JP2002505216A - Glass fiber-reinforced laminate, electronic circuit board and fabric assembling method - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention provides a printed circuit board with a reinforced laminate having a woven reinforced fabric of yarn, the yarn containing E-glass fibers having a coating compatible with the polymer matrix material. The yarn has a loss on ignition in the range of about 0.01 to about 0.6% by weight, and an air jet transport resistance greater than about 1 gram weight per gram mass of yarn, the air jet transport resistance being less than 2 grams. Using a needle air jet nozzle unit with an internal air jet chamber having a diameter of millimeters and a nozzle exit tube having a length of 20 cm, a yarn feed rate of about 300 yards / minute and about It is rated at an air pressure of 310 kilopascals (about 45 pounds per square inch) gauge. The laminate has a flexural strength greater than about 3 × 10 ⁷ kilograms per square meter (about 42.7 kpsi) in the fabric filling direction. The coating of the yarn may comprise polyester and a polymer selected from vinylpyrrolidone polymers, vinyl alcohol polymers, starch and mixtures thereof. Alternatively, the laminate has a coefficient of thermal expansion in the z-direction of less than about 4.5% at a temperature of 288 ° C.

Description

DETAILED DESCRIPTION OF THE INVENTION

(Cross-Reference of Related Applications) The present application discloses “Glass Fiber-Reinforced Laminat”
es, Electronic Circuit Boards and Met
1, entitled "Hods for Assembling a Fabric"
Filed on Aug. 6, 998, B.A. Novich et al. Is a continuation-in-part of US patent application Ser. No. 09 / 130,270. This U.S. patent application Ser.
No. 0,270 describes "Inorganic Lubricant-Coated."
Glass Fiber Strands and Products Inc
, entitled "Ludding the Same", filed March 3, 1998, This is a continuation-in-part of US patent application Ser. No. 09 / 034,525 by Novich et al.

[0002] This application is related to US patent application Ser. No. 09/034, filed Mar. 3, 1998.
No. 078, entitled “Methods for Inhibitin”
g Abrasive Wear of Glass Fiber Stran
ds ". US Patent Application No. 199 by Novich et al.
"Glass Fiber Strands Coated Wi," which is a continuation-in-part of U.S. patent application Ser. No. 09 / 034,663 filed on Mar. 3, 2008.
the Thermally Conductive Inorganic So
lid Particles and Products Included
entitled "The Same". US Patent Application No.
No .; US Patent Application Serial No. 09 / 034,0 filed March 3, 1998;
No. 77, “Impaired Glass Five”
r Strands and Products Included the
B. titled "Same". US Patent Application No. by Novich et al .;
And U.S. Patent Application Serial No. 09 / 034,05, filed March 3, 1998.
No. 6 “Inorganic Particle-Coat”
ed Glass Fiber Strands and Products
Inc. entitled "Including the Same". Novich et al. Each of these applications was filed at the same time as the present application.

FIELD OF THE INVENTION [0003] The present invention relates generally to reinforced laminates for electronic circuit boards, and more particularly, to the matrix resin of the laminate, and to modern air jet looms.
a laminate comprising a glass fiber woven fabric having a coating that facilitates weaving with the same.

BACKGROUND OF THE INVENTION Electronic circuit boards are typically formed from laminated fabric layers composed of reinforcing fibers such as glass fibers, which provide dimensional stability to the board.
The integrity of the electronic circuit mounted on the substrate is maintained. Substrate distortion or warpage caused by different coefficients of thermal expansion of the substrate components caused by temperature gradients during manufacture and use can adversely affect the adhesion of the circuit to the substrate, and thus also its reliability and performance. Can have adverse effects.

[0005] Smoothness of the laminate surface can also affect the adhesion of the electronic circuit to the substrate. In the woven cloth reinforcement, defects such as filament breaks or fuzz can adversely affect surface smoothness and prevent adhesion between the circuit and the laminate. Fuzz occurs when the warp yarn is impacted by the reed or when the weft yarn is blown with a high speed air jet in an air jet loom, when the bundle of glass fiber filaments is severed.
As the speed of modern air jet looms increases, the integrity of the strand and the resistance to fiber breaks imposed by the coating of the strand become increasingly important.

[0006] Coatings on glass fibers also affect the quality of the substrate. Starch is a component in many sizing compositions for glass fibers used in weaving operations and can adversely affect the adhesion between the glass fibers and the laminate matrix material. That is, starch is generally not compatible with the resin matrix material of the laminate. To avoid incompatibility between glass fiber and matrix material,
The coating or sizing composition is typically prepared by pyrolyzing the sizing components (heat treatment or deoiling) or washing with water prior to lamination.
Removed from woven cloth. Conventional thermal cleaning processes include heating the cloth at 380C for 60-80 hours. The cleaned cloth is then recoated with a silane coupling agent to improve the adhesion between the glass fibers and the matrix resin.

[0007] The strength of glass fibers, and more specifically the flexural strength of laminates, can be significantly reduced by these hot fiber coating removal processes. Thermal cleaning of high silica content glass fibers, such as D-glass, S-glass, and Q-glass, is undesirable, especially due to loss of strength and discoloration.

[0008] Many coating compositions for glass fibers that require cleaning with heat or water before being used as reinforcements in composites or laminates,
It is disclosed in the art. Japanese Patent Application No. 9-208,268 states that
Immediately after spinning with starch or synthetic resin and 0.001-20.0 weight percent of inorganic solid particles (e.g., colloidal silica, calcium carbonate, kaolin, and talc) from coated glass fibers A cloth having a formed yarn is disclosed. Prior to forming the laminate, deoiling with heat or water is required.

[0009] US Pat. No. 5,286,562 describes a screen product that can be woven on an air jet loom having a coating of at least 45 weight percent of wax, lubricant, polyvinylpyrrolidone, and an organosilane coupling agent. scree
Textile strand for en product
d) is disclosed. U.S. Pat. No. 5,038,555 discloses epoxy film formers, emulsifiers, lubricants, organofunctional metal coupling agents (or
gano functional metallic coupling ag
twist) for screen products, coated with an aqueous chemical treatment composition comprising polyvinylpyrrolidone, polyethylene and water.
ted bundles are disclosed.

In order to avoid thermal cleaning of the glass fiber cloth, Japanese Patent Application No. 8-1
No. 19,682 discloses a primary sizing agent for glass fibers comprising a water-soluble epoxy resin and having a pH of 5.5 to 7.5. This primary sizing agent facilitates sizing removal with water. Similarly, US Pat.
No. 6,777, at least one water-soluble film-forming agent selected from the group consisting of an amine-modified epoxy resin, an ethylene oxide-added epoxy resin and an ethylene oxide-added bisphenol A, a silane coupling agent And coating the glass yarn with a primary sizing having a lubricant, washing the yarn with water to reduce the primary sizing amount to less than 0.25 weight percent LOI, and treating with a secondary sizing agent. Discloses a method of manufacturing a glass cloth for reinforcing a resin. Japanese Patent Application No. 9-268,
No. 034 discloses a non-twist-free type comprising a water-soluble urethane composition and / or a water-soluble epoxy product modified by an addition reaction with a polyhydric alcohol.
e) discloses a binder for glass fiber yarns.

US Pat. No. 4,933,381 discloses a glass fiber comprising an epoxy film former, a nonionic lubricant, a cationic lubricant, a silane coupling agent, and an acid (eg, acetic acid or citric acid). Discloses a resin-compatible size composition for the following.

Japanese Patent Application No. 8-325,950 discloses a glass fiber sizing agent comprising, as essential components, polyvinylpyrrolidone, a water-soluble epoxy resin amine addition product, and a silane coupling agent, This glass fiber sizing agent does not require heat removal from the completed glass cloth.

Japanese Patent Application No. 7-102,483 discloses a warp secondary sizing agent for glass fibers for weaving glass cloth, which does not require oil removal by heating. The warp secondary sizing agent is mainly composed of polyvinylpyrrolidone and contains additives such as high molecular weight polyethylene oxide. A water-soluble epoxy resin may be included as a binding component.

What is needed is a compatibility with a wide variety of polymer matrix materials,
With glass fiber, which prevents fuzz and fiber breaks from forming during weaving, improves adhesion between laminates and circuits, and is compatible with modern air jet weaving equipment and increases productivity is there.

SUMMARY OF THE INVENTION One aspect of the present invention is a reinforced laminate for an electronic support. The laminate comprises a woven reinforced fabric comprising: (a) a polymer matrix material; and (b) a yarn comprising glass fibers at least partially coated with a coating compatible with the polymer matrix material. The yarn has a loss on ignition of from about 0.01 to about 0.6 weight percent.
an inner diameter of 2 millimeters at a yarn feed rate of about 300 yards per minute and an air pressure of about 310 kilopascals (about 45 pounds per square inch) gauge. Using an air jet chamber and a needle air jet nozzle unit having a nozzle exit tube having a length of 20 centimeters, an air jet transport resistance (Ai) greater than about 100,000 grams weight per gram mass of yarn
r Jet Transport Drag Force). Here, the laminate has a flexural strength in the filling direction of the fabric of greater than about 3 × 10 ⁷ kilograms per square meter (about 42.7 kpsi).

Another aspect of the present invention is a reinforced laminate for an electronic support. The laminate,
(A) a polymer matrix material; and (b) a woven reinforced fabric comprising a yarn comprising glass fibers at least partially coated with a coating compatible with the polymer matrix material. The coating comprises (1
And (2) at least one polymer selected from the group consisting of vinylpyrrolidone polymers, vinyl alcohol polymers and starch.

Another aspect of the present invention is a reinforced laminate for an electronic support. The laminate,
(A) a polymer matrix material; and (b) a woven reinforced fabric comprising a yarn comprising glass fibers at least partially coated with a coating compatible with the polymer matrix material. The coating comprises (1
A) a polyester; and (2) a vinylpyrrolidone polymer.

[0018] Yet another aspect of the present invention relates to (a) a laminate for an electronic support; and (b)
An electronic circuit board including a conductive layer positioned adjacent a selected portion of a selected side of a laminate. The laminate of (a) comprises: (i) a woven fabric comprising a yarn comprising glass fibers; and (ii) a layer of a polymer matrix material applied on at least a portion of the fabric, wherein the yarn comprises about 0.1. 01 ~
Loss on ignition of about 0.6 weight percent and about 274 meters per minute (about 300
Needle with a 2 millimeter diameter inner nozzle and a nozzle exit tube having a length of 20 centimeters at a yarn feed rate of 30 yards) and an air pressure of about 310 kilopascals (about 45 pounds per square inch) gauge. And an air jet transport resistance of greater than about 100,000 gram weight per gram mass of yarn using an air jet nozzle unit.
Here, the laminate has a flexural strength in the filling direction of the fabric of greater than about 3 × 10 ⁷ kilograms per square meter (about 42.7 kpsi).

[0019] Another aspect of the present invention is a method for forming a conductive layer positioned adjacent to a selected portion of a selected side of a laminate, comprising: (a) a laminate for an electronic support; Including,
It is an electronic circuit board. The laminate of (a) comprises (i) (1) a polyester; and (
2) a woven fabric comprising a yarn comprising glass fibers at least partially coated with a coating comprising a vinylpyrrolidone polymer, a vinyl alcohol polymer, and at least one polymer selected from the group consisting of starch; and (ii) A polymer matrix material layer applied on at least a portion of the fabric.

