RU2222123C2 - Fiberglass reinforced laminates (laminated materials), electronic wiring boards, and part assembly processes - Google Patents

Abstract

FIELD: electrical engineering; reinforced laminates for printed- circuit boards. SUBSTANCE: laminate incorporates reinforced fabric of threads including E glass fibers coated with material compatible with polymeric matrix material. Calcination loss for threads amounts to 0.01 - 0.6 mass percent and tractive force in transport under impact of air jet is about 100 000 effective gf per 1 g of yarn mass, amount of loss being evaluated by means of needle air-jet nozzle assembly with internal air-jet chamber, 2 mm in diameter, and nozzle outlet pipe, 20 cm in length, at yarn feed speed of 274 m per minute and air pressure of 310 kPa. Bending strength of such laminate in filling direction is 3•10⁷ kg/sq. m. Thread coating may include polyester and polymer chosen from polymers of vinyl pyrrolidone, vinyl alcohol, starches, and mixtures thereof. Coefficient of thermal expansion of laminate in direction of z axis is below 4.5% at 288 C. EFFECT: enhanced strength characteristics of laminates. 58 cl, 7 dwg, 14 tbl

Description

Technical field
The invention relates mainly to reinforced laminates for electronic circuit boards and, more particularly, to laminates containing fiberglass woven products having a coating that is compatible with laminate matrix resins and facilitates weaving using modern pneumatic shuttleless looms.

State of the art
Electronic circuit boards are usually formed from laminated layers of material consisting of reinforced fibers, such as fiberglass, which ensures dimensional stability of the board to maintain the health of the electronic circuits mounted on it. The curvature or skew of the board due to the difference in the rates of thermal expansion of the board components caused by temperature gradients during manufacturing and use can adversely affect the adhesion of the circuits on the board, and therefore their reliability and characteristics.

 The degree of surface roughness of the laminate can also affect the adhesion of electronic circuits on the board. Defects in the reinforcement of interwoven fabric, such as broken fibers or dust, can adversely affect the degree of roughness and prevent adhesion between the electronic circuit and the laminate. In pneumatic shuttleless looms, dust is generated when fiberglass yarns are separated in bundles, when a reed is exposed to the warp, or when weft is blown with a stream of air at high speed. With increasing speed in modern pneumatic shuttleless looms, the integrity of the strands and the tensile strength of the fiber provided by the coating of the strands are becoming increasingly important.

Fiberglass coating also affects board quality. Starch, which is a component of many glass fiber sizing compositions used in weaving operations, can adversely affect the adhesion between glass fiber and the laminate matrix material, i.e. starch is usually not compatible with the resin material of the laminate matrix. In order to eliminate the incompatibility between fiberglass and matrix materials, usually prior to lamination, the coating or sizing composition is removed from the woven fabric by thermal decomposition of the sizing components (heat treatment or de-oiling) or by washing with water. The traditional method of thermal cleaning involves heating the fabric at 380 ^{° C.} for 60-80 hours. Then, the cleaned fabric is again coated with a silane coupling agent (binder) to improve adhesion between fiberglass and matrix resin.

 The strength of the fiberglass, and more specifically the laminate's flexural strength, can be greatly reduced as a result of these thermal processes of removing the coating from the fibers. Heat treatment of high silica fiberglass, such as D-glass, S-glass and Q-glass, is particularly undesirable due to loss of strength and discoloration.

 Many coating fiberglass coating compositions are known in the art that require heat or water treatment before being used as reinforcement in a composite or laminate. Japanese Patent Application No. 9-208268 describes a fabric for which yarn is made of fiberglass coated immediately after winding with starch or synthetic resin and 0.001-20.0% by weight of inorganic solid particles such as colloidal silicon dioxide, calcium carbonate, kaolin and talc. Before the formation of the laminate, degreasing is required under the influence of heat or water.

 US Pat. No. 5,286,562 discloses textile yarns for screens that are produced on pneumatic shuttleless looms that have at least 45% by weight of a coating of paraffin, lubricants, polyvinylpyrrolidone and organosilicon coupling agents. US Pat. No. 5,038,555 describes twisted fiberglass bundles for producing screens that are coated with an aqueous chemical treatment composition that contains an epoxy film former, an emulsifier, a lubricant, an organometallic combining agent, polyvinylpyrrolidone, polyethylene and water.

 To eliminate the thermal cleaning operations of fiberglass fabric, Japanese Patent Application No. 9-208268 describes a primary sizing agent for fiberglass containing a water-soluble epoxy resin and having a pH of 5.5 to 7.5, which facilitates removal of the sizing by water. Similarly, US Pat. No. 5,236,777 discloses methods for producing fiberglass for resin reinforcement by coating the glass yarn with primary sizing containing at least one water-soluble film-forming agent selected from the group consisting of an amine-modified epoxy resin, ethylene oxide and bisphenol A epoxy resin with the addition of ethylene oxide, a silane coupling agent and a lubricant; washing the yarn with water to reduce the amount of primary sizing to less than 0.25 wt.% calcination loss (LOI) and treatment with a secondary sizing agent. Japanese Patent Application No. 9-268034 describes twisting binders for fiberglass yarn that include a water-soluble urethane compound and / or a water-soluble epoxy product modified by the addition reaction with a polyhydric alcohol.

 US Pat. No. 4,933,381 discloses a resin compatible glass fiber sizing composition comprising an epoxy film former, a nonionic lubricant, a cationic lubricant, a silane coupling agent, and an acid such as acetic or citric.

 Japanese Patent Application No. 8-325950 describes a fiberglass sizing agent comprising, as essential components, polyvinylpyrrolidone, a water-soluble product of the amine addition to an epoxy resin and a silane coupling agent that does not need to be removed by heat treatment from the resulting glass fabric.

 Japanese Patent Application No. 7-102483 describes a secondary sizing agent for a fiberglass backing, from which fiberglass is woven, which does not require thermal oil removal. This base sizing agent mainly consists of polyvinylpyrrolidone and contains an additive such as high molecular weight polyethylene oxide. As a binder component, a water-soluble epoxy resin may be added.

 There is a need for fiberglass that is compatible with a variety of polymer matrix materials that prevent the formation of dust and destruction of fibers during weaving, which can improve adhesion between the laminate and electronic circuitry, and which is compatible with modern pneumatic shuttleless weaving equipment in order to increase productivity.

SUMMARY OF THE INVENTION
One aspect of the present invention is a reinforced laminate for an electrically supported printed circuit board, the laminate comprising: (a) a polymeric matrix material and (b) a reinforced fabric product containing fiberglass yarn that is at least partially coated with a compatible with a polymer matrix material, such a yarn has a value of losses during annealing in the range of 0.01-0.6 wt.% and the value of the transport thrust force under the influence of an air stream of about 100,000 g of effective force per gram of mass of yarn and when using a needle-type air-jet nozzle with an internal air-jet chamber of 2 mm in diameter and a nozzle outlet tube of 20 cm long with a yarn feed speed of 274 m / min and an air pressure of about 310 kilopascals, the laminate has a bending strength in the direction of filling the fabric of more than 3 • 10 ⁷ kg / m ² (about 42.7 kPa).

 Another aspect of the present invention relates to a reinforced laminate for the electrical base of a printed circuit board, which laminate includes: (a) a polymeric matrix material and (b) a reinforced fabric product containing fiberglass yarn, at least partially coated with a coating compatible with polymer matrix material, and such a coating includes (1) a polyester and (2) at least one polymer selected from the group consisting of vinyl pyrrolidone polymers, vinyl alcohol polymers and starches.

 Another aspect of the present invention relates to a reinforced laminate for electronic base, including: (a) a polymer matrix material and (b) a reinforced fabric product containing fiberglass yarn, at least partially coated with a polymer matrix material moreover, such a coating contains (1) a polyester and (2) a vinyl pyrrolidone polymer.

Another aspect of the present invention relates to electronic circuit boards comprising: (a) an electronic backing laminate comprising: (i) a fabric product comprising fiberglass yarn, such a yarn having an annealing loss value in the range of 0.01-0.6 wt.% and the value of the force of the transport thrust under the influence of an air stream of about 100,000 g of effective force per gram of mass of yarn when using a needle air-jet filling device with an internal air-jet chamber with a diameter of 2 mm and an outlet tube adki length of 20 cm at a yarn feed speed 274 m / min and an air pressure of about 310 kilopascals, wherein the laminate has a bending strength in the fill direction of the fabric over 3 • July ¹⁰ kg / m ² (about 42.7 kPa), and (ii) a layer of polymer matrix material deposited on at least a portion of the fabric, and (b) an electrically conductive layer located close to selected areas of selected sides of the laminate.

 Another aspect of the present invention relates to electronic circuit boards comprising: (a) a laminate for an electronic base, comprising: (i) a woven fabric made from fiberglass yarn, at least partially coated with (1) a polyester and (2) at least one polymer selected from the group consisting of polyvinylpyrrolidone polymers, vinyl alcohol polymers and starches, and (ii) a layer of polymer matrix material applied to at least a portion of the fabric, and (b) conductive layer Assumption adjacent to selected sides of the laminate.

Another aspect of the present invention is an electronic circuit board comprising: (a) an electrically-based laminate comprising (i) a first composite layer comprising (1) a fabric product from fiberglass yarn, which yarn has a calcination loss in the range of 0, 01-0.6 wt.% And the value of the force of the transport thrust under the influence of an air stream of about 100,000 g of effective force per gram of mass of yarn when using a needle air-jet nozzle with an internal air-blast chamber diameter m 2 mm and a nozzle exit tube with a length of 20 cm at a yarn feed speed of 274 m / min and an air pressure of about 310 kilopascals, the laminate having a bending strength in the direction of filling the fabric with more than 3 • 10 ⁷ kg / m ² (about 42.7 kPa ), and (2) a layer of polymer matrix material deposited on at least a portion of the fabric; and (ii) a second composite layer different from the first composite layer; and (b) an electrically conductive layer located close to selected portions of selected sides of the laminate.

 Another aspect of the present invention relates to electronic circuit boards comprising: (a) an electrically-based laminate comprising (i) a first composite layer comprising: (1) a woven fabric of yarn containing fiberglass, which is at least partially coated a coating comprising (A) a polyester and (B) at least one polymer selected from the group consisting of polyvinylpyrrolidone polymers, vinyl alcohol polymers and starches, and (2) a layer of polymer matrix material applied to at least a portion of the fabric , and (ii) sec a different composite layer different from the first composite layer; and (b) an electrically conductive layer located close to selected portions of selected sides of the laminate.

Another aspect of the present invention relates to a reinforced copper-clad laminate for electrically-based materials, comprising: (a) a polymer matrix material and (b) one or more strands of a reinforced fabric product, each strand containing 30-75 wt.% Yarn containing fiberglass at least part of which has a coating compatible with the polymer matrix material, the laminate having a coefficient of thermal expansion in the z axis direction of less than 4.5% at a temperature of 288 ^o C.

 A further aspect of the present invention relates to a method for assembling an article by weaving a first yarn with a second yarn to form a fabric, an improvement of this technique being that: the first yarn comprises glass fiber with at least partially coated coating that is compatible with the polymer matrix material moreover, such a coating includes: (1) a polyester and (2) at least one polymer selected from the group consisting of vinylpyrrolidone polymers, vinyl alcohol polymers, starches and mixtures thereof.

