material selected from the group consisting of inorganic polymeric materials, synthetic organic polymeric materials, semi-synthetic organic polymeric materials and natural organic polymeric materials.  13. The strand of fibers according to claim 12, in which at least one particle includes an organic polymeric material selected from the group consisting of thermosetting polymeric materials and thermoplastic polymeric materials.  14. The strand of fibers according to claim 13, wherein the at least one particle comprises a thermoplastic polymer material selected from the group consisting of acrylic polymers, vinyl polymers, thermoplastic polyesters, polyolefins, polyamides, thermoplastic polyurethanes and mixtures thereof.  15. The strand of fibers according to claim 14, in which at least one particle is obtained from an acrylic copolymer, which is a copolymer of styrene and acrylic.  16. The strand of fibers according to claim 13, wherein the at least one particle comprises a thermosetting polymer material selected from the group consisting of thermosetting polyesters, vinyl esters, epoxy materials, phenoplasts, aminos, thermosetting polyurethanes, and mixtures thereof.  17. The strand of fibers according to claim 1, in which the lubricant is selected from the group consisting of oils, waxes, greases and mixtures thereof.  18. The strand of fibers according to claim 17, wherein the lubricant is selected from the group consisting of natural waxes, synthetic waxes, and semi-synthetic waxes.  19. The strand of fibers according to claim 18, wherein the wax is a synthetic wax selected from the group consisting of cetyl palmitate, cetyl laurate, octadecyl laurate, octadecyl myristate, octadecyl palmitate, octadecyl stearate and paraffin.  20. The strand of fibers according to claim 1, in which the lubricant is from about 20 to about 40 wt. % of the polymer-compatible coating composition, based on the total dry matter mass.  21. The strand of fibers according to claim 1, wherein the polymer-compatible coating composition is substantially free of starchy materials.  22. The strand of fibers according to claim 1, in which the particles are the first particles, and a polymer-compatible coating composition also includes many additional discrete, stable particle sizes different from the first particles.  23. The strand of fibers according to claim 22, in which many additional particles are obtained from an inorganic material selected from the group consisting of metals, graphite, oxides, carbides, nitrides, borides, sulfides, silicates and carbonates.  24. The strand of fibers according to claim 22, in which many additional particles are obtained from an inorganic solid lubricant selected from the group consisting of boron nitride, graphite and metal dichalcogenides.  25. The strand of fibers according to claim 1, in which the polymer film-forming material includes a material selected from the group consisting of thermosetting polymeric materials, thermoplastic polymeric materials, natural polymeric materials and mixtures thereof.  26. The strand of fibers according to claim 25, in which the polymer film-forming material includes a thermoplastic polymer material selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polyacrylic acid, as well as their copolymers and mixtures thereof.  27. The strand of fibers according to claim 25, in which the polymer film-forming material is a thermosetting polymer material, which is selected from the group consisting of epoxy materials, polyesters, polyurethanes and polyacrylates.  28. A strand of fibers according to claim 25, in which the polymer film-forming material comprises from about 5 to about 30 wt. % polymer-compatible coating composition, calculated on the total weight of solids.  29. A strand of fibers according to claim 1, in which the particles are non-wax particles.  30. A strand of fibers according to claim 1, which is a twisted strand of fibers.  31. A strand of fibers according to claim 1, which is an untwisted strand of fibers.  32. A strand of fibers according to claim 1, in which at least one fiber is a glass fiber made using the method of forming fibers directly from molten glass.  33. A strand of fibers according to claim 1, in which at least one fiber is a glass fiber made using the method of forming fibers from molten glass balls.  34. The strand of fibers according to claim 1, wherein the polymer-compatible coating composition also includes a polymer-reactive diluent.  35. A strand of fibers according to claim 34, wherein the polymer-reactive diluent is a lubricant comprising one or more functional groups capable of reacting with an epoxy system and selected from the group consisting of amine groups, alcohol groups, anhydride groups, acid groups and epoxy groups.  36. A fabric comprising at least one strand of fibers according to claim 1.  37. A fabric comprising at least one strand of fibers according to claim 15.  38. A fabric comprising at least one strand of fibers according to claim 24.  39. A fabric comprising at least one strand of fibers according to claim 26.  