[0020] Yet another aspect of the present invention relates to (a) a laminate for an electronic support; and (b)
An electronic circuit board including a conductive layer positioned adjacent a selected portion of a selected side of a laminate. The laminate of (a) comprises (i) a first composite layer; and (
ii) including a second composite layer different from the first composite layer, wherein the first composite layer of (i) comprises:
1) a woven fabric comprising a yarn comprising glass fibers; and (2) a layer of a polymer matrix material applied on at least a portion of said fabric;
The yarn has a loss on ignition of about 0.01 to about 0.6 weight percent, a yarn feed rate of about 300 yards per minute (about 274 meters per minute), and a yarn feed rate of about 310 kilopascals (about 45 pounds per square inch). At a gauge air pressure of less than about 100,000 gram weight per gram mass of yarn, using a needle air jet nozzle unit with an internal air jet chamber having a diameter of 2 millimeters and a nozzle exit tube having a length of 20 centimeters Large air jet transport resistance. Here, the laminated board is about 3 per square meter.
It has a flexural strength in the fabric filling direction of greater than × 10 ⁷ kilograms (about 42.7 kpsi).

Yet another aspect of the present invention relates to (a) a laminate for an electronic support; and (b)
An electronic circuit board including a conductive layer positioned adjacent a selected portion of a selected side of a laminate. The laminate of (a) comprises (i) a first composite layer; and (i)
i) including a second composite layer different from the first composite layer, wherein (i) the first composite layer comprises (1)
Woven comprising a yarn comprising glass fibers at least partially coated with a coating comprising: (A) a polyester; and (B) at least one polymer selected from the group consisting of a vinylpyrrolidone polymer, a vinyl alcohol polymer, and starch. And (2) a polymer matrix material layer applied on at least a portion of the fabric.

Another aspect of the present invention is a copper-clad for an electronic support.
) A reinforced laminate. The laminate includes: (a) a polymer matrix material; and (b) one or more plies of a woven reinforced fabric. Each ply includes between about 30 and about 75 weight percent yarns comprising glass fibers at least partially coated with a coating compatible with the polymer matrix material. Here, the laminate has a coefficient of thermal expansion in the z-direction of less than about 4.5 percent at a temperature of 288 ° C.

[0023] Yet another aspect of the invention is a method for assembling a fabric by interweaving a first yarn and a second yarn to form a fabric. Here, the improvement comprises a first yarn comprising glass fibers at least partially coated with a coating compatible with the polymer matrix material. The coating comprises (1) a polyester; and (2) at least one polymer selected from the group consisting of vinylpyrrolidone polymers, vinyl alcohol polymers, starch and mixtures thereof.

[0024] Yet another aspect of the invention provides that the woven fabric is at least partially coated with a polymer matrix material to form a coated fabric, and the coated fabric is heated by heating the coated fabric. A method for forming a laminate of a woven fabric and the polymer matrix material. The woven fabric includes a yarn that includes glass fibers. Wherein the improvements include: the glass fibers are at least partially coated with a coating that is compatible with a polymer matrix material;
With a loss on ignition of about 0.01 to about 0.6 weight percent, a yarn feed rate of about 300 yards per minute (about 300 yards) and an air pressure of about 310 kilopascals (about 45 pounds per square inch) gauge. Air jet delivery greater than about 100,000 gram weight per gram mass of yarn using a needle air jet nozzle unit having an internal air jet chamber having a diameter of 2 millimeters and a nozzle exit tube having a length of 20 centimeters And the laminate has a flexural strength greater than about 3 × 10 ⁷ kilograms per square meter (about 42.7 kpsi) in the filling direction of the fabric.

Another aspect of the invention is that the woven fabric is at least partially coated with a polymer matrix material to form a coated fabric, and the woven fabric is heated by heating the coated fabric. A method of forming a laminate of a synthetic fabric and the polymer matrix material. The woven fabric includes a yarn that includes glass fibers. Here, the improvement comprises that the glass fibers are at least partially coated with a coating compatible with the polymer matrix material. The coating comprises (1)
And (2) at least one polymer selected from the group consisting of vinylpyrrolidone polymers, vinyl alcohol polymers and starch.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The laminate of the present invention provides a laminate with a low coefficient of thermal expansion, good bending strength, thermal stability, hydrolysis stability, high humidity, Strengthened with woven fabrics, including coated fiberglass strands, which can provide low corrosiveness and low reactivity in the presence of acidic acids and alkalis. The coated fiberglass strand is compatible with a variety of polymer matrix materials, which may eliminate the need to heat or water clean the fiberglass fabric prior to lamination.

Another important advantage of the coated glass fiber strands of the present invention is good processability in weaving and knitting, especially in air jet weaving. "Air jet weaving," as used herein, refers to the injection of compressed air from one or more air jet nozzles to fill yarn (
Means one type of fabric weaving (shown in FIG. 5) in which weft yarns are inserted into the warp shed. Air jet transport drag (discussed below) is a measure of the compatibility of the strand with the air jet propulsion process. Higher air jet drag values indicate that the yarn is properly filamented without breakage, and therefore more aerodynamically conductive to air jet propulsion.

Other desirable properties that may be provided by the coated fiberglass strands of the present invention include low fuzz and halo, low filament breakage, and package ringer forming. (Package r
inger) and bobbin ringer
Low strand tension, low strand tension, and flyability (fliabilit
The higher y) and the shorter insertion time, these properties make weaving and knitting easier. In the case of printed circuit boards, the fabric is provided with good smoothness and few surface defects.

Referring now to the drawings, wherein like numerals indicate like parts throughout the drawings, FIG. 1 shows a laminate 10 according to the present invention. Laminate 10 includes a polymer matrix material 12 (described in detail below) reinforced with a woven reinforced fabric 14. Fabric 14 may be formed by any suitable knitting or weaving process, but is preferably formed by an air jet weaving process as described in detail below.

Referring now to FIGS. 2 and 3, fabric 14 includes one or more coated fiber strands 16 that include at least one glass fiber 18. The strand 16 preferably includes a plurality of glass fibers 18. The term "strand" as used herein means one or more individual fibers. The term "fiber" means individual filaments.

The glass fibers 18 may be formed from any type of fiberized glass composition known to those skilled in the art, including “E-glass”, “A-glass”, “C-glass”, “ D
-Glass, "Q-glass", "R-glass", "S-glass", and E-glass derivatives, and the like, and those made from fiberizable compositions. "E
"Glass derivative", as used herein, means a glass composition that contains small amounts of fluorine and / or boron, which is preferably fluorine-free and / or boron-free. Further, by small amounts, as used herein, is meant less than about 1 weight percent fluorine and less than about 5 weight percent boron. Examples of other glass fibers useful in the present invention include basalt and slag cotton fibers. Preferred glass fibers are E
-Formed from glass or E-glass derivatives. Such compositions and methods of making glass filaments therefrom are well known to those skilled in the art, and further discussion thereof is not deemed necessary in view of the present disclosure. If further information is needed, such glass compositions and fiberization methods are described in Loewe
nstein, "The Manufacturing Technology
of Glass Fibers "(3rd edition, 1993), 30-44, 4
7-60, 115-122, and 126-135, and U.S. Patent No. 4,542.
, 106 and 5,789,329 and The Institute
for Interconnecting and Packing El
published by Electronic Circuits (June 1997),
IPC-EG-140, "Specification for Finnish
ed Fabric Woven from 'E' Glass for P
Printed Boards, page 1, and these references are incorporated herein by reference.

The glass fibers have a nominal filament diameter in the range of about 5.0 to about 35.0 micrometers (corresponding to D to U and the filament nomenclature above), and preferably from about 9.0 to about 35.0 micrometers. It may have a nominal filament diameter in the range of 30.0 micrometers. The number of fibers per strand can be from about 100 to about 15,000, preferably from about 200 to about 7000. For more information on nominal filament diameters and glass fiber nomenclature, see Loewenstein's 25-2.
See page 7. This document is incorporated herein by reference.

The coated fiber strands 16 may further comprise fibers formed from other fiberizable natural or man-made materials, such as non-glass inorganic materials, natural materials, organic polymer materials, and combinations thereof, in addition to glass fibers. 20. "Fiberization"
The term, as used herein, means a material that can be formed into generally continuous filaments, fibers, strands or yarns.

[0034] Suitable non-glass inorganic fibers include ceramic fibers formed from silicon carbide, carbon, graphite, mullite, aluminum oxide, and piezoelectric ceramic materials. Non-limiting examples of suitable animal and plant derived natural fibers include:
Cotton, cellulose, natural rubber, flax, ramie, hemp, sisal,
And wool. Suitable man-made fibers include polyamides (such as nylon and aramid), thermoplastic polyesters (such as polyethylene terephthalate and polybutylene terephthalate), acrylics (polyacrylonitrile),
Examples include those obtained from a polyolefin, a polyurethane, and a vinyl polymer (eg, polyvinyl alcohol). Non-glass fibers and methods of preparing and processing such fibers that are believed to be useful in the present invention are described in "Enc
cycledia of Polymer Science and Tec
hnology, Vol. 6 (1967), pages 505-712. This document is incorporated herein by reference. It is understood that if desired, blends or copolymers of any of the above materials and combinations of fibers formed from any of the above materials may be used in the present invention.

Although the present invention is now discussed generally with reference to glass fiber strands, those skilled in the art will understand that strand 16 may further include one or more non-glass fibers as described above. I do.

Referring to FIGS. 2 and 3, in a preferred embodiment, the fibers 18 of the strands 16 are coated with a layer 22 of a coating composition that has been applied to at least a portion of the surface of the fibers 18, The fiber surface is protected from abrasion during processing and fiber 18 is prevented from breaking. Preferably, the coating composition is applied to the entire outer surface or periphery of each fiber 18 of the strand 16.

The coating composition may be present on the fiber, if desired, as a sizing (preferably), as a secondary coating applied on the sizing, and / or as a tertiary or outer coating. The terms "size,""sized," or "sizing," as used herein, refer to a coating composition that is applied to fibers immediately after forming the fibers.
In another embodiment, the terms "size,""sized," or "sizing" are further applied to the fibers after the conventional primary coating composition has been removed by heat, water, or chemical treatment, Refers to the coating composition (also known as finishing size), ie, the finished size imparted to the bare glass fibers incorporated into the fabric formation. The term "secondary coating" refers to the sizing composition after it has been applied,
Refers to a coating composition that is applied second to one or more strands, and is preferably at least partially dried.

The coating composition includes one or more polymer materials, such as a thermosetting or thermoplastic material, that are compatible with the polymer matrix material 12 of the laminate 10. That is, the components of the coating composition include a wet-out and a wet-out of the matrix material on the fiber strands.
easy to provide and provide appropriate physical properties in the composite. The polymeric material preferably forms a substantially continuous film when applied to the surface of the fibers 18. The polymeric material can be water-soluble, emulsifiable, dispersible, and / or curable.

In a preferred embodiment, the coating composition comprises a thermosetting matrix material (eg, F.R.
R-4 epoxy resin, which is a multifunctional epoxy resin and one of the present invention
In one particular embodiment, the material comprises one or more polymer film-forming materials compatible with bifunctional brominated epoxy resins) and polyimides). Electronic Materials Handbook, ASM I
See pages 534-537 of international (1989). This document is incorporated herein by reference. The phrase "compatible with a thermoset matrix material", as used herein, refers to a component of the coating composition that wets and wets out of the matrix material onto the fiber strands. Means to facilitate, provide appropriate physical properties in the composite, be chemically compatible with the thermoset matrix material, and be resistant to hydrolysis. A measure of the state of penetration of the polymer matrix material into the mat is called "wet through". The measure of the state in which the polymer matrix material is able to flow into the glass fiber mass, whereby the entire surface of each glass fiber is substantially completely encapsulated by the polymer matrix material, is called "wet out".

Useful polymeric film forming materials include thermoplastic polyesters, vinyl polymers, polyolefins, polyamides (eg, aromatic polyamides such as aliphatic polyamides or aramids), thermoplastic polyurethanes, acrylic polymers, and mixtures thereof. And thermoplastic polymer materials that are compatible with the thermoset matrix material. Preferred thermoplastic polyesters include DESMOPHE
N2000 and DESMOPHEN 2001KS (both Pittsb
urg., Bayer, Pennsylvania) and RD-847
A polyester resin (Columbus, Ohio's Borden Chemi
cals). Useful polyamides include General
Mills Chemicals, Inc. VERSAMI commercially available from
D products. Useful thermoplastic polyurethanes include Chicago, Il
linois Witco Chemical Corp. WITCOBOND® W-290H commercially available from Hicksville, Ne.
w York's Ruco Polymer Corp. RU commercially available from
COTHANE® 2011L polyurethane latex.