Another aspect of the present invention relates to a method for forming a laminate from a woven fabric and a polymer matrix material by at least partially coating the fabric product with a polymer matrix material to form a coated fabric and exposing it to heat, the fabric product comprising fiberglass yarn, and an improvement of this method consists in the following: a fiber compatible with a polymer matrix material is at least partially coated on fiberglass, yarn has a value of n loss upon ignition in the range of 0.01-0.6 wt.% and the value of the transport force of traction under the action of an air jet of more than 100,000 g per gram of mass of yarn when using a needle air-jet nozzle with an internal air-jet chamber having a diameter of 2 mm, and a nozzle exit tube with a length of 20 cm at a yarn feed speed of 274 m / min and an air pressure of about 310 kilopascals, moreover, such a laminate has a bending strength in the direction of filling the fabric of more than 3 • 10 ⁷ kg / m ² (about 42.7 kilopounds / inch ² ).

 Another aspect of the present invention is a method for forming a laminate from a fabric product and a polymeric matrix material as a result of at least partially applying a coating of a polymeric matrix material to a fabric product to form a coated fabric and expose it to heat, the fabric product containing fiberglass yarn , and an improvement of this method is that: at least partially coated with a glass matrix compatible with the polymer matrix material m, and such a coating includes: (1) a polyester and (2) at least one polymer selected from the group consisting of vinylpyrrolidone polymers, vinyl alcohol polymers and starches.

List of figures
The previous brief description of the invention, as well as the following detailed description of the preferred implementation, will become more clear when they are read in conjunction with the study of the accompanying drawings.

Figure 1 - shows a section of a reinforced laminate according to the present invention;
Figure 2 - shows a top view of the fabric according to the present invention;
Figure 3 is a perspective view of a coated fiber bundle according to the present invention;
FIG. 4 is a cross-sectional view of an electric substrate according to the present invention;
5 is a cross-sectional view of an alternative technical solution for an electrical substrate according to the present invention;
6 is a schematic diagram of a method for assembling an article and forming a laminate according to the present invention; and
Figa - shows an enlarged part of Fig.6.

DETAILED DESCRIPTION OF THE INVENTION
The laminates of the present invention are reinforced with a fabric product including coated fiberglass bundles that can form a laminate with a low coefficient of thermal expansion, good bending strength, thermal stability, hydrolytic stability, low corrosion and reactivity in high humidity conditions, in the presence of reactive acids and alkalis. Coated fiberglass bundles are compatible with many polymer matrix materials, which eliminates the need for heat treatment and water treatment of fiberglass fabric before lamination (delamination).

 Another significant advantage of the coated fiberglass bundles of the present invention is their good processability for weaving and knitting, especially for pneumatic shuttleless weaving. Used in the text, the term "pneumatic shuttleless weaving" refers to one type of weaving (shown in Fig. 5), in which the filled yarn (wefts) is inserted into the fabric by blowing compressed air from one or more air-jet nozzles. The transport force of the thrust under the action of an air stream (discussed below) is a measure of the compatibility of the beam with the process of moving the air stream. Increased values of the transport force of the traction of the air stream indicate that the yarn is properly filaments without breaking and therefore more aerodynamically contributes to the advancement of the air stream.

 Other desirable characteristics are low dust and whisk, low torn threads, a small number of clamps for forming a package, a small number of clamps for bobbins, a low beam tension, a high degree of flexibility and a short insertion time, these properties can be achieved using fiberglass bundles coated with the present invention, whereby the weaving and knitting process is facilitated and, accordingly, a fabric with a good degree of roughness and a small number of surface x defects, which is favorable for the use of printed circuit boards.

 In the figures below, the same numbers indicate the same elements. In FIG. 1 shows a laminate 10 of the present invention. Laminate 10 includes a polymer matrix material 12 (discussed in detail below), which is reinforced with a woven braided fabric 14. The fabric 14 can be made by any known weaving or knitting process, but preferably it is produced by the pneumatic shuttleless weaving method, which is discussed in detail below.

 In FIG. 2 and 3, fabric 14 includes one or more coated fiber strands 16 containing at least one glass fiber 18. Preferably, strand 16 contains a plurality of glass fibers 18. As used herein, the term “strand” refers to one or more individual fibers. The term "fiber" means an individual thread.

 The glass fibers 18 can be formed from any fiber-forming glass composition known to a person skilled in the art, including fiber-forming glass compositions such as E-glass, A-glass, C-glass, D-glass, Q-glass, R-glass, S-glass and derivatives of E-glass. The term "E-glass derivatives" refers to glass compositions comprising small amounts of fluorine and / or boron and preferably not containing fluorine and / or boron. In addition, the term "small amounts" as used refers to amounts of fluorine of the order of 1 wt.% And amounts of boron of less than 5 wt.%. Examples of other glass fibers used in the present invention include basalt fibers and slag. Preferred glass fibers are obtained from E-glass or derivatives of E-glass. Such compositions and methods for producing glass fibers from them are well known in the art and, in the light of the present description, there is apparently no need for further discussion. If further information is needed on this subject, such glass compositions and fiber formation methods are described in K. Loevenstein, The manufacturing technology of glass fibers (3rd ed. 1993), pp. 30-44, 47-60, 115-122 and 126-135, US Pat. Nos. 4,542,106 and 5,789,329, and IPC-EG-140 "Specification for finished fabric woven from" E "glass for printed boards", p. 1, publication The Institute for interconnecting and packaging electronic circuits (June 1997 )

 Fiberglass can have a nominal diameter of the thread in the range of 5.0-35.0 micrometers (which corresponds to the designation of threads with indices from D to U and above), and the preferred nominal diameter of the thread has a value in the range of 9.0-30.0 micrometers. The number of fibers in the bundle may be in the range of 100-15000, preferably 200-7000. For additional information regarding nominal thread diameters and fiberglass designations, see Loewenstein, pages 25 and 27.

 In addition to glass fibers, the coated fiber bundle 16 may further comprise fibers 20 obtained from other fiber-forming natural or synthetic materials such as inorganic materials of non-glass origin, natural materials, organic polymeric materials, and mixtures thereof. As used herein, the term “fiber forming” refers to a material that is capable of forming a continuous thread, fiber, bundle or yarn.

 Suitable non-glass inorganic fibers include ceramic fibers derived from silicon carbide, carbon, graphite, mullite, alumina, and piezoelectric ceramic materials. Examples of suitable natural fibers of animal and vegetable origin that do not limit the scope of the invention include cotton, cellulose, natural rubber, flax, Chinese nettle fiber, hemp, sisal and wool. Suitable synthetic fibers include materials derived from polyamides (e.g. nylon and aramids), thermoplastic polyesters (e.g. polyethylene terephthalate and polybutylene terephthalate), acrylic derivatives (e.g. polyacrylonitriles), polyolefins, polyurethanes and vinyl polymers (e.g. polyvinyl alcohol). Examples of non-glass fibers that are believed to be useful in the present invention, as well as methods for making and processing such fibers, are discussed in detail in Encyclopedia of polymer Science and technology, Vol. 6 (1967), pages 505-712. It should be borne in mind that if desired, in the present invention can be used a mixture of copolymers of any of the above materials, as well as combinations of fibers obtained from any of the above materials.

 Further, the present invention is discussed in the context of fiberglass bundles, although one skilled in the art will appreciate that bundle 16 may further include one or more non-glass fibers of the type discussed above.

 As shown in FIG. 2 and 3, in accordance with a preferred technical solution, the fibers 18 of the bundle 16 are coated with a layer 22 of a coating composition that is applied at least on a part of the surface of the fibers 18 to protect the surface of the fiber from abrasion during use and inhibit the destruction of the fibers 18. Preferably, the coating the composition is applied on the entire outer surface or periphery of each of the fibers 18 of the beam 16.

 The coating composition may be present on the fibers in the form of a sizing (preferably), and if desired, a secondary coating and / or a tertiary coating or an outer coating may be used on the sizing. Used in the text, the terms "adhesive", "glued" or "sizing" refer to the coating composition applied to the fibers immediately after their formation. According to an alternative technical solution, the terms “adhesive”, “glued” or “sizing” further refer to a coating composition (also known as “finishing sizing”), which is applied to the fibers after the traditional primary coating composition is removed by exposure heat, water or as a result of chemical treatment, i.e. to the finishing sizing, which is used on exposed fiberglass incorporated in a fabric form. The term “secondary coating” refers to a coating composition applied secondarily on one or a plurality of bundles after applying the adhesive composition on a preferably at least partially dried material.

 The coating composition includes one or more polymeric materials, for example, thermoset materials or thermoplastic materials, which are compatible with the polymer matrix material 12 of the laminate 10, i.e. the components of the coating composition facilitate the soaking and wetting of the matrix material in fiber bundles and provide adequate physical properties of the composite. Preferably, the polymeric materials form a substantially continuous film when applied to the surface of the fibers 18. The polymeric materials used may be water soluble, emulsifiable, dispersible and / or vulcanizable.

 In accordance with a preferred technical solution, the coating composition contains one or more polymeric film-forming materials that are compatible with thermosetting matrix material, which is used to form laminates intended for printed electrical circuits, for example, FR-epoxy resins, which are multifunctional epoxy resins, and according to one of specific embodiments of the invention, bifunctional brominated epoxysmols and polyimides are used as such. See Electronic Materials Handbook, ASM International (1989), pages 534-537. The phrase “compatible with thermosetting matrix material” used in the text means that the components of the coating composition facilitate the soaking and soaking of the matrix material in fiber bundles, provide adequate physical properties of the composite, are chemically compatible with the thermosetting matrix material, and are resistant to hydrolysis. The measure of penetration of the polymer matrix material through the mat is referred to as “wetting”. A measure of the flowability of the polymer matrix material through the mass of fiberglass, resulting in complete encapsulation of the entire surface of each fiberglass with the polymer matrix material, is referred to as "soaking".

Suitable film-forming materials include thermoplastic polymeric materials such as thermoplastic polyesters, vinyl polymers, polyolefins, polyamides (e.g. aliphatic polyamides or aromatic polyamides such as aramid), thermoplastic polyurethanes, acrylic polymers and mixtures thereof that are compatible with thermosetting matrix material . Preferred thermoplastic polyesters include DECMOPHEN 2000 and DECMOPHEN 2001KS, both of which are commercially available from Bayer of Pittsburgh, Pennsylvania, and RD-847A polyester resin, which is commercially available from Borden Chemicals of Columbus, Ohio. Suitable polyamides include VERSAMID products commercially available from General Mills Chemicals, Ink. Suitable thermoplastic polyurethanes include WITCOBOND ^® W-290H, manufactured by Witco Chemical Corp. Of Chicago, Illinois, and RUCOTHANE ^® 2011L Polyurethane Latex, manufactured by Ruco Polymer Corp. Of Hicksville, New York.

 Suitable thermosetting materials include thermosetting polyesters, epoxy materials, vinyl esters, phenols, aminos, thermosetting polyurethanes, and mixtures thereof, which are compatible with the thermosetting matrix material. Suitable thermosetting polyesters may include STYPOL polyesters sold by Cook Composites and Polymers of Port Washington, Wisconsin, as well as NEOXIL polyesters sold commercially by DSM B.V. of Como, Italy.

Suitable epoxy materials contain at least one epoxy or oxirane group in the molecule, and polyglycidyl ethers of polyhydric alcohols or thiols can be given as examples of such materials. Examples of suitable epoxy polymers include epoxy resins EPON ^® 826 EPON ^® 880 and representing the epoxy functional polyglycidyl ethers of bisphenol A, manufactured by Shell Chemical Company of Houston, Texas. However, it is preferable that the coating composition is substantially free of epoxy materials, i.e. included less than 5 wt.% epoxy materials and more preferably less than 2 wt.%
Preferably, the coating composition contains one or more polyesters (preferably DESMOPHEN 2000 and RD-874A) and one or more additional film-forming polymers selected from the group consisting of vinyl pyrrolidone polymers (preferably), vinyl alcohol polymers and / or starches. Preferred vinyl pyrrolidone polymers used in the present invention include polyvinyl pyrrolidones such as PVP K-15, PVP K-30, PVP K-60 and PVP K-90, each of which can be purchased from ISP Chemicals of Wayne, New Jersey. Suitable starches include materials derived from potato, wheat, corn, wax maize, sago, rice, sweet and mixtures thereof, for example Kollotex 1250 (low viscosity, low amylose potato starch, ethylene oxide esterified) manufactured by AVEBE, Netherlands. The amount of additional polymer is preferably less than 10 wt.% And more preferably 0.1-5 wt.%. Preferably, the coating composition is substantially free of starch, i.e. contains less than 5 wt.% starch and more preferably does not contain starch at all, which is often incompatible with matrix material.