40. A strand of fibers according to claim 1, which includes at least one glass fiber having a dried residue of an aqueous polymer-compatible coating composition on at least a portion of the surface of at least one fiber, wherein the aqueous polymer-compatible coating composition includes: (a) many discrete polymeric organic particles, providing voids between at least one glass fiber and at least one adjacent glass fiber, the particles having an average size of up to about 5 microns; (b) a lubricant selected from the group consisting of oils, waxes, greases and mixtures thereof; (c) a polymeric film-forming material selected from the group consisting of thermosetting polymeric materials, thermoplastic polymeric materials, natural polymeric materials and mixtures thereof, and (d) sizing.  41. The strand of fibers according to claim 40, wherein the plurality of particles are a plurality of hollow particles, including a material selected from the group consisting of inorganic materials, organic materials, polymeric materials, composite materials and mixtures thereof.  42. A strand of fibers according to claim 41, in which at least one of the many hollow particles is obtained from polymeric materials, which are a copolymer of styrene and acrylic.  43. The strand of fibers according to claim 42, in which the particles are first particles, and the coating composition also includes many additional particles, including an inorganic lubricant selected from the group consisting of boron nitride, graphite and metal dichalcogenides.  44. A fabric comprising at least one strand of fibers according to claim 40.  45. A strand of fibers according to claim 1, which includes at least one glass fiber having a dried residue of an aqueous polymer-compatible coating composition on at least a portion of the surface of at least one fiber, wherein the aqueous polymer-compatible coating composition includes: (a) a plurality of particles, including: (i) at least one particle obtained from an acrylic copolymer, which is a copolymer of styrene and acrylic; and (ii) at least one particle obtained from an inorganic solid lubricant selected from the group consisting of boron nitride, graphite and metal dichalcogenides, the particles having an average size of up to about 5 microns and are from about 35 to about 55 wt. % of a coating composition compatible with polymers, based on the total weight of solids; (b) a lubricant selected from the group consisting of cetyl palmitate, cetyl laurate, octadecyl laurate, octadecyl myristate, octadecyl palmitate, octadecyl stearate and paraffin, the lubricant being from about 20 to about 40 wt. % of a coating composition compatible with polymers, based on the total weight of solids; (c) a thermoplastic polymer film-forming material selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polyacrylic acid and their copolymers and mixtures, wherein the thermoplastic polymer film-forming material is from about 5 to about 30 wt. % of a coating composition compatible with polymers, based on the total weight of solids; and (d) sizing.  46. A fabric comprising at least one strand of fibers according to claim 45.  47. A fabric comprising a plurality of strands of fibers comprising at least one fiber, wherein at least a portion of the fabric is a residue of a polymer-compatible coating composition comprising: (a) a plurality of discrete, stable particle sizes obtained from materials selected from the group consisting of organic materials, polymeric materials, composite materials and mixtures thereof, providing voids between at least one fiber and at least one adjacent fiber, the particles having an average size of from about 0.1 to about 5 microns; (b) at least one lubricant; (c) at least one polymeric film-forming material; and (d) at least one sizing.  48. The fabric of claim 47, wherein at least a portion of the fabric includes a twisted strand of fiberglass.  49. The fabric of claim 47, wherein at least a portion of the fabric includes an untwisted strand of fiberglass.  50. The fabric of claim 47, wherein the at least one fiber is glass fiber made using a method of spinning fibers directly from molten glass.  51. The fabric of claim 47, wherein the at least one fiber is glass fiber made using a method of forming fibers from molten glass beads.  52. The fabric of claim 47, which is a nonwoven fabric.  53. The fabric of claim 47, which is a woven fabric.  54. The fabric of claim 47, which is a fabric woven on a pneumatic weaving machine.  55. The fabric of claim 54, wherein the at least one fiber is glass fiber made by a method of spinning fibers directly from molten glass and at least a portion of the fabric comprises a twisted strand of glass fibers.  56. The fabric of claim 53, which is woven on a rapier loom.  57. The fabric of claim 56, wherein the at least one fiber is glass fiber made by a method of forming fibers directly from molten glass and at least a portion of the fabric includes a twisted strand of glass fibers.  58. The fabric of Claim 56, wherein the at least one fiber is glass fiber made using a method for forming fibers from molten glass beads and at least a portion of the fabric includes an untwisted strand of glass fibers.  59. The fabric of claim 47, which is selected from the group consisting of woven fabrics, non-woven fabrics, and knitted fabrics. Priority on points:
10/13/1998 - according to paragraphs 1 -6, 8-10, 12-14, 16-18, 20, 22, 24, 25, 27, 28, 30, 31, 36, 38, 40, 41, 43, 44, 47-49, 52- 54, 56 and 59;
05/07/1999 - on pp. 7, 11, 15, 19, 21, 23, 26, 29, 37, 39, 42, 45, and 46;
07/07/1999 - on pp. 32-35, 50, 51, 55, 57 and 58.

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