Useful thermoset polymeric materials include thermoset polyesters, epoxy materials, vinyl esters, phenols, amino plastics, thermoset polyurethanes, which are compatible with thermoset matrix materials. And mixtures thereof. Suitable thermoset polyesters include Port Washington, W.
cook Composites and Polymer of isconsin
and STYPOL polyester available from Como, Italy.
SM B. V. NEOXIL polyester which is commercially available from

Useful epoxy materials contain at least one epoxy or oxirane group in the molecule, such as a polyglycidyl ether of a polyhydric alcohol or thiol.
An example of a suitable epoxy polymer is an epoxy-functional polyglycidyl ether of bisphenol A, and Shell Chemic of Houston, Texas.
EPON® 826 and EPON® 880 epoxy resins, commercially available from al Company. However, preferably, the coating composition is substantially free of epoxy material. That is, the coating composition comprises less than about 5 weight percent epoxy material, and more preferably less than about 2 weight percent epoxy material.

Preferably, the coating composition comprises one or more polyesters (preferably D
ESMOPHEN 2000 and RD-847A) and one or more additional film-forming polymers selected from the group consisting of vinylpyrrolidone polymers (preferably), vinyl alcohol polymers, and / or starch. Preferred vinylpyrrolidone polymers useful in the present invention include PVP
Polyvinylpyrrolidone such as K-15, PVP K-30, PVP K-60, and PVP K-90. Each of these polyvinylpyrrolidones is commercially available from ISP Chemicals of Wayne, New Jersey. Useful starches include potato, corn, wheat, soft corn, sago starch, such as Kollotex 1250 (a low viscosity, low amylose potato-based starch etherified with ethylene oxide, commercially available from AVEBE of Netherlands). And rice, milo, and mixtures thereof. The amount of additional polymer is preferably less than about 10 weight percent, more preferably from about 0.1 to about 5
Weight percent range. The coating composition is preferably substantially free of starch. That is, the coating composition comprises less than about 5 weight percent starch, and more preferably is free of starch. Starch is often incompatible with the matrix material.

In an alternative preferred embodiment for a printed circuit board laminate, the polymer material of the coating composition is RD-847A polyester resin, PVP K
Includes a mixture of -30 polyvinylpyrrolidone, DESMOPHEN2000 polyester, and VERSAMID polyamide. The coating composition comprises:
It comprises a mixture of one or more thermoplastic polymer materials and one or more thermoset polymer materials.

Generally, the amount of polymeric material will be from about 1 to about 99%, preferably from about 1 to about 50%, more preferably from about 1 to about 2% by weight of the coating composition, based on total solids.
It may be in the range of 5% by weight.

With respect to the addition or replacement of the polymeric materials discussed above, the coating composition preferably comprises an organosilane coupling agent, a transition metal coupling agent, a phosphonate coupling agent, an aluminum coupling agent, an amino-containing Wern.
er coupling agents, and one or more coupling agents, such as mixtures thereof. These coupling agents typically have a dual function. Each metal or silicon atom was contacted with one or more groups that could react or be compatible with the fiber surface and / or components of the coating composition. As used herein, "fit (
The term "compatibilize" means that the group is, for example, polar, wet,
It means that it is attracted rather than chemically bonded to its fiber surface and / or components of the coating composition by solvation. Examples of hydrolysable groups include:

[0047]

Embedded imageCyclic C of monohydroxy and / or 1,2- or 1,3-glycol_Two -C_ThreeResidues, where R¹Is C₁-C_ThreeAlkyl; R^TwoIs H or C₁-C_FourAlkyl; R^ThreeAnd R^FourIs H, C₁-C_FourAlkyl or C ₆ -C₈Independently selected from aryl; and R^FiveIs C_Four-C₇It is alkylene. A suitable compatibilizing group or functional group
Examples of groups include epoxy, glycidoxy, mercapto, cyano, allyl, alkyl
, Uretano, halo, isocyanate, ureido, imidazolinyl, vinyl,
Relates, methacrylates, amino or polyamino groups are mentioned.

[0048] Functional organosilane coupling agents are suitable for use in the present invention. Examples of useful functional organosilane coupling agents include γ-aminopropyl trialkoxysilane, γ-isocyanatopropyltriethoxysilane, vinyl-trialkoxysilane, glycidoxypropyl trialkoxysilane and ureidopropyl trialkoxysilane Is mentioned. Preferred functional organic silane coupling agents are A-187 γ-glycidoxypropyltrimethoxysilane, A-174
γ-methacryloxypropyltrimethoxysilane, A-1100 γ-aminopropyltriethoxysilane silane coupling agent, A-1108 aminosilane coupling agent and A-1160 γ-ureidopropyltriethoxysilane (each reagent is OSi Specialties, Inc., Tarryto
wn, commercially available from New York). The organosilane coupling agent may be hydrolyzed with water at least partially, preferably in a stoichiometric ratio of about 1: 1 with water, or if desired, into a non-hydrolysable form. Can be applied.

Suitable transition metal coupling agents include titanium, zirconium, yttrium,
And chromium coupling agents. Suitable titanate and zirconate coupling agents are available from Kenrich Petrochemical.
Commercially available from al Company. Suitable chromium complexes are described in E.I. I. du
It is commercially available from Pont de Nemours, Wilmington, Delaware. Amino-containing Werner-type coupling agents are complex compounds in which a trivalent nucleus such as chromium is coordinated with an organic acid having an amino functionality. Other metal chelates and coordinating coupling agents known to those of skill in the art may also be used herein.

[0050] The amount of coupling agent can range from about 1 to about 99%, preferably from about 1 to about 10% by weight of the coating composition, based on total solids.

Referring to FIG. 3, in a preferred embodiment of the present invention, the coating composition comprises one or more solid particles disposed between the outer surfaces of the fibers 18 or adhered to the outer surfaces of the fibers 18. 24. Glass fiber 26 adjacent to strand 16
, 28, these solid particles 24 may generally provide an interstitial region 30 corresponding to an average particle size 32 of the solid particles 24. As used herein, a "solid" refers to a material that hardly flows under moderate stress, has a defined endurance to a resistance that tends to deform the substrate, and under normal conditions, A substrate that maintains a defined size and shape. Webster's Third New
International Dictionary of the Engl
See islanguage-Unbridged (1971) p. 2169. Further, the term "solid" as used herein includes crystalline and non-crystalline materials.

The solid particles 24 are from about 0.01 to greater than 5 μm, preferably from about 1 to about 10
It may have an average particle size 32 (corresponding to a spherical diameter) in the range of from 00 μm, more preferably from about 1 to about 25 μm. Preferably, the minimum average particle size 32 of the solid particles 24 generally corresponds to the average nominal diameter of the glass fibers.

As described above, the structure or shape of the solid particles 24 is generally spherical (as desired).
Beads, microbeads, or solid hollow spheres), cubes, plates, or needles (extended or fibrous). For more information on suitable particle properties, see Katz et al. (Eds.), (Handbook of Fill
ers and Plastics) (1987) pp. 9-10 (hereby incorporated by reference). The solid particles are preferably less than 5 μm (preferably, less than 5 μm) in the coating composition under typical glass fiber processing conditions such as being exposed to temperatures up to about 25 ° C. (more preferably, up to about 400 ° C.). (3 μm or more) does not grind, deform or dissolve.

The glass fibers may be in contact with adjacent glass fibers and / or raised portions of other solid objects or materials (the glass fibers contact during molding and subsequent processing, such as, for example, weaving or roving). Susceptible to abrasive wear due to contact. As used herein, "abrasive wear" refers to the removal of small pieces of glass fiber surfaces by frictional contact with particles, edges or elements of a material that is sufficiently hard to damage the glass fibers. Scraps or cuts or broken glass fibers. K. Lu
by Dema (Friction, Wear, Lubrication,) (
(1996) at page 129 (hereby incorporated by reference). Abrasive wear of glass fiber strands can result in strand breaks during processing as well as woven fabric (w
Surface defects occur in products such as open cloth and composites, thereby increasing waste and manufacturing costs.

In order to minimize abrasive wear, the solid particles have a hardness value not exceeding, ie less than or equal to the hardness value of the glass fiber (s). The hardness value of the solid particles and glass fibers is determined by any conventional hardness measurement method, such as Vickers or Brinell hardness, but is preferably determined by the original Mohs hardness scale, which is the relative scratching of the surface of the material. Shows resistance.
The Mohs hardness value of the glass fibers generally ranges from about 4.5 to about 6.5, and is preferably about 6. R. Handbook of Ch by Weast (ed.)
emistry and Physics, CRC Press (1975) F
-22 (incorporated herein by reference). The Mohs hardness value of the solid particles preferably ranges from about 0.5 to about 6. In the present invention, Mohs hardness values of some non-limiting examples of solid particles suitable for use are shown in Table A below.

[0056]

[Table 1] 1K. By Ludema (Friction, Wear, Lubricati
on), (1996) p. 27 (incorporated herein by reference). 2R. By Hand (edited) (Handbook of Chemistry)
and Physics), CRC Press (1975) F-22. 3R. Lewis, Sr. , (Hawley's Condensed Che
medical Dictionary, (12th edition, 1993) p. 793 (hereby incorporated by reference). 4 (Hawley's Condensed Chemical Dictio)
nary), (12th edition 1993) p. 1113 (herein incorporated by reference). 5 (Hawley's Condensed Chemical Dictio)
nary), (12th edition 1993) p. 784 (hereby incorporated by reference). 6 (Handbook of Chemistry and Physics)
, F-22. 7 (Handbook of Chemistry and Physics)
, F-22. 8 (Friction, Wear, Lubrication), page 27. 9 (Friction, Wear, Lubrication), page 27. 10 (Friction, Wear, Lubrication), page 27. 11 (Friction, Wear, Lubrication), page 27. 12 (Handbook of Chemistry and Physics)
) F-22. 13 (Handbook of Chemistry and Physics)
) F-22. 14 (Handbook of Chemistry and Physics)
) F-22. 15 (Handbook of Chemistry and Physics)
) F-22. 16 (Handbook of Chemistry and Physics)
) F-22. 17 (Handbook of Chemistry and Physics)
) F-22. 18 (Handbook of Chemistry and Physics)
) F-22.

As mentioned above, the Mohs hardness scale relates to the resistance of a material to scratching.
Accordingly, the present invention contemplates particles having a hardness at the particle surface that is different from the hardness of the internal particles below the particle surface, and more particularly, the surface of the particle coats, cladding, or It can be modified in any known manner, including encapsulation or chemically altering the surface properties using known techniques. as a result,
The surface hardness of the particles is not greater than the hardness of the glass fibers, while the hardness of the particles below the surface is greater than the hardness of the glass fibers. For example, but not limited to, the present invention, inorganic particles such as silicon carbide and aluminum nitride can provide silica, carbonate, or nanoclay coatings. Further, the silane coupling agent having an alkyl side chain reacts with the surface of many oxide particles,
It may provide a "softer" surface.

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

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

[0060] Preferably, the inorganic solid particles 24 are also solid lubricants. As used herein, "solid lubricant" means that the inorganic solid material 24 has a unique crystal habit, and from the crystal habit, the inorganic solid particles are sheared into a thin flat plate so as to be slippery with each other, This results in a glass fiber surface and adjacent solid surface (at least one of which is moving)
A lubricating effect of reducing wear. (R. Lewis, Sr., (Hawl
eye's Condensed Chemical Dictionary),
(Twelveth Edition, 1993) p. 712 (incorporated herein by reference). Friction is the resistance of one solid to sliding on another. F. Clau
(Solid Lubricants and Self-Lubr)
icating Solids), (1972) p. 1 (incorporated herein by reference).