 According to an alternative preferred technical solution for printed circuit board laminates, the polymer coating materials comprise a mixture of RD-847A polyester resin, PVP K-30 polyvinylpyrrolidone, DESMOPHEN 2000 polyester and VERSAMID polyamide. The coating composition may comprise a mixture of one or more thermosetting polymeric materials with one or more thermoplastic polymeric materials.

-O-N=C-R⁵
и моногидрокси и/или циклический C₂-С₃ остаток 1,2- или 1,3-гликоля, где R¹ представляет собой C₁-С₃ алкил; R² представляет собой Н или C₁-C₄ алкил; R³ и R⁴, независимо друг от друга, выбирают из Н, C₁-C₄ алкила или С₆-C₈ арила; а R⁵ представляет собой С₄-С₇ алкилен. Примерами способствующих совмещению или функциональных групп могут служить эпокси, глицидокси, меркапто, циано, аллильные, алкильные, уретано, гало, изоцианато, уреидо, имидазолинильные, винильные, акрилато, метакрилато, амино или полиамино группы.Typically, the amount of polymer material may be 1-99 wt.% Based on the weight of the coating composition based on the dry matter, preferably 1-50 wt.% And more preferably 1-25 wt.%
In addition to or instead of the polymeric materials described above, the coating composition preferably contains one or more crosslinking agents such as organosilicon coupling agents, transition metal coupling agents, phosphonate crosslinking agents, aluminum based coupling agents, Werner amine containing crosslinking agents, and mixtures thereof. Such crosslinking agents typically have dual functionality. Each metal or silicon atom is connected to one or more groups that can react or facilitate alignment with the surface of the fiber and / or the components of the coating composition. Used in the text, the term "compatibility" refers to the fact that existing groups are chemically attracted, but do not bind to the surface of the fiber and / or components of the coating composition, for example, under the influence of polar, wetting or solvation forces. Examples of hydrolyzable groups include

-ON = CR ⁵
and monohydroxy and / or cyclic C ₂ -C ₃ residue of 1,2- or 1,3-glycol, where R ¹ represents C ₁ -C ₃ alkyl; R ² represents H or C ₁ -C ₄ alkyl; R ³ and R ⁴ , independently of one another, are 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 facilitating alignment or functional groups are epoxy, glycidoxy, mercapto, cyano, allyl, alkyl, urethane, halo, isocyanato, ureido, imidazolinyl, vinyl, acrylato, methacrylate, amino or polyamino groups.

 In the present invention, it is preferable to use functional organosilane crosslinking agents. Examples of suitable organosilane crosslinking agents include gamma-aminopropyltrialkoxysilanes, gamma-isocyanatopropyltriethoxysilanes, vinyltrialkoxysilanes, glycidoxypropyltrialkoxysilanes and ureidopropyltrialkoxysilanes. Preferred functional organosilane crosslinkers include A-187 gamma-glycidoxypropyltrimethoxysilane, A-174 gamma-methacryloxypropyltrimethoxysilane, A-1100 gamma-aminopropyltriethoxysilane cross-linking agents, A-1108 aminosilane cross-linking agent and A-1160 Osi Specialties, Ink. Of Tarrytown, New York). Prior to use on fibers, the organosilane crosslinking agent may be at least partially hydrolyzed with water, preferably in a 1: 1 stoichiometric ratio or, if desired, used in a non-hydrolyzed form.

 Suitable transition metal crosslinking agents include titanium, zirconium, yttrium and chromium binding agents. Suitable titanate crosslinking agents and zirconate crosslinking agents are available from the Kenrich Petrochemical Company. Suitable chromium complexes are available from E.I. du Font de Nemours of Wilmington, Delaware. Aminer-containing Werner-type crosslinking agents are complex compounds in which a trivalent atom of the nucleus, for example a chromium atom, is coordinated with an organic acid having amine functionality. For this purpose, other metal chelating and coordinating type crosslinking agents known to those skilled in the art can be used.

 The amount of crosslinking agent may be 1-99% by weight of the weight of the coating composition based on the dry matter, preferably 1-10% by weight.

 In FIG. 3, regarding a preferred technical solution of the present invention, it is shown that the coating composition contains one or more solid particles 24 located between or glued to the outer surfaces of the fibers 18. When placed between adjacent fiberglass 26, 28 of the beam 16 such solid particles 24 can provide intermediate spaces 30, which generally correspond to an average particle size of 32 solid particles 24. As used herein, the term “solid” refers to a substance that is not capable of perceptible leakage at moderate load. uzke possessing a certain margin of resistance forces preventing deformation and stores the specific size and shape under normal conditions. See Webster's Third New International Dictionary of the English Language - Unabridged (1971), p. 2169. In addition, the term “solid” as used throughout the text refers to both crystalline and non-crystalline materials.

 The solid particles 24 may have an average grain size of 32 (equivalent spherical diameter) in the range from 0.01 to more than 5 micrometers, preferably 1-1000 micrometers and more preferably 1-25 micrometers. Preferably, the minimum average particle size 32 of the solid particles 24 corresponds to the average nominal diameter of the glass fiber.

The configuration or shape of the solid particles 24, in the General case, can be spherical (for example, as in granules, microspheres or solid hollow spheres), cubic, flat or acicular (elongated or fibrous). For more information on the characteristics of suitable particles, see H. Katz et al. (Ed.) Handbook of Fillers and Plastics, pp. 9-10. Such solid particles should preferably not crumble, deform, or dissolve in the coating composition to a grain size of less than 5 micrometers and preferably not less than 3 micrometers under typical glass fiber processing conditions, such as temperatures up to 25 ^{° C.} and more preferably up to 400 ^° C.

 Glass fibers undergo abrasion as a result of contact with the roughness of neighboring glass fibers and / or other solid objects or materials with which the glass fiber contacts during its formation and subsequent processing, for example, weaving or transmission. Used in the text, the term "abrasive wear" refers to the scraping or cutting of pieces of glass fiber surface, or the rupture of the glass fiber as a result of frictional contact with particles, edges or the material itself, and such contact is intense enough to cause damage to the glass fiber. See the book by K. Ludema, Friction, Wear, Lubrication, (1966), p. 129. The abrasive wear of glass fiber bundles causes the beam to break during processing and the formation of surface defects in products such as woven fabric and composites, which leads to an increase in the number waste and increase production costs.

 In order to minimize the degree of abrasion, solid particles have a hardness not exceeding, i.e. less or equal, fiberglass hardness. The hardness values of solid particles and glass fibers can be determined by the traditional method of measuring hardness, for example, Vickers or Brinell hardness, however, it is preferable to measure according to the original Mohs hardness scale when the relative surface resistance of the material to scratching is determined. The Mohs fiber glass hardness value is typically in the range 4.5-6.5, and is preferably 6. R. Weast (eds.) Handbook of Chemistry and Physics, CRS, Press (1975), p. F-22. Mohs solids hardness is preferably in the range of 0.5-6. Table A shows the Mohs hardness values of some non-limiting examples of particulate matter suitable for use in the present invention.

 As noted above, the Mohs hardness scale refers to the scratch resistance of the material. In this regard, the present invention contemplates particles having a hardness on their surface different from the hardness of the internal parts of the particle below the surface level. In more detail, the surface of the particle can be modified in any known manner, including, but not limited to, coating, plating, or encapsulating the particle or chemically altering its surface characteristics using known techniques, as a result of which the hardness of the surface of the particle will not exceed fiberglass hardness, while particle hardness below surface level is higher than fiberglass hardness. Thus, for example, without limiting the scope of the invention, inorganic particles such as silicon carbide and aluminum nitride can be coated with mica, carbonate or nanoclay. In addition, silane coupling agents with alkyl side chains can react with the surface of many oxide particles to produce a “softer” surface.

 As a rule, solid particles 24 used in the present invention can be formed from inorganic materials, organic materials, or mixtures thereof. Preferably, solid particles 24 are formed from inorganic materials selected from the group consisting of ceramic materials and metallic materials. Suitable ceramic materials include metal nitrides, metal oxides, metal carbides, metal sulfides, metal borides, metal silicates, metal carbonates and mixtures thereof.

 A non-limiting invention, a suitable metal nitride is boron nitride, which is the preferred inorganic material from which the solid particles used in the present invention are obtained. A non-limiting example of a suitable metal oxide is zinc oxide. Suitable metal sulfides include molybdenum disulfide, tantalum disulfide, tungsten disulfide, and zinc sulfide. Useful metal silicates include aluminum silicates and magnesium silicates, for example vermiculite. Suitable metallic materials include graphite, molybdenum, platinum, palladium, nickel, aluminum, copper, gold, iron, silver, and mixtures thereof.

 Preferably, the inorganic solid particles 24 are also solid lubricants. As used in the text, the term “solid lubricant” means that inorganic solid particles 24 have a characteristic crystalline shape, which causes them to cut into thin flat plates that slide easily against each other and thus produce an antifriction lubricating effect between the surface of the glass fiber and the adjacent solid surface, at least one of which is in a state of motion. (See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary (12th ed. 1993), p. 712). Friction is the sliding resistance of one solid material over another. F. Clauss, Solid Lubricants and Self-Lubricating Solids, (1972), p. 1.

 According to a preferred technical solution, the solid lubricant particles have a layered structure. Particles having a layered or hexagonal crystalline structure consist of layers or planes of atoms in a hexagonal orientation with strong bonding inside the layers and weak Vandervaals binding between the layers, which provides a low tensile strength between the layers. Friction, Wear, Lubrication, p. 125, Solid Lubricants and Self-Lubricating Solids, p. 19-22, 42-54, 75-77, 80-81, 82, 90-102, 113-120 and 128, as well as W. Campbell "Solid Lubricants", Boundary Lubrication: An Appraisal Of World Literature, ASME Research Committee on Lubrication (1969), pp. 202-203. Inorganic solids having a buckyball laminar structure can also be used in the present invention.

 Non-limiting examples of particles of a suitable inorganic solid lubricating agent having a layered structure include boron nitride, graphite, metal dichalcogenides, mica, talc, gypsum, kaolinite, calcite, cadmium iodide, silver sulfide, and mixtures thereof. Preferred inorganic solid lubricant particles include boron nitride, graphite, metal dichalcogenides and mixtures thereof. Suitable metal dichalcogenides include molybdenum disulphide, molybdenum diselinide, tantalum disulphide, tantalum disulide, tungsten disulphide, tungsten diselide and mixtures thereof.

Most preferred for use in aqueous adhesive compositions are boron nitride particles with
hexagonal crystal structure. Particles of boron nitride, zinc sulfide and montmorillonite also provide a good degree of whiteness of composites with such polymer matrix materials as nylon 6,6.