[0061] In a preferred embodiment, the solid lubricant particles have a lamellar structure. Particles having a lamellar or hexagonal crystal structure are composed of atomic sheets or plates that have strong bonds inside the sheets and have a weak van der Waals force between the sheets in a hexagonal array, with low inter-sheet Provides shear strength. (Fri
ction, Wear, Lubrication) page 125, (Solid L
ublicants and Self-Lubricating Solid
s) 19-22, 42-54, 75-77, 80-81, 82, 90
-102, 113-120, and 128; Campbel
l “Solid Lubricants” (Boundary Lubrica)
tion; An Appraisal of World Literacy
e), ASME Research Committee on Lubrica
Tion (1969) pp. 202-203 (hereby incorporated by reference).
Inorganic solid particles having a lamellar fullerene (buckyball) structure are also useful in the present invention.

Non-limiting examples of suitable inorganic solid lubricant particles having a lamellar 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 disulfide, molybdenum diselenide, tantalum disulfide, tantalum diselenide, tungsten disulfide, tungsten diselenide, and mixtures thereof.

[0063] Boron nitride particles having a hexagonal structure are most preferred for use in aqueous sizing compositions. Boron nitride particles, zinc sulfide particles, and montmorillonite particles also provide good whiteness in composites having a polymer matrix material such as nylon 6,6.

In the present invention, non-limiting examples of boron nitride particles suitable for use include Po
larTherm (registered trademark) 100 series (PT120, PT140, PT
160 and PT180), 300 series (PT350) and 600
Series (PT620, PT630, PT640, and PT670) are boron nitride powder particles, the particles of which are Advanced Ceramics Cor.
It is commercially available from the University of Lakewood, Ohio. Ad
vanced Ceramics Corporation of Lake
Good, Ohio (1996), "PolarTherm (registered trademark) Thermally Conductive Fillers for."
Polymeric Materials "(herein incorporated by reference). These particles have a thermal conductivity of about 250-300 W / mK at 25 ° C., a dielectric constant of about 3.9, and a volume resistivity of about 10 ¹⁵ Ωcm. The 100 series powder has an average particle size in the range of about 5 to about 14 μm, the 300 series has an average particle size in the range of about 100 to about 150 μm, and the 600 series has an average particle size of about 16 to about 14 μm. It has an average particle size in the range of greater than about 200 μm.

The solid lubricant particles 24 can be in a dispersed state, ie, in water as a suspension or emulsion. Other solvents such as mineral oils or alcohols (preferably less than about 5% by weight) can be included in the sizing composition if desired. About 25 in water
Non-limiting examples of preferred dispersants for boron nitride particles by weight are ZYP Coatin
gs, Inc. ORPAC BORON NITRIDE RELEASECOAT-CONC, commercially available from Oak Ridge, Tennessee
It is. ZYP Coatings, Inc. "ORPAC"
BORON NITRIDE RELEASECOAT-CONC "(herein incorporated by reference). According to the supplier, the boron nitride particles of this product have an average particle size of less than about 3 μm. This dispersant contains about 1% magnesium-
It contains aluminum silicate and, according to the supplier, binds the boron nitride particles to the substrate to which the dispersant is applied. Other useful products commercially available from ZYP Coatings include BORON NITRIDE LUBRICOAT® paint, BRAZE STOP and WELD RELEASE products.

Although not preferred, the coating composition may include a hydratable or hydrated inorganic solid lubricating material. Non-limiting examples of such hydratable inorganic solid lubricant materials, mica (e.g., muscovite) is the clay mineral phyllosilicates, including talc, montmorillonite, kaolinite, and gypsum (CaSO ₄ · 2H ₂ O) . As used herein, "hydratable" means that the solid inorganic lubricant particles react with water molecules to form hydrates and contain water of hydration or water of crystallization. I do. "Hydrate" is formed by the reaction of a molecule of water with a substrate (in which H-OH bonds are not cleaved). (R. Lewis, Sr., (Hawley's C
dependent Chemical Dictionary, (12th
Ed. 1993) 609-610; Perros, (Chemis
try), (1967) pp. 186-187 (hereby incorporated by reference).
checking). In the chemical formula of the hydrate, the addition of water molecules is customarily indicated by a central point, for example 3MgO.4SiO ₂ .H ₂ O (talc), Al ₂ O ₃ .2S
iO ₂ · 2H ₂ O (kaolinite). Hydrates are used to coordinate cations in the hydrated material and to add coordinated water that cannot be removed without destroying the structure, and / or electrostatic energy without reversing the charge balance. Includes structural water that is occupied by gaps in the structure. R. Evans, (An Int
production to Crystal Chemistry), (194)
8) page 276 (incorporated herein by reference).

Preferably, the coating composition is essentially free of hydratable inorganic solid lubricant particles or abrasive silica particles or calcium carbonate, ie less than 20% by weight, based on total solids. It contains possible inorganic lubricant particles, wear silica particles or calcium carbonate, more preferably less than about 5% by weight, and most preferably less than 0.001% by weight.

In an alternative embodiment, the solid particles 24 may be formed from an organic polymeric material selected from the group consisting of a thermoset material, a thermoplastic material, a starch, and mixtures thereof. Suitable thermoset materials include thermoset polyesters, vinyl esters,
Including epoxy materials, phenolic resins, aminoplasts, thermoset polyurethanes, and mixtures thereof, which are discussed below. Suitable thermoplastic materials are
Including vinyl polymers, thermoplastic polyesters, polyolefins, polyamides, thermoplastic polyurethanes, acrylic polymers, and mixtures thereof. Preferred organic solid particles are in the form of microbeads or hollow spheres.

In an alternative preferred embodiment, the solid particles 24 are thermally conductive, ie, have a thermal conductivity of greater than about 30 W / mK (eg, boron nitride, graphite, and metal-inorganic solid lubricants described above). The thermal conductivity of solid materials is determined by ASTM
It can be determined by any method known to those skilled in the art, such as a protected hot plate method, at a temperature of about 300 K according to C-177-85 (incorporated herein by reference).

In another alternative embodiment, the inorganic solid particles 24 are electrically insulated or have a high electrical resistivity. That is, for example, about 1000 μΩ such as boron nitride
cm.

The solid lubricant particles comprise about 0.001 of the coating composition on a total solids basis.
To about 99% by weight, preferably about 1 to about 80% by weight, more preferably about 1 to about 80% by weight.
It may contain about 40% by weight.

The coating composition can further include one or more organic lubricants that are chemically different from the polymeric materials discussed above. On the other hand, the coating composition may include up to about 60% by weight of an organic lubricant, preferably the coating composition is essentially free of organic lubricant, ie, contains less than about 10% by weight of the organic lubricant, Preferably, it contains from about 1 to about 5% by weight of an organic lubricant. Examples of such organic lubricants are
Cationic, nonionic, or anionic lubricants and mixtures thereof (eg, amine salts of fatty acids, alkylimidazoline derivatives (eg, CATION X)
, Rhone Poulenc of Prince, New Jersey
tonnes), acid-soluble fatty acid amides, concentrates of fatty acids and polyethyleneimine, and polyethyleneimines substituted with amides (eg, EM
ERY® 6717 (Henke, Kankakee, Ill.
l Partially amidated pottyethyleneimine, commercially available from Corporation).

[0073] The coating composition comprises components (eg, inorganic particles) of the coating composition.
May include one or more emulsifiers for emulsifying or dispersing the Non-limiting examples of suitable emulsifiers or surfactants include polyoxyalkylene block copolymers (eg, PLURONIC ^™ F-108 polyoxypropylene-polyoxyethylene copolymers, which are available from BASF Corporation of P.C.
arsippany, commercially available from New Jersey), ethoxylated alkylphenols (eg, IGEPAL CA-630 ethoxylated octylphenoxyethanol (GAF Corporation, W
ayne, commercially available from New Jersey)), polyoxyethylene octylphenyl glycol ether, ethylene oxide derivatives of sorbitol esters, polyoxyethylated vegetable oils (e.g., ALKAMULS EL-71).
9 (which is commercially available from Rhone-Poulenc)), and nonylphenol surfactants (e.g., MACOL NP-6 (which is a
Parsippany, commercially available from New Jersey)). Generally, the amount of emulsifier will be about 1 to about 1% of the coating composition on a total solids basis.
It can range from about 30 weight percent.

The coating composition may include one or more water-soluble emulsifiable or dispersible wax materials (eg, plant, animal, mineral, synthetic, or petroleum waxes). A preferred wax is petroleum wax (eg, MICHEM® LUBE296 microcrystalline wax, POLYMEKON® SPP).
-W microcrystalline wax and PETROLITE 75 microcrystalline wax (these are Michelman Inc., Cincinnati, Ohio, and the Petrolite Corporation, Tulsa, Ok, respectively)
laoma))). Generally, the amount of wax may be from about 1 to about 10 weight percent of the coating based on total solids.

[0075] Crosslinking materials such as melamine formaldehyde and plasticizers such as phthalate, trimellitate, and adipate can also be included in the coating composition. The amount of crosslinker or plasticizer can range from about 1 to about 5 weight percent of the coating composition, based on total solids.

[0076] Other additives may be included in the coating compositions, such as silicones, fungicides, bactericides, and antifoam materials, generally in amounts less than about 5 weight percent.
An organic and / or inorganic acid or base and / or base may also be included in an amount sufficient to provide a coating composition having a pH of from about 2 to about 10. Non-limiting example of a suitable silicone emulsion is LE-9300
An epoxidized silicone emulsion, which is an OSi Special
ties, Inc. , Danbury, Connecticut. An example of a suitable fungicide is the Biomet 66 antimicrobial compound, which is available from M &
It is commercially available from T Chemicals, Rahway, New Jersey. Suitable defoaming materials are SAG materials (which are OSi Specialties
s, Inc. , Danbury, Connecticut)
, And MAZU DF-136 (which are available from BASF Company, Par
sipany, available from New Jersey). Ammonium hydroxide may be added to the coating composition for stabilization, if desired. The water, preferably deionized water, is preferably in an amount sufficient to facilitate application of a substantially uniform coating on the strands (typically from about 25 to about 99
(In percent by weight) in the coating composition. The weight percent of solids in the aqueous coating composition generally ranges from about 1 to about 75 weight percent.

The coating composition is preferably essentially free of glass material. As used herein, "essentially free of glass material" means that the coating composition comprises less than 20 volume percent of the glass matrix material to form the glass composite, preferably about Means less than 5 volume percent, and more preferably means having no glass material. Examples of such glass matrix materials include black glass ceramic matrix materials or aluminosilicate matrix materials, as is well known to those skilled in the art.

In one embodiment for weaving fibers for printed circuit boards, the glass fibers of the coated fiber strands of the present invention may comprise a water-based sizing composition (PolarTherm® 160 boron nitride powder) And / or BORON NITRIDE RELEASECOAT dispersion, EPON
826 epoxy film forming material, PVP K-30 polyvinylpyrrolidone, A
-187 Epoxy functional organic silane coupling agent, ALKAMULS EL-
719 polyoxyethylated vegetable oil, IGEPAL CA-630 ethoxylated octylphenoxyethanol, KESSCO PEG 600 polyethylene glycol monolaurate (which is available from Stepan Company, Chi
cago, Illinois), as well as a first layer of a dried residue of polyethyleneimine (including EMERY® 6717), which is partially amidated.

In a preferred embodiment for weaving the fibers, the glass fibers of the coated fiber strands of the present invention have an aqueous sizing composition (Po
larTherm® 160 boron nitride powder and / or BORON
NITRIDE RELEASECOAT dispersion, RD-847A polyester, PVP K-30 polyvinylpyrrolidone, DESMOPHEN2000 polyester, A-174 acrylic functional organic silane coupling agent, and A-1
87 epoxy functional organic silane coupling agent (including a dry residue).

[0080] The coating composition of the present invention can be prepared by any suitable method, such as conventional mixing steps well known to those skilled in the art. Preferably, the components discussed above are diluted with water to have the desired weight percent solids, and are mixed together. The powdered thermally conductive inorganic solid particles can be pre-mixed with water or added to the polymeric material before mixing with the other components of the coating.

The layer of coating can be applied to the fibers in a number of ways (eg, by contacting the filaments with a roller or belt applicator, by spraying, or by other means). The coated fibers are
Preferably, it is dried at room temperature or high temperature. The dryer removes excess moisture from the fibers (
Remove (if present) and cure any curable coating composition components. The temperature and time during which the glass fibers are dried depend on variables such as, for example, the percentage of solids in the coating composition, the components of the coating composition, and the type of glass fiber. The coating composition is typically present as a dried size residue on the fibers in an amount between about 0.1 and about 25 weight percent after drying. The loss on ignition of the fibers is generally less than about 0.6 weight percent, preferably less than about 0.5 weight percent, and more preferably less than about 0.5 weight percent.
It ranges from 01 to about 0.45 weight percent. The loss on ignition of a sample of coated fibers can be determined by heating the fibers in a muffle furnace at a temperature of 1200 ° C. for 20 minutes.

A second layer of the second coating composition may be applied over the layers of the coating composition discussed above, in an amount effective to coat or soak portions of the strand (eg, applying the composition By dipping the strands into a bath containing the composition, by spraying the composition onto the strands, or by contacting the strands with the applicator as discussed above). The coated strand may pass through a die to remove excess coating composition from the strand and / or at least partially dry or cure the second coating composition, as discussed above. Can be dried for a sufficient time. The method and apparatus for applying the second coating composition to the strand is determined in part by the arrangement of the strand materials.
The strand is preferably dried after application of the second coating composition in a manner well known in the art.

[0083] A suitable second coating composition comprises one or more film-forming materials, a lubricant,
And other additives as discussed above. The second coating is
Different from sizing composition. That is, the second coating comprises (1) at least one component that is chemically different from the components of the sizing composition, or (2) at least one component in an amount different from the amount of the same component included in the sizing composition. Contains ingredients. Non-limiting examples of suitable second coating compositions (including polyurethanes) are described in U.S. Patent Nos. 4,762,750 and 4,762,751, which are incorporated herein by reference. ).

In an alternative preferred embodiment according to the present invention, the glass fibers of the fiber strands are dried against a conventional sizing composition or a sizing composition which may comprise any of the sizing compositions in the amounts discussed above. A first layer of the residue obtained may be applied. An example of a suitable sizing composition is Loewenstein's 237
291 (3rd edition, 1993) and U.S. Patent Nos. 4,390,647 and 4,795,678, each of which is incorporated herein by reference. The second or first layer of the second coating composition according to the present invention is applied at least partially on the first layer and preferably over the entire outer surface. The second coating composition may include one or more types of solid particles discussed above and / or the solid particles shown in Tables C, D, and E below.

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4] Molybdenum disulfide and magnesium oxide are other inorganic solid particles that are useful in the second and third coatings of the present invention. One skilled in the art will understand that mixtures of any of the above inorganic solid particles can be used in the present invention.

[0088] The amount of inorganic particles in the second coating composition can range from about 1 to about 99% by weight, preferably from about 20 to about 90% by weight, based on total solids. Water soluble second
The percentage of solids in the coating composition generally ranges from about 5 to about 75% by weight.

In an alternative embodiment, a third layer of the third coating composition may be applied to at least a portion of the surface of the second layer, preferably over the entire surface of the second layer. That is, such a fiber strand has a first layer of sizing, a second layer of a second coating composition, and a third outer layer of a third coating. The third coating is a sizing composition (sizing compo).
position) and the second coating composition, ie, the third coating composition contains (1) at least one component that is chemically different from the components of the sizing composition and the second coating composition. Or (2) contains at least one component in an amount different from the amount of the same component contained in the sizing composition or the second coating composition.

In this embodiment, the second coating composition comprises one or more polymeric materials as described above (eg, polyurethane) and the third coating composition comprises powdered thermally conductive inorganic particles (eg, as described above). Polar Therm® boron nitride particles). Preferably, the powder coating is applied by passing through a strand having a liquid second coating composition applied thereto by a fluidized bed or spray device to adhere the powder particles to the tacky second coating composition. Applied. Alternatively, as shown in FIG.
The strands are applied to the fabric 1 before the third coating layer 140 is applied.
14 can be assembled. The weight percent of powdered thermally conductive inorganic solid particles adhered to the coated strand can range from about 0.1% to about 75% by weight of the total weight of the dried strand. The third coating may also include one or more of the polymeric materials described above (eg, acrylic polymers, epoxies, or polyolefins), conventional stabilizers and other conditioning agents known in the art for such coatings, preferably dried. It may be contained in powder form.

[0091] The fiber strands may be processed into a woven fabric 14, preferably by knitting or weaving. The woven fabric 14 is used as a reinforcement to reinforce the polymer matrix material 12 to form a composite or laminate 10 as shown in FIG. 1, preferably for use in a printed circuit board. You. Prior to weaving, the vertical strands of the fabric 14 may be twisted by any conventional twisting techniques known to those skilled in the art, for example, using a twist frame that twists the strands at about 0.5 to about 3 revolutions per inch. It may or may not be twisted.

[0092] The reinforced fabric 14 may include from about 5 to about 100 vertical strands per centimeter, and preferably from about 3 to about 25 picks per centimeter (about 1 to about 15 picks per inch). Has lateral strands. The woven structure may be a conventional plain weave, but any other weaving mode known to those skilled in the art, such as twill or sword weave, may be used.

[0093] Anderson, South Ca, incorporated herein by reference.
rolina's Clark-Schwebel, Inc. Technical Report "Fa
As disclosed in the Bricks Around the World (1995), the fabric 14 is preferably woven in a manner suitable for use in laminates for printed circuit boards. E225E-A preferred fabric style using fiberglass is 118 vertical yarns and 114 horizontal yarns per 5 square centimeter area (60 vertical yarns and 5 vertical yarns per square inch).
(8 horizontal yarns), using 722 1 × 0 (E225 1/0) vertical and horizontal yarns, a nominal fabric thickness of 0.094 mm (0.037 inch), and 103.8 g / m ² ( Form 2116, having a fabric weight of 3.06 ounces per square yard. A preferred fabric style using G75E fiberglass is 87 longitudinal yarns and 6 per square centimeter area.
It has one horizontal yarn (44 vertical yarns and 31 horizontal yarns per square inch), uses 968 1 × 0 (G75 1/0) vertical and horizontal yarns, and uses 0 horizontal yarns.
. Nominal fabric thickness of 173 mm (0.0068 inches), and 203.4
Form 7628, with a fabric weight of 6.00 ounces per square yard (g / m ² ). A preferred fabric style using D450E glass fiber has 118 vertical yarns and 93 horizontal yarns per area of 5 square centimeters (60 vertical yarns and 47 horizontal yarns per square inch); Using 511 1 × 0 (D450 1/0) vertical and horizontal yarns, 0.05
Form 1 having a nominal fabric thickness of 3 mm (0.0021 inches) and a fabric weight of 46.8 g / m ² (1.38 ounces per square yard)
080. A detailed description of these and other useful fabric modalities can be found in The Institute for Interc, which is incorporated herein by reference.
connecting and Packing Electronic C
publications, IPC-EG-140 "Specifications"
for Finished Fabric Woven from 'E'
Glass for Printed Boards "(June 1997).

[0094] A suitable woven reinforcement fabric 14 may be formed using any conventional loom known to those skilled in the art, such as a shuttle loom or a rapier loom, but is preferably formed using an air jet loom. Is done. Suitable air jet looms are model number 103, commercially available from Tsudakoma (Japan), and Zuri.
ch, Switzerland's Sulzer Brothers Ltd. Sulzer Ruti model numbers L-5000 or L-5 commercially available from
100. Sulzer RutiL, incorporated herein by reference.
5000 and L5100 Product Bulletins of Su
lzer Ruti Ltd. , Switzerland.

As used herein, “air jet weave” refers to compressed air 514 from one or more air jet nozzles 518 (shown in FIGS. 6 and 6a), as described above.
Means a type of fabric weaving using an air jet loom 526 (shown in FIG. 6) in which a fill yarn (weft) 510 is inserted into the warp shed by the air blowing. The fill yarn 510 is compressed by the compressed air into the fabric 52.
8 is propelled across a width 524 (about 10 to about 60 inches), and more preferably about 0.91 meters (about 36 inches).

The air jet filling system may have one main nozzle 516,
Preferably, a plurality of auxiliary relay nozzles along the warp shed 512 to provide an auxiliary air blast 522 to the fill yarn 510 to maintain a desired air pressure while the yarn 510 traverses the width 524 of the fabric 528. 520.
The pressure (gauge) supplied to the main air nozzle 516 is preferably about 103
From about 15 to about 60 pounds per square inch (psi), and more preferably about 45 kpsi (310 kPa).
It is. The preferred mode of the main air nozzle 516 is a 2 millimeter diameter 517
Ruti Needle Air Jet Nozzle Unit (Model No. 044455001) with an internal air jet chamber with a nozzle and a nozzle outlet tube 519 with a length 521 of 20 centimeters (Spartanbu)
rg, commercially available from Sulzer Ruti of North Carolina). Preferably, the air jet filling system has 15 to about 20 auxiliary air nozzles 520 that provide an auxiliary air blast in the direction of advancement of the fill yarn 510 and assist in advancing the yarn 510 across the loom 526. Auxiliary air nozzle 5
The pressure (gauge) supplied to each of the 20 preferably ranges from about 3 to about 6 bar.

[0097] The fill yarn 510 may be supplied at about 180 to about
About 550 meters, preferably about 274 meters per minute (about 300 yards)
At a supply speed of. The fill yarn 510 is supplied to the main nozzle 518 through a clamp. The air blast advances a predetermined length of yarn (approximately equal to the desired width of the fabric) through a confusor guide. Upon completion of the insertion, the end of the yarn distal to main nozzle 518 is cut by cutter 534.

The compatibility and aerodynamic properties of the different yarns in the air jet weave process can be determined by the following method, commonly referred to herein as the “air jet transport resistance” test method. The air jet transport resistance test is used to measure the attraction or traction ("resistance") over a yarn as it is drawn into the air jet nozzle by the force of the air jet. In this manner, a 2 millimeter diameter 51 at a speed of about 300 yards per minute.
7 and a length 521 of 20 centimeters
Sulzer Ruti Needle Air Jet Nozzle Unit with Nozzle Exit Tube 519 (Model No. 044455001) (Spartan
Each of the yarn samples is supplied at about 310 kilopascals (about 45 pounds per square inch) gauge through burg, North Carolina (commercially available from Sulzer Ruti). At a position before the yarn enters the air jet nozzle, a tensiometer is positioned to contact the yarn. Tensiometers measure the gram weight (resistance) exerted on a yarn by an air jet as the yarn is drawn into an air jet nozzle.

The drag force per unit mass can be used as a basis for a relative comparison of yarn samples. For relative comparison, resistance measurements are standardized on one centimeter long yarns. The gram mass of a one centimeter long yarn can be determined by equation (I).

Gram mass = (π (d / 2) ² ) (N) (ρ _glass ) (1 cm long yarn) (I) where d is the diameter of one fiber of the yarn bundle , N is the number of fibers in the yarn bundle and ρ _glass is the specific gravity of the glass at a temperature of about 25 ° C. (about 2.6 grams per cubic centimeter). Table F lists the diameter and number of fibers in the yarn for some typical glass fiber yarn products.