Non-limiting examples of boron nitride particles suitable for use in the present invention include PolarTherm ^® powdered boron nitride particles of the 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), which are commercially available from Advanced Ceramics Corporation of Lakewood, Ohio. "PolarTherm ^® Thermally conductive Fillers for Polymeric Materials," Technical Bulletin of Advanced Ceramics Corporation of Lakewood, Ohio (1966). Such particles have a thermal conductivity of 250-300 W / m • K at 25 ^o C, a dielectric constant of 3.9 and volume resistivity of the order of 10 ¹⁵ Ohm • cm. The 100 series powder has an average particle size in the range of 5-14 micrometers, the 300 series has an average particle size in the range of 100-150 micrometers and the 600 series has an average particle size in the range of 16 to more than 200 micrometers.

Particles of solid lubricant 24 may be present in a dispersion, suspension or emulsion in water. If desired, other solvents may be included in the adhesive compositions, for example mineral oil or alcohol (preferably in an amount of less than 5 wt.%). A non-limiting example of a preferred dispersion containing 25% by weight of boron nitride in water is ORPAC BORON NITRIDE RELEASECOAT-CONC, which is commercially available from ZYP Coatings, Inc. Of Oak Ridge, Tennessee. ORPAC BORON NITRIDE RELEASECOAT-CONC, ZYP Coatings, Inc. Technical Bulletin According to the supplier’s instructions, boron nitride particles in such a product have an average particle size of less than 3 micrometers. This dispersion contains 1% magnesium aluminum silicate, which, according to the manufacturer, binds boron nitride particles to the substrate on which the dispersion is applied. Other suitable products available from Zyp Coatings include BORON NITRIDE LUBRICOAT ^® , BRAZE STOP and WELD RELEASE products.

Although not a preferred option, the coating composition may contain hydratable or hydrated inorganic solid lubricants. Non-limiting examples of such hydratable inorganic solid lubricants are clay-based mineral phosilicates, including mica (eg, muscovite), talc, montmorillonite, kaolinite and gypsum (CaSO ₄ • 2H ₂ O). As used herein, the term "hydratable" means that particles of a solid inorganic lubricant react with water molecules to form hydrates and contain hydrated water or crystallization water. A "hydrate" is obtained by the reaction of water molecules with a substance in which the H-OH bond is not cleaved. (See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary (12th ed. 1993), pp. 609-610 and T. Perros, Chemistry (1967), pp. 186-187). In the chemical formulas of hydrates, the addition of water molecules is usually indicated by a dot in the center, for example 3MgO • 4SiO ₂ • H ₂ O (talc), Al ₂ O ₃ • 2SiO ₂ • 2H ₂ O (kaolinite). Hydrates contain coordinate water, which coordinates the cations in the hydrated material and cannot be removed without destroying the structure, and / or structural water, which occupies gaps in the structure in order to add electrostatic energy without disturbing the charge balance. R. Evans, An Introduction to Crystal Chemistry (1948), p. 276.

Preferably, the coating composition is substantially free of particles of hydratable inorganic lubricant or particles of abrasive silicon dioxide or calcium carbonate, i.e. contains less than 20 wt.% hydratable inorganic lubricant particles, particles of abrasive silicon dioxide or calcium carbonate calculated on the dry matter, more preferably less than 5 wt.% and most preferably less than 0.001 wt.%
According to an alternative technical solution, solid particles 24 can be formed from organic polymeric materials selected from the group consisting of thermoset materials, thermoplastic materials, starches and mixtures thereof. Suitable thermosetting materials include thermosetting polyesters, vinyl esters, epoxy materials, phenols, aminos, thermosetting polyurethanes, and mixtures thereof, discussed below. Suitable thermoplastic materials include vinyl polymers, thermoplastic polyesters, polyolefins, polyamides, thermoplastic polyurethanes, acrylic polymers and mixtures thereof. Preferred organic solids are in the form of microspheres or hollow spheres.

According to an alternative preferred technical solution, solid particles 24 have thermal conductivity, i.e. have a thermal conductivity of more than 30 W / m • K, as is the case with boron nitride, graphite and the metallic inorganic solid lubricants discussed above. The thermal conductivity of a solid material can be determined by any method known to a person skilled in the art, for example, using the sheltered hot plate method according to ASTM C-177-85 at a temperature of the order of 300 ^o C.

 According to another alternative technical solution, inorganic solid particles 24 are electrically insulating materials or have high electrical resistance, for example, have an electrical resistance of more than 1000 μm • cm, as in the case of boron nitride.

Particulate lubricants, if present, may be present in an amount of 0.001-99 wt.% Based on the weight of the coating composition based on the dry matter, preferably 1-80 wt.%, More preferably 1-40 wt.%
The coating composition may further comprise one or more organic lubricants that are chemically different from the polymeric materials discussed above. Although the coating composition may contain up to 60% by weight of organic lubricants, preferably the coating composition is substantially free of organic lubricant, for example, contains less than 10% by weight of organic lubricant and more preferably contains 1-5% by weight of organic lubricants. Examples of such organic lubricants include cationic, non-ionic or anionic lubricants or mixtures thereof, for example, amine salts of fatty acids, alkylimidazoline derivatives such as CATION X, which is commercially available from Rhone Poulenc of Princeton, New Jersey, acid-solubilized amides fatty acids, condensates of fatty acids and polyethyleneimine, as well as amido substituted polyethylene imines, such as EMERY ^® 6717, a partially amidated polyethylene imine commercially available from Henkel Corporation of Kankakee, Illinois.

The coating composition may include one or more emulsifying agents for emulsifying or dispersing components of the coating composition, for example, inorganic particles. Non-limiting examples of suitable emulsifying agents or surfactants include polyoxyalkylene block copolymers (e.g., the polyoxypropylene-polyoxyethylene copolymer PLURONIC ^™ F-108, which is manufactured by BASF Corporation of Parsippany, New Jersey), ethoxylated alkyl phenols (e.g. ethoxylated CA ethylene EPI -630, manufactured by GAF Corporation of Wayne, New Jersey), polyoxyethylene octyl phenyl glycol esters, sorbitol ethylene oxide derivatives, polyoxyethylene vegetable oils (e.g. ALKAMULS EL-719, manufactured by Rhone-Poulenc), as well as nonylphenol surfactants (e.g., MACOL NP-6, manufactured by BASF of Parsippany, New Jersey). Typically, the amount of emulsifying agent may be 1-30 wt.% Of the weight of the coating composition based on the weight of dry matter.

The coating composition may contain one or more water-soluble, emulsifiable or dispersible waxy materials, for example, plant, animal, mineral, synthetic or petroleum waxes. Preferred waxes include petroleum waxes such as microcrystalline wax is MICHEM ^® LUBE 296 microcrystalline wax PETROLITE 75 manufactured by Michelman Inc. Of Cicinnati, Ohio, and Petrolite Corporation of Tulsa, Oklahoma, respectively. Typically, the amount of wax may be 1-10 weight. % by weight of the coating based on dry matter.

 Crosslinking materials such as melamine formaldehyde and plasticizers such as phthalates, trimellitates and adipates may also be included in the coating composition. The amount of crosslinking agent or plasticizer may be 1-5 wt.% Of the weight of the coating composition, calculated on the dry matter.

 Other additives may be incorporated into the coating compositions, for example, silicones, fungicides, bactericides and anti-foaming agents, usually in an amount of less than 5% by weight. Organic and / or inorganic acids and bases may also be added in an amount sufficient to create a pH of 2-10 in the coating composition. A non-limiting example of a suitable silicone emulsion is the LE-9300 epoxidized silicone emulsion manufactured by Osi Specialites, Inc. Of Danbury, Connecticut. An example of a suitable bactericide is the antimicrobial compound Biomet 66, which is available from M&T Chemicals of Rahway, New Jersey. Suitable antifoam materials are SAG materials manufactured by Osi Specialites, Inc. Of Danbury, Connecticut, and MAZU DF-136, available from the BASF Company of Parsippany, New Jersey. If desired, ammonium hydroxide may be added to stabilize the coating composition. Water (preferably deionized) is preferably included in the coating composition in an amount sufficient to ensure the application of a substantially uniform coating on the beam, usually in an amount of 25-99 wt.%. The weight percent solids of the aqueous coating composition is usually 1-75 wt.%.

 Preferably, the coating composition is substantially free of glass materials. Used in the test, the term "glass materials" means that the coating composition contains less than 20 vol.% Matrix materials based on glass for the formation of glass composites, preferably less than 5 vol.% And more preferably when such materials are absent. Examples of such glass matrix materials are dark glass ceramic matrix materials or aluminosilicate matrix materials that are well known to those skilled in the art.

In accordance with one of the technical solutions relating to tissue products for the printed circuit boards, glass fiber coated yarns of the present invention applies a primary layer of a dried residue of an aqueous adhesive composition comprising powdered boron nitride grade Polar Therm ^® 160 and / or dispersion BORON NITRIDE RELEASECOAT, epoksiplenkoobrazuyuschy material EPON 826, polyvinylpyrrolidone PVP K-30, epoxy functional organosilane crosslinking agent A-187, polyoxyethylated vegetable oil ALKAMULS EL-719, ethoxylated octylpheno sietanol IGEPAL CA-630, polyethylene glycol monolaurate, KESSCO PEG 600, which are produced Stepan Company of Chicago, Illinois, and a partially amidated polyethyleneimine EMERY ^® 6717.

According to an advantageous technical solution concerning the woven fabric, glass fiber yarns with a coating of the present invention applies a primary layer of a dried residue of an aqueous sizing composition comprising particulate boron nitride grade Polar Therm ^® 160 and / or dispersion BORON NITRIDE RELEASECOAT, polyester RD-847A, polyvinylpyrrolidone PVP K-30, DESMOPHEN 2000 polyester, A-174 acrylic functional organosilane crosslinking agent, and A-187 epoxy functional organosilane crosslinking agent.

 Opaque compositions of the present invention can be obtained by any suitable method, for example, traditional mixing, well known to the person skilled in the art. Preferably, the above components are diluted with water to obtain the desired weight percent solids and mixed with each other. Powdered, heat-conducting, inorganic solid particles can be mixed with water or added to the polymer material before mixing with other coating components.

The coating layer can be applied to the fibers in various ways, for example by contacting the threads with a roller or tape applicator, spraying, or other methods. Coated fibers are preferably dried at room temperature or at elevated temperature. Excess moisture is removed from the fibers in the dryer and, if present, curing components of the composition are cured. The temperature and drying time of the glass fibers will depend on factors such as the percentage of solids in the coating composition, the nature of the components of the coating composition and the type of fiberglass. After drying, the coating composition is usually present in the form of a dried adhesive residue on the fibers in an amount of 0.1-25 wt.%. The weight loss of the fibers after calcination is usually less than 0.6 wt.%, Preferably less than 0.5 wt. % and more preferably have a value in the range of 0.01-0.45 wt.% Loss upon calcination of a coated fiber sample can be determined by heating the fiber for 20 minutes in a muffle at a temperature of 1200 ^o C.

 The secondary layer of the secondary coating composition can be applied to the coating composition layer discussed above in an amount effective to coat or impregnate part of the strands, for example, by immersing the strand in a bath containing the composition, spraying the composition in a beam or by contacting the strand with the applicator mentioned above. The coated bundle may be passed through a die to remove excess coating composition from the beam and / or dried, as noted above, for a time sufficient to at least partially dry or vulcanize the secondary coating composition. The method and apparatus for applying the secondary coating composition to the beam is partially determined by the configuration of the beam material. Preferably, the bundle is dried after applying the secondary coating composition using well-known techniques.

 A suitable secondary coating composition may contain one or more of the film-forming materials, lubricants, and other additives mentioned above. The secondary coating is different from the adhesive composition, for example, (1) it contains at least one component that is chemically different from the components of the sizing composition, or (2) contains at least one component, the amount of which differs from the amount of the same component, contained in a sizing composition. Non-limiting examples of suitable secondary coating compositions comprising polyurethanes are disclosed in US Pat. Nos. 4,762,750 and 4,762,751.