[0101]

[Table 5] For example, the gram mass of a 1 cm long G75 yarn is (π (9 × 10^-Four/ 2) ^Two ) (400) (2.6 grams per cubic centimeter) (1 centimeter long yarn) = 6.62 x 10^-FourIt is a gram mass. About D450 yarn
Means that the gram mass is 1.34 × 10^-FourIt is a gram mass. Relative per unit mass
Resistance (air jet transport resistance) is the resistance determined by the tensiometer.
By dividing the drag measurement (gram weight) by the gram mass of the yarn being tested
Is calculated. For example, for a sample of G75 yarn,
When the data measurement was 68.5, the air jet transfer resistance was the gram mass of the yarn.
6.62 × 10^-Four= Equivalent to 68.5 divided by 103,474 grams weight.

The air jet transport resistance of the yarns used to form the woven fabric for laminates according to the present invention is determined by the air jet transport resistance test method described above, which is based on the gram weight of the yarn. Greater than about 100,000 gram weight, preferably from about 100,000 to about 400,
000 grams weight, more preferably about 1 / gram weight of yarn.
It ranges from 20,000 to about 300,000 grams weight.

Referring now to FIG. 1, a fabric 14 is formed by laminating the laminate 10 by coating and / or impregnating one or more layers of the fabric 14 with a polymeric thermoplastic or thermoset matrix material 12. Can be used to form. The laminate 10 is suitable for use as the electronic support 30. As used herein, "electronic support" refers to active electronic components, passive electronic components, printed circuits associated with elements including, but not limited to, connectors, sockets, retaining clips, and heat sinks. , Mechanically supporting and / or electrically interconnecting elements including, but not limited to, integrated circuits, semiconductor devices and other hardware.

The matrix materials useful in the present invention include thermosetting polyesters, vinyl esters, epoxides (including at least one epoxy or oxirane group in the molecule, such as polyglycidyl ethers of polyhydric alcohols or thiols), phenols , Aminoplasts, thermoset polyurethanes, derivatives and mixtures thereof. Suitable matrix materials for forming laminates for printed circuit boards are FR-4 epoxy resins, polyimides, liquid crystalline polymers, the compositions of which are well known to those skilled in the art. If more information is needed about such compositions, see 1 “Electronic Materials Ha
ndbook ^™ ”, 53 of ASM International (1989).
See pages 4-537.

Non-limiting examples of suitable thermoplastic polymer matrix materials include polyolefins, polyamides, thermoplastic polyurethanes and thermoplastic polyesters, vinyl polymers, and mixtures thereof. Further examples of useful thermoplastic materials include polyimide, polyethersulfone, polyphenylsulfone, polyetherketone, polyphenylene oxide, polyphenylene sulfide, polyacetal, polyvinyl chloride, and polycarbonate.

A useful matrix material formulation consists of EPON 1120-A80 epoxy resin, dicyandiamide, 2-methylimidazole, and DOWANOL PM.

Other components that may be included in the polymer matrix material, and reinforcements in the composite, include colorants or pigments, lubricants or processing aids, ultraviolet (UV) stabilizers, antioxidants, other fillers. Agents and bulking agents.

[0108] The fabric 14 may be, for example, a R.C.R. Tu
mmala (eds.), “Microelectronics Packaging
The fabric 14 can be coated and impregnated by dipping the fabric 14 into a bath of the polymer matrix material 12, as described in Handbook (1989), pages 895-896. Polymer matrix material 12 and fabric 14 may be formed into composite or laminate 10 by a variety of methods depending on factors such as the type of polymer matrix material used. For example, for thermoset matrix materials, the laminate may be formed by compression or injection molding, pultrusion, hand lay-up, or by sheet molding followed by compression or injection molding. Thermoset polymer matrix materials can be cured, for example, by including a crosslinker in the matrix material and / or applying heat. Suitable crosslinking agents useful for crosslinking the polymer matrix material are as described above. The temperature of the thermoset polymer matrix material and the time it takes to cure depend on factors such as the type of polymer matrix material used, other additives in the matrix system, and the thickness of the composite, but these factors Is just one example.

For thermoplastic matrix materials, suitable methods of forming the composite include direct molding or extrusion compounding followed by injection molding. Methods and apparatus for forming composites by the methods described above are described in I.S. Rubin, "Handbook of Plastic Material
rials and Technology "(1990) 955-106.
2, page 1179-1215 and pages 1225-1271.

In a particular embodiment of the present 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 squeezed between a set of metering rolls to leave a measured amount of matrix material, to form an electronic support in the form of a semi-cured substrate or prepreg. And dried. Electrically conductive layer 4
0 may be positioned along a portion of the side 42 of the prepreg in a manner described below herein, where the prepreg is cured and the laminate 10 acting as an electronic support 50 for the electrically conductive layer is disposed. Form. In another embodiment of the present invention, which is more typical in the electronic support industry, two or more prepregs are combined with an electrically conductive layer, laminated together, cured and cured in a manner well known to those skilled in the art. Form the support. Without limiting the invention, for example, the prepreg stack may be raised for a predetermined length of time to cure the polymer matrix and form a laminate of the desired thickness, e.g., between polished steel plates. Stacking may be accomplished by compressing the stack at a specified temperature and pressure. A portion of the one or more prepregs may include an electrically conductive layer either before or after lamination and curing, and the resulting electronic support may include at least one electrically conductive layer along a portion of the exposed surface. A laminate having layers (hereinafter, referred to as a “cladding laminate”).

The circuit may then be formed from a single layer or multiple layers of the electronic support's electrically conductive layer (s) using techniques well known to those skilled in the art, including a printed circuit board or printed circuit board (hereinafter, referred to as a printed circuit board). , Collectively referred to as “electronic circuit boards”). If necessary, apertures or holes (also referred to as "vias") can be formed in the electronic support in any suitable manner known in the art, including but not limited to mechanical and laser drilling. Enables electrical interconnection between circuits and / or components on opposing surfaces of the electronic support. More specifically, after formation of the aperture, a layer of electrically conductive material is deposited on the walls of the aperture or the aperture is filled with the electrically conductive material to provide the necessary electrical interconnects and / or Or facilitate heat dissipation.

The electrically conductive layer 40 can be formed by any method known to those skilled in the art. For example, but not by way of limitation, the electrically conductive layer may be formed by laminating a thin sheet or foil of a metallic material to at least a portion of the side of a semi-cured or cured prepreg or laminate. obtain. Alternatively, the electrically conductive layer may be a semi-cured or cured side of the prepreg or laminate using a well-known technique, including, but not limited to, electrolytic plating, electroless plating, or sputtering. By laminating at least a part of
Can be formed. Suitable metallic materials for use as the electrically conductive layer include, but are not limited to, copper (preferred), silver, aluminum, gold, tin, tin-lead alloy, palladium, and combinations thereof.

In another embodiment of the present invention, the electronic support comprises one or more clad laminates (
And / or a multilayer electronic circuit board constituted by laminating together one or more prepregs (above). If necessary, additional electrically conductive layers can be incorporated into the electronic support, for example, along a portion of the exposed side of the multilayer electronic circuit board. Further, if necessary, additional circuitry can be formed from the electrically conductive layer in the manner described above. It should be understood that the substrate may have both internal and external circuits, depending on the relative positions of the layers of the multilayer electronic circuit board. As described above, additional apertures may be partially or completely formed through the substrate to allow electrical interconnection between layers at selected locations. It should be understood that the resulting structure may have some apertures extending completely through the structure, some apertures extending only partially through the structure, and apertures completely within the structure. It is.

Preferably, the thickness of the laminate forming the electronic support 50 is about 0.051 mm (
0.002 inches), more preferably in the range of about 0.13 mm (0.005 inches) to about 2.5 mm (about 0.1 inches). For an 8 ply laminate of 7628 style fabric, the thickness is typically about 1.32 mm (0.05 mm).
2 inches). The number of layers of fabric 14 in laminate 10 can vary based on the desired thickness of the laminate. For simplicity of the drawing, only one layer of the fabric is shown in FIGS. The number of layers can range from 1 to about 40. Preferably, the laminate has eight layers of fabric or prepreg.

The resin content of the laminate is from about 35 to about 80 weight percent, more preferably
It can range from about 40 to about 75 weight percent. The amount of fabric in the laminate can range from about 20 to about 65 weight percent, and more preferably, from about 25 to about 60 weight percent.

For a laminate formed from a woven E-glass fabric and having a minimum glass transition temperature of about 110 ° C. using an FR-4 epoxy resin matrix material, T
he Institute for Interconnecting and
Publication of Packaging Electronic Circuits, I
PC-4101 "Specification for Base Mater
ials for Rigid and Multilayer Printe
According to d Boards "29 pp (December 1997), the desired minimum bend strength of the cross machine or transverse direction (generally is perpendicular to the longitudinal axis of the fabric) is, 3 × 10 ⁷ kg / m greater than ^2, preferably greater than about ^{3.52 × 10 7 kg / m 2} ( about 50 kpsi), more preferably about 4.9 × 10 ⁷ kg /
greater than m ² (about 70 kpsi). IPC-4101 is hereby incorporated by reference in its entirety. In the length direction, the desired minimum bending strength in the length direction (substantially parallel to the longitudinal axis of the fabric) is greater than about 4 × 10 ⁷ kg / m ² , preferably 4.23 × 10 ⁷ kg / M ² . The bending strength is Th
e Institute for Interconnecting and
ASTM D-790 and I from Packaging Electronics
According to the Test Method Manual for PC-TM-650 (December 1994) (incorporated herein by reference), section 3.8.2 of IPC-4101.
. 4. And the metal cladding is completely removed by etching and measured. Advantages of the electronic support of the present invention include high flexural strength (tensile and compressive strength) and high modulus that can reduce the deformation of circuit boards, including laminates.

The electronic support of the present invention in the form of a copper-clad FR-4 epoxy laminate has a laminate at 288 ° C. across the z-direction (“Z-CTE”) of the laminate, ie, the thickness of the laminate. The coefficient of thermal expansion is determined by the IPC test method (herein incorporated by reference).
According to 4.41, it is preferably less than about 4.5 percent, more preferably in the range of about 0.01 to about 4.5 weight percent. Each such laminate preferably includes eight layers of a 7628 style fabric, but alternatively a style 1080 or 2116 style fabric may be used. Laminates having a low coefficient of thermal expansion are generally less susceptible to expansion and contraction and minimize deformation of the substrate.

The present invention further provides at least one composite layer made according to the teachings herein and in a manner different from the composite layers taught herein, for example, at least one made using conventional glass fiber composite technology. It is intended for the manufacture of multilayer laminates and electronic circuit boards comprising one composite layer. More specifically, as is well known to those skilled in the art, filaments of continuous fiberglass strands conventionally used to weave fabrics are:
Lowenstein (3rd edition, 1993), which is incorporated herein by reference.
Or partially or fully dextrinized starch, or a starch comprising amylose, a hydrogenated vegetable oil, a cationic wetting agent, an emulsifier and water, including but not limited to those disclosed on pages 237-244 of / Processed with oil sizing. The vertical yarns produced from these strands are then, before weaving,
For example, treated with a solution such as poly (vinyl alcohol) disclosed in U.S. Pat. No. 4,530,876, column 3, line 67 to column 4, line 11, incorporated herein by reference. During the weaving process, the strands are protected from wear. This operation is usually called thrashing. Poly (vinyl alcohol) and starch / oil sizes are generally not compatible with the polymer matrix materials used by composite manufacturers, and essentially impregnate all organic materials with glass prior to impregnation of the woven fabric. To remove from the surface of the fiber, the fabric is
Must be cleaned. This is achieved in various ways, for example by rubbing the fabric or, more generally, by heat treating the fabric in a manner well known in the art. As a result of the cleaning operation, there is no proper interface between the polymer matrix material used to impregnate the fabric and the cleaned fiberglass surface, which results in the coupling agent being applied to the fiberglass surface. There must be. This operation is sometimes called finishing by those skilled in the art. The coupling agents most commonly used in finishing operations are described in E.C. P. Plueddem
silanes, including, but not limited to, those disclosed on pages 146-147 of "Silane Coupling Agents" (1982). See also Lowenstein (3rd edition, 1993) at pages 249-256. After treatment with the silane, the fabric is impregnated with a compatible polymer matrix material, squeezed between a set of metering rolls and dried, as described above,
Form a semi-cured prepreg. It should be understood that depending on the nature of the sizing, cleaning operation, and / or matrix resin used in the composite, the slashing and / or finishing steps may be omitted. One or more prepregs incorporating conventional glass fiber composite technology are then incorporated into one or more prepregs incorporating the present invention.
It can be combined with one or more prepregs to form an electronic support, especially a multilayer laminate or an electronic circuit board, as described above. For further information on the manufacture of electronic circuit boards, see 1 Electronni, which is incorporated herein by reference.
c Materials Handbook (R) ", ASM Inte
national (1989), pp. 113-115; Tummala (
Ed.), "Microelectronics Packaging Handb
book "(1989), pp. 858-861 and 895-909; W.
Jawitz, "Printed Circuit Board Handbod
ok "(1997), pages 9.1-9.42, and C.I. F. Coombs,
Jr. (Ed.), "Printed Circuits Handbook" (3rd edition, 1988), pp. 6.1-6.7.