 In accordance with an alternative preferred technical solution of the present invention, a primary layer of the dried residue of a traditional sizing composition or a sizing composition, which may contain any of the adhesive components in the above amounts, can be applied to the fiberglass fiber bundle. Examples of suitable sizing compositions are given in Loewenstein, pp. 237-291 (3rd ed. 1993) and US Pat. surface of the primary layer. The secondary sizing composition may contain one or more types of solid particles, discussed above, and / or those particles that are listed in tables C, D and E.

 Molybdenum disulfide and magnesium oxide are other organic solid particles that are used to create the secondary and tertiary coatings of the present invention. One skilled in the art will appreciate that mixtures of any of the above inorganic solid particles may be used in the present invention.

 The amount of inorganic particles in the secondary coating composition may be 1-99 wt.% Of the total weight of solids, preferably 20-90 wt. % The percentage of solids in the aqueous secondary coating composition is usually in the range of 5-75% by weight.

 According to an alternative technical solution, the tertiary layer of the tertiary coating composition can be applied at least on a part of the surface and preferably on the entire surface of the secondary layer, i.e. such fibrous yarn will comprise a primary sizing layer, a secondary layer of a secondary coating composition, and a tertiary, outer layer of a tertiary coating. The tertiary coating is different from the sizing composition and the second coating composition, i.e., the tertiary coating composition (1) contains at least one component that is chemically different from the components of the sizing and secondary coating composition, or (2) contains at least one component in an amount that differs from the amount of the same component contained in a sizing or secondary coating composition.

According to such a technical solution, the secondary coating composition contains one or more of the above-mentioned polymeric materials, such as polyurethane, and the tertiary coating composition contains powdered, heat-conducting inorganic particles, for example, the above-mentioned PolarTherm ^® boron nitride particles. Preferably, the powder coating is applied by passing the beam with the liquid secondary coating composition applied thereon, through a fluidized bed or spray device, in order to adhere the powder particles to the sticky secondary coating composition. Alternatively, the tufts (strands) may adhere to the fabric 114 before applying the tertiary coating layer 140, as shown in FIG. The weight percent of the powdered, heat-conducting inorganic solid particles adhered to the coated beam may be 0.1-75% by weight of the total weight of the dry beam. The tertiary coating may also contain one or more of such polymeric materials as mentioned above, for example acrylic polymers, epoxides or polyolefins, traditional stabilizers and other modifiers known in the field of applying such coatings, preferably in dry powder form.

Fibrous bundles can be processed into a fabric article 14, preferably by knitting or weaving. The fabric article 14 is used as a reinforcing system for reinforced polymer matrix materials 12 to produce the composite or laminate 10 shown in FIG. 1, preferably for printed electronic circuits. The main bundles of fabric 14 can be twisted or remain in the initial state before weaving using the style of 1080, in which 118 warp threads and 93 weft threads fall on an area of 5 cm ² , 5 11 1 • 0 (D450 1/0) main and weft thread; nominal tissue thickness is 0.053 mm; the specific gravity of such a fabric is 46.8 g / m ² . Descriptions of these and other styles are given in IPC-EG-140 "Specification for finished Fabric Woven from 'E' Glass for Printed Boards", published by The Institute for Interconnecting and Packaging Electronic Circuits (June 1997). A suitable woven reinforced article 14 can be made using a conventional weaving machine known to one skilled in the art, for example a shuttle or rapier weaving machine, however it is preferable to use a pneumatic shuttleless weaving machine. Preferred shuttleless looms are available from Tsudakoma of Japan as Model # 103 and Sulzer Ruti Model # L-5000 or L-5100 from Sulzer Brothers Ltd. of Zurich, Switzerland. Sulzer Ruti L-5000 and L-5100 - Product bulletins of Sulzer Ruti Ltd., Switzerland. As used herein, the term “pneumatic shuttleless weaving” refers to a type of fabric manufacturing using a shuttleless weaving loom 526 (shown in FIG. 6), in which filled yarn (wefts) 510 is inserted into the base skirt by purging with compressed air 514 from one or more air-jet nozzles 518 (shown in FIGS. 6 and 6a). The yarn 510 moves along the guide 524 of the fabric 528 (10-6 inches) and more preferably about 0.91 m under the influence of compressed air.

 The air-jet system may have a single main nozzle 516, but preferably it also contains a plurality of additional interchangeable nozzles 520 together with the base 512 to provide additional air 522 to be blown into the thread 510 to maintain the desired air pressure as the thread 510 crosses the width 524 fabric 528. The pressure of the air supplied to the main air nozzle 516 is preferably 103-413 kilopascals (kPa), more preferably 310 kPa. The preferred execution style of the main air nozzle 516 is a model 044455001 needle air nozzle assembly, which has an internal air jet chamber with a diameter of 517 mm in 2 mm and an nozzle outlet tube 519 with an element length of 521 20 cm (manufactured by Sulzer Ruti of Spartanburg, North Carolina). Preferably, the air-jet filling system has 15-20 additional air nozzles 520 that provide additional air purges in the direction of movement of the thread 510 to facilitate the movement of the thread 510 on the machine 526. The air pressure generated in each of the additional air nozzles 520 is preferably 3-6 bar.

 The filament 510 is pulled out of the feed unit by means of a feed system 532 at a speed of 180-550 meters / minute, preferably 274 meters / minute. Filling thread 510 is fed into the main nozzle 518 through the clamp. Air blowing drives a predetermined length of yarn (approximately equal to the width of the fabric) through a mixing guide. After completing the firmware, the end of the thread, remote from the main nozzle 518, is cut with a cutting tool 534.

 The compatibility and aerodynamic properties of various threads with the pneumatic shuttleless spinning method can be determined by the following method, which is usually referred to in the text as a test method for the "driving force of a vehicle under the influence of an air stream". Such a test is used to measure the pulling or pulling force (“driving force”) created when a thread is pushed into the air jet nozzle under the influence of the force of an air stream. In this method, each yarn sample is fed at a speed of 274 meters / minute through a Sulzer Ruti model 044455001 needle air jet nozzle having an internal air jet chamber with a diameter of 517 equal to 2 mm and a tube exiting the nozzle with an element length 521 of 20 centimeters ( manufactured by Sulzer Ruti of Spartanburg, North Carolina) at an air pressure of about 310 kilopascals. The tensiometer is placed in contact with the yarn in a position in front of its entrance to the air jet nozzle. The tensiometer measures the force in grams (driving force) that occurs in the yarn under the influence of an air stream, as the yarn is pulled into the air nozzle.

The value of the driving force per unit mass can be used as the basis for comparing yarn samples. For the purposes of relative comparison, the measurement of the pulling force is normalized per yarn 1 cm long. The gram-mass of the yarn one centimeter long can be determined by the formula
Gram mass = (p (d / 2) ² (N) (ρ _glass ) (1 centimeter of yarn length), (I)
in which d is the diameter of a single fiber of the yarn bundle, N is the number of fibers in the yarn bundle, and ρ _glass is the density of the glass at a temperature of about 25 ^{° C.} (about 2.6 g / cm ³ ). Table F lists the yarn fiber diameters of some typical fiberglass products.

So, for example, the gram-mass of one centimeter of the length of the yarn G75 is (p (9 • 10 ^-4 / 2) ² ) (400) (2.6 g / cm ³ ), (1 centimeter of the length of the yarn) = 6.62 • 10 ^-4 gram mass. For D450 yarn, the gram-mass is 1.34 • 10 ^-4 gram-mass. The relative tensile force per unit mass (“traction force of pneumatic transport”) is calculated by dividing the magnitude of the tensile force (gram-force), which is measured using a tensiometer, by gram-mass for this type of yarn tested. So, for example, if for a sample of G75 yarn the tensile force measurement with a tensiometer was 68.5, then the value of the driving force of the transport under the action of an air jet is 68.5 divided by 6.62 • 10 ^-4 = 103.474 gram-force per gram masses of yarn.

 The tensile force of the transport of yarn under the action of the air stream used to form the woven product for the laminate of the present invention, the value of which is determined according to the test method of the tensile force of the transport under the influence of the air stream described above, is more than 100,000 gram-force per gram of mass of yarn, preferably 100,000 -400,000 gram-forces per gram of mass of yarn, and more preferably 120000-300000 gram-forces per gram of mass of yarn.

 As shown in figure 1, the fabric 14 can be used to obtain a laminate 10 by coating and / or impregnating one or more layers of fabric 14 with a polymer thermoplastic or thermosetting matrix material 12. Laminate 10 is intended for use as an electronic base for a printed circuit board 30. Used in throughout the text, the term "electronic base" means a structure that mechanically supports and / or electrically combines elements including, but not limited to, active electronic components, passive electronic components tapes, printed circuits, integrated circuits, semiconductor devices and other structural elements associated with such elements, including, but not limited to, connectors, sockets, retaining clips and heat sinks.

The matrix materials used in the present invention include thermosetting materials such as thermosetting polyesters, vinyl esters, epoxides (containing at least one epoxy or oxirane group in a molecule, such as polyglycidyl ethers of polyhydric alcohols or thiols), phenolic compounds, amines, thermosetting polyurethanes , their derivatives and mixtures. Preferred matrix materials for forming laminates for printed circuit boards are FR-4 epoxies, polyimides and liquid crystal polymers, the compositions of which are well known to those skilled in the art. If you need additional information regarding such compositions, it is necessary to refer to the Electronic Materiels Handbook ^TM, ASM International (1989), pp. 534-537.

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

 A suitable matrix material formulation consists of epoxysmol EPON 1120-A80, dicyandiamide, 2-methylimidazole and DOWANOL PM.

 Other components that can be incorporated into the polymer matrix materials and the reinforcing material in the composite include dyes or pigments, lubricants or processing aids, stabilizers from ultraviolet (UV) light, antioxidants, and other fillers and diluents.

 The fabric 14 can be coated and impregnated by immersing it in a bath of polymer matrix material 12, for example, as described by R. Tummala (ed.) Microelectronics Packaging Handbook, (1989), pp. 895-896. The polymer matrix material 12 and fabric 14 can be formed into a composite or laminate 10 in a variety of ways, which depend on factors such as the type of polymer matrix material used. For example, in the case of a thermosetting matrix material, the laminate can be formed by direct or injection molding, using the process of obtaining a uniaxially oriented fibrous plastic, manually layering or sheet forming followed by direct or injection molding. Thermosetting polymer matrix materials can be vulcanized by incorporating structuring agents into the matrix material and / or by applying heat. Suitable crosslinking agents used to crosslink the polymer matrix material are discussed below. The temperature and duration of the cure of the thermosetting polymer matrix material depends on factors such as the type of matrix material used, the presence of other additives in the matrix system, and the thickness of the composite.

 Suitable methods for forming a composite from a thermoplastic matrix material include direct molding or extrusion compounding followed by injection molding. The method and apparatus for forming the composite by the above methods are described by I. Rubin, Handbook of Plastic Materials and Technology (1990), pp. 955-1062, 1179-1215 and 1225-1271.

 In the specific technical solution of the invention shown in Fig. 4, the composite or laminate 10 includes a fabric 14 impregnated with a compatible matrix material 12. The impregnated fabric can then be pressed between a number of measuring rollers to store the measured amount of matrix material and dried to form an electronic support in the form semi-vulcanized substrate or prepreg (semi-finished product). The conductive layer 40 can be placed on the side portion 42 of the prepreg using the method described below, and the resulting prepreg is vulcanized to form a laminate 10, which acts as an electronic support 50 with an electrically conductive layer. According to another technical solution of the invention, which is more typical for industrial electrosupport, two or more prepregs are combined with an electrically conductive layer and packaged and vulcanized together using a method well known to one skilled in the art to form a multilayer electronic support. Thus, for example, without limiting the scope of the invention, the prepreg package can be formed layer by layer, for example, between polished steel plates, at elevated temperatures and pressures for a certain time in order to cure the polymer matrix and obtain a laminate of the desired thickness. Parts of one or more prepregs may be provided with an electrically conductive layer before or after layer-by-layer formation and vulcanization so that the resulting electrical substrate is a laminate containing at least one electrically conductive layer located along part of the exposed surface (hereinafter referred to as " coated laminate ").

 The circuit can then be obtained from an electrically conductive layer from one of the layers of a multilayer electrical base in the form of a printed circuit board or a printed circuit board (hereinafter in the text these structures are collectively referred to as "circuit boards"). If desired, openings or openings (referred to hereinafter as “Vias”) can be made in the electronic substrates in order to provide a connection between the circuits and / or components on opposite surfaces of the electrical substrate, these operations being carried out by conventional methods known in the art. which include, without limiting the scope of the invention, mechanical drilling and laser drilling. More specifically, after the formation of the openings, a layer of electrically conductive material is applied to the walls of such an opening or the aperture is filled with electrically conductive material in order to facilitate electrical connection and / or heat dissipation.

 The electrical conductive layer 40 may be formed by any method well known to a person skilled in the art. So, for example, without limiting the scope of the invention, the electrically conductive layer can be formed by layering a thin plate or foil of a metal material, at least on a part of the side of the semi-vulcanized prepreg or laminated product. Alternatively, an electrically conductive layer can be formed by applying a layer of metallic material to at least a portion of the side of a semi-vulcanized or vulcanized prepreg or laminate using well-known techniques that do not limit the scope of the invention, such as plating, chemical deposition or spraying. Metallic materials suitable for use as an electrically conductive layer include, but are not limited to, copper (which is the preferred metal), silver, aluminum, gold, tin, tin-lead alloys, palladium, and combinations thereof.

 According to another technical solution of the present invention, the electronic base of the printed circuit board can be in the form of a multilayer circuit board, designed by jointly layering one or more electrical circuit boards (described above) in the presence of one or more cladding laminate (described above) and / or one or more prepregs (pre-soaked strands). If desired, additional electrically conductive layers may be applied to the base of the electronic printed circuit board, for example, along a portion of the unexposed side of the multilayer circuit board. In addition, if required, additional circuits can be formed from 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, such a board may have external and internal circuits.

 Additional openings are formed, as indicated earlier, partially or completely through the board in order to ensure electrical connection between the layers in the selected positions. It should be borne in mind that the resulting structure may contain a certain number of openings that completely pass through the structure, a certain number of openings that only partially pass through the structure, and some part of the openings that are completely in the structure.

 Preferably, the thickness of the laminate constituting the electric base of the printed circuit board 50 is greater than 0.051 mm, more preferably 0.13-2.5 mm. For an eight-layer layered 7628 style fabric, the thickness is usually 1.32 mm. The number of layers of fabric 14 in the laminate 10 can vary depending on the desired thickness of the laminate. For purposes of clarity, a single layer of fabric is shown in the laminates in FIGS. 1, 4, and 5. The number of such layers may be from one to forty. Preferably, such a laminated article has eight layers of fabric or prepreg.

 The resin content in the laminate may be 35-80 wt.%, More preferably 40-75 wt.%. The amount of fabric in the laminate may be 20-65% by weight, and more preferably 25-60% by weight.

For a laminate formed from stitched E-fiberglass, using an epoxy resin matrix material with a minimum glass transition temperature of about 110 ^° C, the desired minimum bending strength across the machine or in width (usually perpendicular to the longitudinal axis of the fabric) is more than 3 • 10 ⁷ kg / m ² , preferably more than 3.52 • 10 ⁷ kg / m ² and more preferably above 4.9 • 10 ⁷ kg / m ² in accordance with IPC-4101 "Specification for base materials for rigid and multilayer printed boards", page . 29, publication of The Institute for interconnecting and packaging Electronic circuits (December 1997). In the direction of the length of the material (usually parallel to the longitudinal axis of the fabric), the desired minimum bending strength is more than 4 • 10 ⁷ kg / m ² and preferably more than 4.23 • 10 ⁷ kg / m ² . Bending strength is measured in accordance with ASTM D-790 and IPC-TM-650 Test Methods Manual of the Institute for Interconnecting and Packaging Electronics (December 1994), the metal plating being completely removed by etching according to IPC-45101 section 3.8.2.4. The advantages of the electronic foundations of the present invention include high bending strength (tensile and compressive strength) and a high modulus, which can reduce the deformation of the circuit board, including the layered product.

The electronic bases of the present invention in the form of copper-clad FR-4 laminates preferably have a coefficient of thermal expansion at 288 ^° C in the z-axis direction of the laminate ("Z-CTE"), i.e. across the thickness of the laminate, less than 4.5% and more preferably 0.01-4.5 wt.%, according to IPC Test Method 2.4.41. Each such laminate preferably contains eight layers of style 7628 fabric, although fabrics of styles 1080 and 2116 can also be used. Laminates with low thermal expansion coefficients are usually less susceptible to expansion and contraction and can minimize board deformation.

The present invention also provides for the production of multilayer laminates and electronic circuit boards, which include at least one composite layer obtained by the described method, and at least one composite layer obtained by a method different from the described method of obtaining a composite layer, for example, using traditional fiberglass composite technology. As is well known to a person skilled in the art, according to traditional practice, yarns in solid fiberglass strands used in a woven product are treated with sizing from a starch / oil mixture that contains partially or fully dextrinized starch or amylose, hydrogenated vegetable oil, a cationic wetting agent, an emulsifier and water, i.e. contains components, but is not limited to those described by Lowenstein on pages 237-244 (3rd ed. 1993). The main yarn obtained from such yarns is then treated with a solution before weaving to protect the yarns from abrasion during the weaving process, for example with polyvinyl alcohol described in US Pat. No. 4,530,876. Usually, this operation is referred to as “slashing”. Polyvinyl alcohol, like sizing from a mixture of starch with oil, is usually not compatible with the polymer matrix material used by the manufacturers of the composite, and the fabric must be cleaned to remove almost all organic materials from the surface of the glass fiber before impregnating the woven product. This operation can be carried out in a variety of ways, for example using a scrubber to wash the fabric or using a more conventional heat treatment of the fabric using well-known methods. As a result of the cleaning operation, the interface between the polymeric matrix material used to impregnate the fabric and the cleaned glass fiber surface disappears, as a result of which the binder can be applied on the glass fiber surface. Such an operation, experts in this field are called finishing. As binders for finishing operations, silanes are traditionally used, not limited to the substances described by E.R. Plueddeman, Silane Coupling Agents (1982), pp. 146-147. See also Lowenstein, pp. 249-256 (3rd ed. 1993). After silane treatment, the fabric is impregnated with a compatible polymer
matrix material, passed between the counting rollers and dried to obtain a semi-vulcanized prepreg, as described above. It should be borne in mind that depending on the nature of the sizing, the cleaning operation and / or the matrix resin used in the composite, the slashing and / or finishing steps may be omitted. One or more prepregs obtained using conventional fiberglass composite technology can then be combined with one or more prepregs obtained in accordance with the present invention to form the electronic substrate discussed above, and in particular a multilayer laminate or circuit board. For more information concerning the receipt of electronic circuit boards, ^{see. Electronic Materials Handbook TM, ASM International} ( 1989), pp. 113-115, R. Tummala (ed.), Microelectronics Packaging Handbook (1989), pp. 858-861 and 895-909, MW Jawitz, Printed Circuit Board Handbook (1997), pp. 9.1-9.42 and CF Coombs, Jr (ed.), Printed Circuit Handbook (3rd ed.), 1988, pp. 6.1-6.7.

 Composites and laminates for forming the electronic bases of the present invention can be used to produce packages used in the electronics industry, more specifically for packages of the first, second and / or third level, such as, for example, those described in Tummala, p. . 25-43. In addition, the present invention can also be used for other packaging levels.

 The present invention also encompasses a method for glueing fabric 14 by interlacing the first yarn (weft) with the second yarn (main yarn) to form fabric 14, for example using the pneumatic shuttleless weaving discussed above. The improvement includes a first yarn containing coated E-glass fibers that are compatible with the polymer matrix material, which coating includes (1) one or more polyesters and (2) at least one polymer selected from the group consisting of vinyl pyrrolidone polymers, polymers vinyl alcohol, starches and mixtures thereof (which are discussed in detail above).

Another aspect of the present invention is a method of forming a layered material from woven fabric and a polymer matrix material by coating a woven product with a polymer matrix material to form a coated fabric and to apply heat to it. The woven product includes yarn containing E-fiberglass. The improvement is that the E-glass fibers have a coating that is compatible with the polymer matrix material, the yarn having a transport pulling force of more than 100,000 gram-force per gram of mass of yarn using an air needle nozzle described in detail above, moving at a speed of 274 meters per minute with an air pressure of about 310 kilopascals, and the layered product has a bending strength in the direction of filling the fabric of more than about 3 • 10 ⁷ kg / m ² .

 Another aspect of the present invention is a method of forming a laminate from a woven product and a polymeric matrix material by coating the woven product with a polymeric matrix material to form a coated fabric and expose it to heat. The fabric product contains yarn comprising E-fiberglass. The improvement is that E-glass fibers have a coating that is compatible with the polymer matrix material, which coating includes (1) a polyester and (2) at least one polymer selected from the group consisting of vinyl pyrrolidone polymers, vinyl alcohol polymers and starches.

Information confirming the possibility of carrying out the invention
Further, the present invention is illustrated by the following specific examples, not limiting its scope.

Example 1
The compatibility of the samples of some different types of yarn with the pneumatic shuttleless spinning process was determined using the test method "Air Jet Transport Drag Force", which is discussed in detail above.

Samples of yarn according to the present invention were coated with aqueous AF forming adhesives compatible with the matrix resin according to Table 1A and evaluated using the Air Jet Transport Drag Force test method. Less than 1% by weight of acetic acid was added to each composition. Each of the forming adhesive compositions contained 2.5 wt.% Solids. Each coated fiberglass yarn was twisted to form yarn and wound on bobbins in the same way using traditional twisting equipment. Sample _{Bac was} coated with the aqueous forming adhesive composition B, but dried in vacuo at 190 ^° F for 46 hours. Each of the AF samples had a calcination loss of less than 1 wt.%. Samples C _hi and D _hi had loss values on ignition of 1.59 and 1.66 wt.%, Respectively.

Commercial samples of yarn coated with a starch-oil system of grades 631 and 633 D-450; yarns coated with starch oil grades 690 and 695, as well as commercial G-yarns PPG Industries, Inc., were also evaluated using the Air Jet Transport Drag Force test method. Three comparative samples X1, X2 and X3, each of which was coated with the same aqueous forming composition X described in Table 1B, were also subjected to a similar test. Comparative sample X1 contained 2.5 wt.% Solid material. Comparative sample X2 contained 4.9 wt.% Solid material and was dried in air for 8 hours at 25 ^° C. Comparative sample X3 contained 4.6 wt.% Solids.

 Each yarn sample was fed at a speed of 274 meters / minute through a Sulzer Ruti model 044455001 needle air nozzle nozzle, which had a 2 mm diameter internal air jet chamber and a 20 cm nozzle outlet tube (commercially available from Sulzer Ruti of Spartanburg, North Carolina) at air pressure 310 kilopascals. The tensiometer was placed in a state of contact with the yarn at a point before the yarn entered the air jet nozzle. Using a tensiometer, measurements were made of the gram force (traction force) affecting each yarn sample, under the influence of an air jet on the corresponding yarn sample, drawn into the air nozzle. The obtained values are presented in table 1C.