The composites and laminates forming the electronic support of the present invention can be used in packaging used in the electronics industry, and more particularly in T
Ummala may be used to form first, second and / or third level packaging, as disclosed on pages 25-43. Further, the invention can be used for other levels of packaging.

The present invention also provides that the first yarn (weft) is interlaced with the second yarn (warp) to form the fabric 14, eg, by air jet weaving as described above. 14 assembling method. Improvements include:
A first yarn comprising E-glass fibers having a coating compatible with the polymer matrix material, (1) one or more polyesters and (2) vinylpyrrolidone polymer, vinyl alcohol polymer, starch and mixtures thereof (see details above) A coating comprising at least one polymer selected from the group consisting of:

[0121] Another aspect of the invention is to laminate the woven fabric by coating the woven fabric with a polymer matrix material and applying heat to the coated fabric to form a coated fabric. A method for forming a plate and a polymer matrix material. The woven fabric comprises a yarn comprising E-glass fibers. Improvements include E glass fibers having a coating compatible with the polymer matrix material, and yarns having an air jet transport resistance greater than about 100,000 gram weight per gram mass of yarn. As described in detail above, the yarn is fed to the needle air jet nozzle unit at a feed rate of about 274 meters (about 300 yards) per minute and a pressure of about 310 kilopascals (about 45 pounds per square inch) gauge. And the laminate has a fabric fill direction bending strength of greater than about 3 × 10 ⁷ kilograms per square meter (about 42.7 kpsi).

[0122] Another aspect of the invention is to laminate the woven fabric by coating the woven fabric with a polymer matrix material and applying heat to the coated fabric to form a coated fabric. A method for forming a plate and a polymer matrix material. The woven fabric includes a yarn that includes E glass fiber. Improvements include E-glass fibers having a coating compatible with the polymer matrix material, wherein the coating is
(1) a polyester and (2) at least one polymer selected from the group consisting of vinylpyrrolidone polymers, vinyl alcohol polymers, and starch.

Next, the present invention is illustrated by the following specific, non-limiting examples.

Example 1 The compatibility of the air jet weaving process with several different yarn samples was measured using the “air jet transport resistance” test method described in detail above.

A yarn sample according to the present invention was coated with a matrix resin compatible aqueous forming size composition AF according to Table 1A below and "air jet transport resistance".
It was evaluated using the test method. Each composition contained less than 1 weight percent acetic acid. Each formed size composition had about 2.5 weight percent solids. Each of the coated glass fiber strands was twisted to form a yarn and wound on a bobbin in a similar manner using conventional twisting equipment. Sample B _vac was coated with aqueous formed size composition B, but vacuum dried at a temperature of 190 ° F for about 46 hours. The value of loss on ignition for each of Samples AF was less than 1 weight percent. Samples C _hi and D _hi had loss on ignition values of 1.59 weight percent and 1.66 weight percent, respectively.

[0126]

[Table 6] ⁸² RD-847A polyester resin, commercially available from Borden Chemicals, Columbia, Ohio ⁸³ DESMOPHEN 2000 polyethylene adipate diol, commercially available from Bayer, Pittsburgh, Pennsylvania ⁸⁴ Shell Chem., Houston, Texas. EPI-REZ® 3522-W-66 ⁸⁵ available from Shell Chemical Co. of Houston, Texas. Commercially available from, EPON 826 ⁸⁶ Wayne, commercially available from ISP Chemicals of New Jersey, PVP K-30 polyvinyl pyrrolidone ⁸⁷ Tarrytown, New York in OSi Specialties
, Inc. A187 gamma-glycidoxypropyltrimethoxysilane ⁸⁸ OSi Specialties from Tarrytown, New York
, Inc. A174 gamma-methacryloxypropyltrimethoxysilane ⁸⁹ OSi Specialties from Tarrytown, New York, commercially available from
, Inc. A-1100 amino-functionalized organosilane coupling agent ⁹⁰ , commercially available from BASF Corporation of Parsippany, NJ
PLURONIC ^™ F-108 polyoxypropylene-polyoxyethylene copolymer ⁹¹ IGEPAL CA-630 ethoxylated octylphenoxyethanol ⁹² General Mills Chemicals, Inc., available from GAF Corporation of Wayne, New Jersey. ARKAMULS EL-, commercially available from VERSAMID 140 polyamide ⁹³ Rhone-Poulenc, commercially available from
719 polyoxyethylated vegetable oil ⁹⁴ MACOL NP-6 nonylphenol surfactant ⁹⁶ eKak, commercially available from KESSCO PEG 600 polyethylene glycol monolaurate ⁹⁵ , available from BASF from Stepan Company of Chicago, Illinois, Parsippany, NJ Henkel Corporation, Illinois
EMERY® 6717 partially amidated polyethylenimine ⁹⁷ , commercially available from Henkel Corporation of Kankakee, Ill.
n is commercially available from, EMERY (TM) 6760 lubricant ⁹⁸ Danbury, commercially available from Union Carbide of Connecticut, POLYOX WSR-301 polyoxyethylene polymer ⁹⁹ Lakewood, Ohio of Advanced Ceramics Cor
PolarTherm® PT, commercially available from the Corporation
160 Boron Nitride Powder Particles ¹⁰⁰ Oak Ridge, Tennessee, ZYP Coatings, Inc. ORPAC BORON NITRIDE REL, commercially available from
EASECOAT-CONC Dispersion of boron nitride particles in water.

[0127] Also commercially available starch oil coated yarns of 631 and 633 D-450, starch oil coated yarns of 690 and 695, and 1383 G-75 yarn (PPG Industries, I
nc. From the market) and "Air jet transfer resistance" test method. Also, three comparative samples X1, X2 and X3, each coated with the same aqueous forming composition X, were tested. For the aqueous forming composition X, see FIG.
Is described in. Comparative sample X1 had a solids content of 2.5 weight percent. Comparative sample X2 had a solids content of 4.9 weight percent and was air dried at about 25 ° C. for about 8 hours. Comparative sample X3 had a solids content of 4.6 weight percent.

[0128]

[Table 7] ¹⁰¹ RD-847A polyester resin, commercially available from Borden Chemicals, Ohio, ^102. DESMOPHEN 2000 polyethylene adipate diol, commercially available from Bayer, Pittsburgh, Pennsylvania. ¹⁰³ Tarrytown, New York, NY. A187 gamma-glycidoxypropyltrimethoxysilane ¹⁰⁴ , available from OSi Specialties, Inc. of Tarrytown, New York. A174 gamma-methacryloxypropyltrimethoxysilane ¹⁰⁵ commercially available from BASF Corporation of New Jersey, Parsippany, Pluronic ^™ F-108 polyoxypropylene-polyoxyethylene copolymer ¹⁰⁶ General Mills Chemicals, Inc. VERSAMID 140 polyamide ¹⁰⁷ commercially available from BASF of Parsippany, New Jersey, MACOL NP-6 nonylphenol surfactant ¹⁰⁸ POLYOX WSR-301, commercially available from Union Carbide of Danbury, Connecticut. Ethylene polymer.

Each yarn sample was loaded into an internal air jet chamber 2 mm in diameter,
Having a nozzle-like outlet tube having a length of 0 centimeters
Ruti needle-shaped air jet nozzle unit (Model No. 044 455 0)
01) (Sparte of Spartanburg, North Calolina)
(commercially available from R. Ruti) at an air pressure of 310 kilopascal gauge (45 pounds per square inch) at a rate of 274 meters (300 yards) / min. The tensiometer was placed in contact with the yarn before the yarn entered the air jet nozzle. The tensiometer provided a measurement of the gram weight (resistance) exerted on each yarn sample by the air jet as each yarn sample was sucked into the air jet nozzle. These values are set forth in Table 1C below.

[0130]

[Table 8] * Coated with starch oil sizing formulation As shown in Table 1C above, each yarn coated with a polymer matrix material compatible siding composition according to the present invention has an air jet transport resistance greater than 100,000. I had. Only starch oil sized commercial strands, which are generally incompatible with the polymer matrix materials described above,
It had an air jet transport resistance greater than zero. Sample yarns C _hi and D _hi with a polymer matrix compatible coating had an air jet transport resistance of less than 100,000 due to the higher coating level of the yarn. That is, the loss on ignition was greater than about 1.5%, which prevented the yarn from being filamentized by the air jet.

[0131] To evaluate the laminate strength of 7628 style fabric (the style parameters described above), and 695 of the sample, and the sample B, (described above) Sample B _{va c} G-75 yarn Formed from each. Each eight ply fabric sample was laminated with an FR-4 resin system of EPON 1120-A80 epoxy resin, dicyandiamide, 2-methylimidazole, and DOWANOL PM to form a laminate.

Each laminate was instituted for Int with the metallization completely removed by etching according to IPC-4101 section 3.8.2.4.
erconnecting and Packaging Electroni
Evaluated by ASTM D-790 and IPC-TM-650 Test Method Manual (December 1994) (the reference is incorporated herein by reference) for flexural strength (maximum fracture stress) of cs. did. Further, regarding the shear strength (short beam shear strength) in the laminated plate, 15.9 millimeter (5/8 inch) intervals and ASTM D-2344 (this document is incorporated herein by reference). With a crosshead speed of 1.27 millimeters (0.05 inches) / min according to
Each laminate was evaluated. The results of these evaluations are shown in Table 1D below.

[0133]

[Table 9] As shown in FIG. 1D, laminate sample B and B _{va c} produced according to the present invention, when compared with laminate samples made from 695 starch oil coated glass fiber yarn, higher flexural strength and It had a short beam shear strength equivalent to the bending value.

Example 2 The laminate samples were evaluated for thermal expansion coefficient (“Z-CTE”) in the z-direction of the laminate, ie, across the thickness of the laminate. Each sample consisted of 7628 style fabrics made of eight layers made from coated yarn sample _Bvac (Sample A) and 695 starch oil coated yarns (described above). (Control). This laminate was prepared using the FR-4 epoxy resin described in Example 1 above, and subjected to IPC test method 2.4.41 (this document is incorporated herein by reference). Was coated with copper according to For each laminate sample, the coefficient of thermal expansion in the z-direction was evaluated at 288 ° C according to IPC test method 2.4.41. Table 2 below shows the results of these evaluations.
Shown in

[0135]

[Table 10] As shown in Table 2, for laminate samples A1 to A3 according to the present invention, the coefficient of thermal expansion in the z-direction of the laminate was the thermal expansion coefficient of control samples 1 and 2 made from a 695 starch oil coated yarn. It was smaller than the coefficient.