As follows from the presented table 1C, each yarn coated with an adhesive composition compatible with the polymer matrix material according to the invention had traction transport values under the action of an air jet above 100,000. Only commercial strands glued with a starch-oil mixture, which are usually incompatible with the polymer discussed above matrix material, the values of traction transport under the influence of an air stream above 100000. Samples of yarn C _hi and D _hi with coatings compatible with the polymer matrix had transport values traction under the action of an air stream of less than 100,000 due to the large amount of coating on the yarn, i.e. they had losses on ignition of more than 1.5 wt.%, which inhibited filamentization of yarn under the influence of an air stream.

In order to evaluate the strength of the layered product, style 7628 fabrics (stylistic parameters discussed above) were formed from samples 695, sample B, and sample B _vac G75 (discussed above), respectively. Eight layers of each tissue sample were sandwiched with a FR-4 resin system from the epoxy resin group EPON 1120-A80, dicyandiamide, 2-methylimidazole and DOWANOL PM to produce laminates.

 Each laminated product was evaluated for bending strength (maximum breaking load) by testing according to ASTM D-790 and IPC-TM-650 Test methods Manual of the Institute for Interconnecting and Packaging Electronics (December 1994) (these methods are referenced in the present description ), the metal cladding being completely removed by etching according to Section 3.8.2.4 of IPC 4101, and by the shear strength between the layers (short-beam strength) using a span of 15.9 mm and a movement speed of the transverse tip of 1.27 mm / min, according to ASTM D-2344, moreover, this method is referred to in the present general description. The results of such evaluations are presented in table 1D.

As follows from the results presented in table 1D, the layered samples B and B _vac obtained according to the present invention had a higher bending strength than layered samples made from fiberglass yarn 695 coated with starch with oil.

Example 2
The coefficient of thermal expansion of the laminate in the z-axis direction (Z-CTE), i.e. according to the thickness of the laminate, was evaluated for layered samples, each of which consisted of eight layers of style 7628 fabric made from samples of coated B _vac yarn (Sample A) and 695 yarns coated with a starch-oil system (discussed above) (control samples). A laminate was prepared using the FR-4 epoxy resin described in Example 1 and clad with copper according to IPC Test Method 2.4.41. The coefficient of thermal expansion in the direction of the z axis was evaluated for each sample of the layered product at 288 ^o C according to the test method IPC 2.4.41. The results of this assessment are presented in table 2.

 As follows from the results presented in table 2, samples of layered products A1-A3 according to the present invention have lower coefficients of thermal expansion in the z axis direction of the laminates than the corresponding values for control samples 1 and 2, which were prepared from yarn 695 coated with a starch mixture oil.

Example 3
The aqueous forming adhesive compositions AD (discussed in Table 1A of Example 1) and comparative sample 31 were applied to E-glass fiber yarn. The formulation of comparative sample 31 is shown in table 3. Each of the forming adhesive compositions contained 2.5 wt.% Solids. Each coated fiberglass strand was twisted to form yarn and wound on bobbins in the same manner using traditional twisting equipment.

The yarns of samples AD, comparative sample 1 and comparative sample 2 ¹¹⁷ were evaluated by some physical properties, such as loss on ignition (LOI), compatibility with the air stream (air draft), friction force and the number of broken threads.

 The average weight loss on ignition (weight percent solids of the forming sizing composition divided by the total weight of glass and the dried forming adhesive composition) in three successive determinations for each sample are shown in Table 4. Each yarn was evaluated by the value of the air force or tension by feeding the yarn with a controlled speed of 274 m / min through a voltage recorder with which voltage was generated in the yarn and a Ruti air nozzle with a diameter of 2 mm at an air pressure of 310 kPa.

 Samples and comparative samples were also evaluated for friction by creating a stress of approximately 30 grams on each yarn sample as the sample was passed at a speed of 274 m / min through a pair of traditional voltage measuring devices with a stationary chrome post 5 centimeters in diameter mounted between them to marking yarn at a distance of about 5 cm from the straight path between the voltage measuring devices. The difference in force values, expressed in grams, is presented in Table 4. The friction force test is designed to simulate the friction forces that the yarn undergoes during spinning operations.

 Each sample and comparative sample were also evaluated for the presence of broken filaments using an abrasion test. A voltage of two hundred grams was created on each test sample as it passed at a speed of 0.46 m / min for 5 minutes through an abrasive test device. Two tests were performed on each sample and comparative sample, and the average value of the number of destroyed filaments is presented in table 4. The abrasion tester consists of two parallel rows of steel reels, each row located at a distance of 1 inch from the other. Each test yarn sample was tucked between two adjacent birch bark from the first row of birch bark, then tucked between two adjacent birch bark from the second row of the birch, and the distance between these rows was half an inch (1.27 cm). Groups of bird feathers moved back and forth at a distance of 4 inches (10.2 cm) in a direction parallel to the movement of yarn at a speed of 240 cycles per minute. Table 4 presents the results of measuring air traction, friction, and the number of destroyed filaments under abrasion conditions for samples A-D and comparative samples.

 As follows from the data given in table 4, samples A and B, which were coated with adhesive compositions containing boron nitride according to the present invention, contained a small number of broken filaments, low friction and high air draft values were observed compared to comparative samples . Samples C and D also had higher values of air traction than comparative samples. The air draft test is a relative test designed to simulate the insertion process of a weft of a pneumatic shuttleless loom in which the yarn is advanced along the loom under the action of the driving force of the air stream. Yarns that are easier to filamenize under the influence of an air stream provide a large surface area for the driving force of the air stream, as a result of which the movement of the yarn across the machine can be facilitated and the process productivity can be increased. The air draft values for samples A-D (samples prepared according to the present invention) are higher than the corresponding values for comparative samples, which indicates excellent compatibility with the air stream.

Example 4
Each of the components in the amounts indicated in Table 5 was mixed to form the forming adhesive compositions E, F, G and H according to the present invention, and a comparative sample was obtained by a method similar to that described above. Less than 1% by weight of acetic acid, based on the total weight of the composition, was added to each composition.

 Each of the aqueous forming adhesive compositions of Table 5 was applied to strands of G75 E-glass fiber. Each of the forming adhesive compositions contained 6-25 wt.% Solids.

 Each coated fiberglass strand was twisted to form yarn and wound on bobbins in the same way using traditional twisting equipment. Yarn from samples F and H showed minimal creep sizing during twisting, while samples E and G showed a significant creep sizing during twisting.

 The yarns of samples EH and a comparative sample were evaluated for air draft in the same manner as described in example 3, except that the values of air draft were determined for two bobbins at pressures shown in table 6. Each yarn was evaluated for the average number of destroyed elementary yarns at 1200 meters of yarn at a speed of 200 meters / min using a Shirley Model 84041L Shattered Filament Detector manufactured by SDL International Inc. of England. These values represent the average of measurements taken on four bobbins with each of the yarns. The values of the number of destroyed filaments were recorded from parts taken from a full bobbin, 136 g and 272 g of yarn wound from a bobbin.

 Each yarn was also evaluated for the gate voltage, and the results of such a test are shown in Table 6. The number of broken filaments, measured according to the gate voltage method, was determined by winding a yarn sample from a bobbin at a speed of 200 meters / min, threading the yarn through a series of 8 parallel ceramic studs and passing yarn through a Shirley shattered filament detector to count the number of shattered filaments.

 Although the results presented in table 6 show that the samples of the present invention EH have significantly higher abrasion resistance than the comparative samples, it is assumed that the results are not final, since the polyethylene emulsion component of the comparative example, which is not in the samples EH, affects the abrasive properties of yarn.

 From the above description, it can be seen that the present invention provides laminates having good flexural strength, as well as a modulus and coefficient of thermal expansion in the z direction and other desirable distinguishing features that find application in a large number of applications such as reinforcement (reinforcement ) mounting printed circuit boards.

 One skilled in the art will appreciate that the described technical solutions may be modified without violating the broad inventive concept of the invention. Therefore, it should be borne in mind that the present invention is not limited to the described specific technical solutions and covers a variety of modifications falling within the scope of the invention, as indicated in the attached claims.

Claims (60)

1. A reinforced laminate for the backbone of electronic printed circuit boards, comprising (a) a polymeric matrix material and (b) a woven material including fiberglass filaments at least partially coated with a coating compatible with the polymeric matrix material, and the loss on ignition for yarn is 0, 01-0.6 wt.%, And the transport tractive force under the action of an air stream is more than 100,000 gram-forces per gram-mass of yarn, when using a needle air-jet nozzle unit including an internal air-blast chamber dia 2 mm and the nozzle exit tube 20 cm long, at a yarn feed speed of 274 m / min and an air pressure of 310 kPa, the laminate having a bending strength in the direction of the woven material of more than 3 × 10 ⁷ kg / m ² . 2. The reinforced laminate according to claim 1, characterized in that the polymer matrix material includes at least one material selected from the group consisting of thermoset matrix materials and thermoplastic matrix materials. 3. The reinforced laminate according to claim 2, characterized in that the polymer matrix includes at least one thermosetting matrix material selected from the group consisting of thermosetting polyesters, vinyl esters, epoxides, phenolic compounds, amino plastics, thermosetting polyurethanes and mixtures thereof . 4. The reinforced laminate according to claim 3, characterized in that the thermoset matrix material includes epoxide. 5. The reinforced laminate according to claim 2, characterized in that the polymer matrix material includes at least one thermoplastic matrix material selected from the group consisting of polyolefins, polyamides, thermoplastic polyurethanes, thermoplastic polyesters, vinyl polymers, polyimides, polyethersulfones, polyphenyl sulfones, polyether ketones, polyphenylene oxides, polyphenylene sulfides, polyacetals, polycarbonates and mixtures thereof. 6. The reinforced laminate according to claim 1, characterized in that the coating of fiberglass threads of the woven material includes a lubricant consisting of solid inorganic particles. 7. The reinforced laminate according to claim 6, characterized in that the solid inorganic particles of the lubricant have a lamellar structure. 8. The reinforced laminate according to claim 6, characterized in that the particles of solid inorganic lubricant include at least one particle selected from the group consisting of particles of non-hydratable solid inorganic lubricant, particles of hydratable solid inorganic lubricant and mixtures thereof. 9. The reinforced laminate according to claim 8, characterized in that the particles of a non-hydratable solid inorganic lubricant include at least one particle selected from the group consisting of graphite, boron nitride, metal dichalcogenides, cadmium iodide, silver sulfide and mixtures thereof. 10. The reinforced laminate according to claim 9, characterized in that the particles of non-hydratable solid inorganic lubricants include particles of boron nitride having a hexagonal crystal structure. 11. The reinforced laminate according to claim 9, characterized in that the particles of a non-hydratable solid inorganic lubricant include at least one metal dichalcogenide selected from the group consisting of molybdenum disulfide, molybdenum diselinide, tantalum disulfide, tantalum disulide, tungsten disulfide, disyleneide tungsten and mixtures thereof. 12. The reinforced laminate according to claim 8, characterized in that the particles of non-hydratable solid inorganic lubricant include at least one particle selected from the group consisting of indium, thallium, tin, copper, zinc, gold, silver, calcium carbonate, calcium fluoride, zinc oxide and mixtures thereof. 13. Reinforced laminate according to claim 8, characterized in that the particles of hydratable solid inorganic lubricant include phyllosilicates. 14. The reinforced laminate according to item 13, wherein the phyllosilicates include at least one phyllosilicate selected from the group consisting of mica, talc, gypsum, kaolinite, montmorillonite and mixtures thereof. 15. The reinforced laminate according to claim 8, characterized in that the hardness of the particles of solid inorganic lubricant is less than or equal to the hardness of the E-glass fibers. 16. The reinforced laminate according to claim 1, characterized in that the coating of glass fiber filaments of the woven material includes a film-forming polymer. 17. The reinforced laminate according to claim 1, characterized in that at least one of the glass fiber strands is obtained from a fiber-forming material selected from the group consisting of non-glass inorganic materials, natural materials, organic polymeric materials, and combinations thereof. 18. The reinforced laminate according to claim 1, characterized in that the bending strength in the filling direction is higher than 4.9 × 10 ⁷ kg / m ² . 19. Reinforced laminate for the backbone of electronic printed circuit boards, comprising (a) a polymer matrix material and (b) a reinforced woven material including fiberglass strands at least partially coated with a polymer matrix compatible coating comprising (1) polyester and (2 ) at least one polymer selected from the group consisting of polymers of vinyl pyrrolidone, polymers of vinyl alcohol and starches. 20. The reinforced laminate according to claim 19, characterized in that the polymer matrix material includes at least one material selected from the group consisting of thermosetting matrix materials and thermoplastic matrix materials. 21. The reinforced laminate according to claim 20, characterized in that the polymer matrix material includes at least one thermosetting matrix material selected from the group consisting of thermosetting polyesters, vinyl esters, epoxides, phenolic compounds, amino plastics, thermosetting polyurethanes and their mixtures. 22. The reinforced laminate according to item 21, wherein the thermoset matrix material includes epoxide. 23. The reinforced laminate according to claim 20, characterized in that the polymer matrix material includes a thermoplastic matrix material selected from the group consisting of polyolefins, polyamides, thermoplastic polyurethanes, thermoplastic polyesters, vinyl polymers, polyimides, polyethersulfones, polyphenylsulfones, polyethersulfones, polyphenylene polyphenylene sulfides, polyacetals, polycarbonates and mixtures thereof. 24. The reinforced laminate according to claim 19, characterized in that the coating of fiberglass yarns of the woven material further includes solid inorganic lubricant particles. 25. Reinforced laminate according to paragraph 24, wherein the solid inorganic lubricant particles have a lamellar structure. 26. The reinforced laminate according to paragraph 24, wherein the particles of solid inorganic lubricant include at least one particle selected from the group consisting of particles of non-hydratable solid inorganic lubricant, particles of hydratable solid inorganic lubricant and mixtures thereof. 27. The reinforced laminate according to p. 26, characterized in that the particles of non-hydratable solid inorganic lubricants include at least some particles selected from the group consisting of graphite, boron nitride, metal dichalcogenides, cadmium iodide, silver sulfide and mixtures thereof. 28. The reinforced laminate according to item 27, wherein the particles of non-hydratable solid inorganic lubricants include particles of boron nitride having a hexagonal structure. 29. The reinforced laminate according to item 27, wherein the particles of non-hydratable solid inorganic lubricants include at least one metal dichalcogenide - molybdenum disulfide. 30. The reinforced laminate according to item 26, wherein the particles of non-hydratable solid inorganic lubricants include at least one particle selected from the group consisting of indium, waist, tin, copper, zinc, gold, silver, calcium carbonate, calcium fluoride, zinc oxide and mixtures thereof. 31. The reinforced laminate according to claim 26, wherein the particles of hydratable solid inorganic lubricant include phyllosilicates. 32. Reinforced laminate according to p. 31, wherein the phyllosilicates include at least one phyllosilicate selected from the group consisting of mica, talc, gypsum, kaolinite, montmorillonite and mixtures thereof. 33. The reinforced laminate according to paragraph 24, wherein the hardness of the particles of solid inorganic lubricant is less than or equal to the hardness of the glass fibers. 34. The reinforced laminate according to claim 19, characterized in that the coating of glass fiber strands from E-glass fibers of a woven material includes a film-forming polymer. 35. The reinforced laminate according to claim 19, characterized in that at least one of the glass fiber strands is obtained from a fiber-forming material selected from the group consisting of non-glass inorganic materials, natural materials, organic polymeric materials, and combinations thereof. 36. The reinforced laminate according to claim 19, characterized in that the loss on ignition for filaments is 0.01-0.6 wt.%, The force of the transport thrust under the influence of an air stream is more than 100,000 grams of force per gram of mass of yarn when using a needle air jet nozzle assembly with an internal air-blasting chamber with a diameter of 2 mm and a nozzle outlet tube 20 cm long, with a yarn feed speed of 274 m / min and an air pressure of 310 kPa. 37. The reinforced laminate according to claim 19, characterized in that the bending strength in the filling direction is more than 3 × 10 ⁷ kg / m ² . 38. A reinforced laminate for the backbone of electronic printed circuit boards, comprising (a) a polymer matrix material and (b) a reinforced woven material comprising fiberglass strands at least partially coated with a compatible polymer matrix material, a coating comprising (1) polyester and ( 2) vinylpyrrolidone polymer. 39. The reinforced laminate according to § 38, wherein at least one of the glass fibers is selected from the group consisting of E-glass fibers, D-glass fibers, S-glass fibers, Q-glass fibers, fibers - derivatives of E-glass, and combinations thereof. 40. An electronic printed circuit board comprising (a) a laminate for warp, comprising (i) a woven material comprising fiberglass yarns, wherein the losses on ignition for the yarns are 0.01-0.6 wt.% And the transport force due to air jet more than 100,000 grams of force per gram of mass of yarn, using a needle air-jet nozzle assembly with an internal air-jet chamber with a diameter of 2 mm and an outlet tube of a nozzle 20 cm long, with a yarn feed speed of 274 m / min and an air pressure of 310 kPa, and the laminate has a durable nce to bending in the direction of filling the above 3 × July ¹⁰ kg / m ^2, and (ii) a layer of a polymeric matrix material applied to at least a portion of the woven fabric, and (b) an electrically conductive layer disposed on selected portions of a laminate of selected sides . 41. An electronic circuit board comprising (a) a backing laminate comprising (i) a woven fabric comprising fiberglass strands at least partially coated with a coating comprising (1) polyester and (2) at least one polymer selected from the group consisting of vinyl pyrrolidone polymers, vinyl alcohol polymers and starches, and (ii) a layer of polymer matrix material deposited on at least part of the woven material, and (b) an electrically conductive layer located on selected areas of selected sides of the laminate . 42. An electronic circuit board comprising (a) a laminate for warp, comprising (i) a first composite layer comprising (1) a woven material comprising fiberglass yarns, wherein the annealing loss for yarns is 0.01-0.6 wt.% and the transport thrust force under the influence of an air stream is more than 100,000 gram-forces per gram-mass of yarn, using a needle air-jet nozzle assembly with an internal air-jet chamber with a diameter of 2 mm and an outlet tube of a nozzle 20 cm long, with a yarn feed speed of about 274 m / min and crushed and air 310 kPa, the laminate having a flexural strength in the filling direction above 3 × 10 ⁷ kg / m ² , and (2) a layer of polymer matrix material deposited on at least part of the woven material, and (ii) a second composite a layer different from the first composite layer, and also (b) an electrically conductive layer located on the necessary areas of the desired sides of the laminate. 43. An electronic circuit board comprising (a) a laminate for a substrate, comprising (i) a first composite layer comprising (1) a woven fabric comprising fiberglass strands at least partially coated with a coating comprising (A) polyester and (B) at least one polymer selected from the group consisting of vinyl pyrrolidone polymers, vinyl alcohol polymers and starches, and (2) a layer of polymer matrix material deposited on at least part of the woven material, and (ii) a second composite layer, different from the first composite Loy, and (b) an electrically conductive layer disposed on the necessary areas of the right sides of the laminate. 44. The electronic circuit board according to item 43, wherein at least one of the glass fibers is selected from the group consisting of E-glass fibers, D-glass fibers, S-glass fibers, Q-glass fibers, fibers derivatives of E-glass and their combinations. 45. The electronic circuit board according to any one of paragraphs.40-43, characterized in that it further includes at least one hole passing through at least part of the printed circuit board. 46. Electronic circuit board according to any one of paragraphs.40-43, characterized in that it includes the packaging of the first, second or third level. 47. Copper-clad reinforced laminate for the backbone of electronic printed circuit boards, comprising (a) a polymer matrix material and (b) one or more layers of reinforced woven material, each layer comprising at least partially 30-75 wt.% Glass fiber strands coated with a polymer matrix material coating, and the laminate has a coefficient of thermal expansion in the direction of the z axis of less than 4.5% at a temperature of 288 ° C. 48. The laminate according to item 47, wherein the coefficient of thermal expansion in the direction of the z axis is in the range of 1-4.5% at a temperature of 288 ° C. 49. The laminate according to claim 47, wherein at least one of the glass fibers is selected from the group consisting of E-glass fibers, D-glass fibers, S-glass fibers, Q-glass fibers, E derivatives fibers -glass, and combinations thereof. 50. The laminate according to clause 47, characterized in that it further includes at least in one of the layers one hole passing through at least part of the printed circuit board. 51. The laminate according to item 47, wherein the packaging includes a first, second or third level. 52. The laminate according to item 47, wherein it contains eight layers of woven material style 7628. 53. A method of producing a woven material by interlacing the first yarn with the second yarn to form a fabric, the method comprising the step of: at least partially covering the first fiber-glass filament with a polymer matrix material comprising (1) polyester and (2) at least one polymer selected from the group consisting of vinylpyrrolidone polymers, vinyl alcohol polymers, starches and mixtures thereof. 54. The method according to item 53, wherein at least one of the glass fibers is selected from the group consisting of E-glass fibers, D-glass fibers, S-glass fibers, Q-glass fibers, fibers of derivatives E- glass and their combinations. 55. A method of producing a laminate from a woven material and a polymeric matrix material by at least partially coating the woven material with a polymeric matrix material to obtain a coated woven material and applying heat to this coated woven material, the woven material comprising yarn comprising fiberglass yarns, comprising in that the fiberglass yarns are at least partially coated with a coating compatible with the polymer matrix material, and the loss on ignition for yarn is 0.01- 0.6 wt.% And the transport thrust force under the influence of an air stream is more than 100,000 gram-forces per gram-mass of yarn, using a needle air-jet nozzle assembly having an internal air-jet chamber with a diameter of 2 mm and an outlet tube of the nozzle 20 cm long at a speed yarn supply 274 m / min and an air pressure of about 310 kPa, and the laminate has a bending strength in the filling direction of more than 3 × 10 ⁷ kg / m ² . 56. The method according to § 55, wherein at least one of the glass fibers is selected from the group consisting of E-fibers, E-glass, D-glass fibers, S-glass fibers, Q-glass fibers, fibers derivatives of E-glass and their combinations. 57. A method of producing a laminate from a woven material and a polymer matrix material by at least partially coating the woven material with a polymer matrix material to obtain a coated woven material and applying heat to this woven material, the woven material comprising fiberglass yarns, the method comprising that the glass fiber strands are at least partially coated with a coating compatible with the polymer matrix material, comprising (1) a polyester, and (2) at least one polymer selected from the group consisting consisting of polymers of vinyl pyrrolidone, polymers of vinyl alcohol and starches. 58. The laminate according to clause 57, wherein at least one of the glass fibers is selected from the group consisting of E-fibers, E-glass, D-glass fibers, S-glass fibers, Q-glass fibers, fibers derivatives of E-glass and their combinations. Priority on points: 03.03.1998 - claims 1-17, 20-35, 39, 44-46, 49-51, 54, 56, 58; 08/06/1998 - pp. 18-19, 36-38, 40-43, 47-48, 52-53, 55, 57.

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