Example 3 Aqueous Forming Size Compositions A-D (described in Table 1A of Example 1 above)
And Comparative Sample No. 1 was coated on an E-glass fiber strand. Comparative sample No. Formulations for one are described in Table 3 below. Each formed sizing composition had about 2.5 weight percent solids.
Each coated glass fiber strand was twisted to form a yarn and wound on a bobbin in a similar manner using conventional twisting equipment.

[0137]

[Table 11] ¹⁰⁹RD-847A polyester resin, commercially available from Borden Chemicals of Columbia, Ohio¹¹⁰ DESMOPHEN2000 polyethylene adipate diol, commercially available from Bayer, Pittsburgh, Pennsylvania¹¹¹ Tarrytown, New York's OSi Specialties, Inc. A-187 γ-glycidoxypropyl tri
Methoxysilane¹¹² Tarrytown, New York's OSi Specialties, Inc. A174 [gamma] -methacryloxypropyl ester commercially available from
Limethoxysilane¹¹³ PLURONIC, commercially available from BASF Corporation of Parsippany, New Jersey^TMF-108 polyoxypropyl
Len-polyoxyethylene copolymer¹¹⁴ General Mills Chemicals, Inc. VERSAMID 140 polyamide, commercially available from¹¹⁵ MACOL NP-6 nonylphenol surfactant, commercially available from BASF of Parsippany, New Jersey¹¹⁶ POLYOX WSR-301 polyoxyethylene polymer, commercially available from Union Carbide of Danbury, Connecticut ¹¹⁷ A commercially available glass fiber yarn product, PPG Industries, Inc. 1383.

The yarns of Samples A to D and Comparative Sample No. 1 and Comparative Sample No. 2 ¹¹⁷ Were evaluated for several physical properties such as loss on ignition (LOI), air jet compatibility (air resistance), frictional force, and broken filaments.

Table 4 shows the average value of the ignition loss (weight percent of the solids content of the formed size composition divided by the total weight of the glass and the dried sizing composition) of each sample run three times. Is shown.

Each yarn was passed through a checkline tensiometer (which imparts tension to the yarn) and further through a 2 mm diameter Ruti air nozzle at an air pressure of 310 kPa (45 pounds per square inch). 2
Air resistance or tension was evaluated by feeding the yarn at a controlled feed rate of 74 meters (300 yards) / min.

Also, by applying about 30 grams of tension to each yarn sample as the sample is pulled at a rate of 274 meters (300 yards) / min through a pair of conventional tension measurement devices, Comparative samples were evaluated for frictional force. Between these tension measuring devices is approximately 5 centimeters (2
An inch) diameter fixed chrome post is mounted, which causes the yarn to move about 5 cm from a straight path between the tension measuring devices. Table 4 below shows the difference in force in grams. This friction test is intended to simulate the friction on the yarn during the weaving operation.

Further, each sample and a comparative sample were evaluated for filament breakage using an abrasion tester. 200 grams of tension was applied to each test sample as each test sample was pulled through the abrasion tester apparatus at a rate of 0.46 meters (18 inches) / min for 5 minutes. Each sample and the comparative sample were evaluated by performing the test twice. FIG. 4 below shows the average number of broken filaments. The abrasion tester consisted of two parallel rows of steel leads, each row spaced about 1 inch apart. Each test yarn sample was passed between two adjacent leads of the first lead row, and then passed between two adjacent leads of the second lead row, and between these lead rows, It was moved a distance of 1/2 inch.
These leads are 4 inches long and 240 times / parallel to the direction of yarn movement.
Moved back and forth at a speed of minutes. FIG. 4 below shows the results of air drag, friction, and filament breakage under abrasion for Samples AD and Comparative Samples.

[0143]

[Table 12] As shown in Table 4, Sample A and Sample B coated with the sizing composition containing boron nitride according to the present invention had less filament breakage, lower frictional force, and lower air resistance than the comparative sample. It was higher. Samples C and D also had higher air resistance values than the comparative samples.
This air resistance test is a relative test intended to simulate the weft insertion process of an air jet loom that transports yarn through the loom by air jet propulsion. The easier the air jet to filamentize the yarn, the greater the surface area for air jet propulsion, which can facilitate the movement of the yarn through the loom and increase productivity. The air resistance of Samples AD (samples made according to the present invention) is higher than the air resistance of the comparative sample. This indicates better air jet compatibility.

Example 4 An aqueous formed size composition E according to the present invention was prepared by mixing each of the components in the amounts shown in Table 5.
, F, G and H were formed, and comparative samples were formed in the same manner as described above. Each composition contained less than about 1 weight percent acetic acid on a total weight basis.

Each aqueous formed size composition of Table 5 was coated on a G-75E glass fiber strand. The solids content of each formed size composition was about 6 to about 25 weight percent.

[0146]

[Table 13] ¹¹⁸ Houston, commercially available from Texas of Shell Chemical, EPON 826 ¹¹⁹ Wayne, commercially available from ISP Chemicals of New Jersey, which is commercially available from PVP K-30 polyvinyl pyrrolidone ¹²⁰ Rhone-Poulenc, ALKAMULS EL -719 poly oxyethylated vegetable oil ¹²¹ Wayne, commercially available from GAF Corporation of New Jersey, IGEPAL CA-630 ethoxylated octylphenoxyethanol ¹²² Chicago, are city sales from Stepan Company of Illinois, KESSCO PEG 600 polyethylene glycol monolaurate ester ¹²³ Tarrytown OSi Spe of New York ialitie s, Inc. A-187 gamma-glycidoxypropyltrimethoxysilane ¹²⁴ , commercially available from Henkel Corporation of Kankake, Illinois. EMERY® 6717 partially amidated polyethyleneimine ¹²⁵ Sybron, Birmingham, NJ. Protolube HD High Density Polyethylene Emulsion ¹²⁶ , commercially available from Chemi cals, PolarTherm® P, commercially available from Advanced Ceramics Corporation of Lakewood, Ohio.
T160 boron nitride powder particles ¹²⁷ Oak Ridge, Tennessee, ZYP Coatings, Inc. ORPAC BORON NITRIDE REL, commercially available from
EASECOAT-CONC Dispersion of boron nitride particles in water.

Each coated glass fiber strand was twisted to form a yarn and wound on a bobbin in a similar manner using conventional twisting equipment. The yarns of Samples F and H exhibited minimal sizing openings during twisting, and the yarns of Samples E and G exhibited severe sizing openings during twisting.

The yarns of Samples E to H and the yarn of the comparative sample were measured in the same manner as in Example 3 except that the air resistance values of the two bobbin samples were measured at the pressures shown in Table 6. The air resistance was evaluated. Each yarn was converted to a British SDL I
international Inc. Shirley model no. Using an 84041L filament break detector at 200 meters / minute,
The average number of filament breaks per 1200 meter yarn was evaluated. These values represent the average of the measurements made on the four bobbins of each yarn.
The breaking value of the filament was recorded in a portion taken from the entire bobbin and was 136 grams (
3/10 pounds and 272 grams (6/10 pounds) of yarn unraveled from the bobbin.

Each yarn was also evaluated for a gate tension test. Table 6 shows the results. The number of filament breaks measured according to the gate tension test method was determined by unraveling the yarn sample from the bobbin at 200 meters / minute, passing the yarn through a series of eight parallel ceramic pins, and breaking the yarn through the Sirley break described above. It is measured by counting the number of broken filaments passed through a filament detector.

[0150]

[Table 14] The test results shown in Table 6 appear to indicate that samples EH according to the present invention generally had higher abrasion resistance compared to the comparative samples, but were present in samples EH. These results were considered inconclusive as it was believed that the polyethylene emulsion component of the comparative sample that did not have contributed to the wear properties of the yarn.

From the above description, it can be seen that the present invention has good flexural strength and flexural modulus, coefficient of thermal expansion in the z-direction, and other desirable properties that are useful in a variety of applications, such as reinforcement for printed circuit boards. It can be seen that providing a laminate having advantages.

It will be appreciated by those skilled in the art that the above-described embodiments may be modified without departing from the broad inventive concept thereof. Accordingly, it is not intended that the invention be limited to the specific embodiments disclosed, as defined by the appended claims, but that the invention include modifications that fall within the spirit and scope of the invention. It is understood that

[Brief description of the drawings]

The foregoing summary as well as a detailed description of the preferred embodiments will be better understood when read in conjunction with the appended drawings.

FIG. 1 is a cross-sectional view of a reinforced laminate according to the present invention.

FIG. 2 is a top view of a fabric according to the present invention.

FIG. 3 is a perspective view of a coated fiber strand according to the present invention.

FIG. 4 is a cross-sectional view of an electronic support according to the present invention.

FIG. 5 is a cross-sectional view of another embodiment of the electronic support according to the present invention.

FIG. 6 is a schematic diagram of a method for assembling a fabric and forming a laminate according to the present invention.

FIG. 6a is an enlarged view of a part of FIG. 6;

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // B29K 105: 08 C08L 101: 00 C08L 101: 00 C03C 25/02 N (31) Claim number 09 / 170,578 (32) Priority date October 13, 1998 (Oct. 13, 1998) (33) Priority claiming country United States (US) (81) Designated country EP (AT, BE, CH, CY, DE) , DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML) , MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD) , RU, TJ , TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN , MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZW ( 72) Inventor C. Shan United States of America Pennsylvania 15044, Gibsonia, Amres Drive 5165 F term (reference) 4F072 AA07 AA08 AB09 AB24 AB28 AC04 AD04 AD08 AD12 AD13 AD23 AD33 AD37 AD38 AD41 AD42 AD43 AD44 AD45 AD46 AE11 AF01 AF02 AF06 AG03 AG16 AH AJ04 AJ11 AL12 AL13 4F100 AA0 1A AA09A AA25A AA33A AC04A AC05A AC10A AE06A AG00A AK01A AK01B AK03A AK03B AK23A AK23B AK33A AK33B AK35A AK35B AK41A AK41B AK46A AK46B AK49A AK49B AK51A AK51B AK53A AK53B AK55A AK55B AK56A AK56B AK57A AK57B BA03 BA07 BA10A BA10C DG01A DH01A GB43 JB13A JB13B JB16A JB16B JG01C 4G060 BA01 BB02 BC00 BD05 CA00 CB02 CB05 CB09 CB12 CB22 CB23 CB24 CB26

Claims (73)

[Claims] 1. A reinforced laminate for an electronic support, wherein the laminate is at least partially coated with: (a) a polymer matrix material; and (b) a coating compatible with the polymer matrix material. Woven reinforced fabric comprising a yarn containing glass fiber, wherein the yarn has a loss on ignition in the range of about 0.01 to about 0.6% by weight, and about 100,000 grams per gram mass of yarn. Having a greater air jet transport resistance, the air jet transport resistance using a needle air jet nozzle unit with an internal air jet chamber having a diameter of 2 mm and a nozzle exit tube having a length of 20 cm. Yarn feed rate of about 300 yards / minute, and about 310 kilopascals (about 45 points). Evaluated at air pressure of de / square inch) gauge, wherein the laminate plate in the filling direction of the fabric, has a greater flexural strength than about 3 × 10 ⁷ kilogram / square meter (about 42.7Kpsi), woven Reinforced fabrics, including, reinforced laminates. 2. The reinforced laminate according to claim 1, wherein the polymer matrix material comprises at least one material selected from the group consisting of a thermosetting matrix material and a thermoplastic matrix material. 3. The thermoset matrix material of claim 1, wherein the polymer matrix material is at least one selected from the group consisting of thermoset polyesters, vinyl esters, epoxides, phenolic resins, aminoplasts, thermoset polyurethanes, and mixtures thereof. The reinforced laminate according to claim 2, comprising: 4. The thermoset matrix material comprises an epoxide.
The reinforced laminate according to item 1. 5. The method according to claim 1, wherein the polymer matrix material is polyolefin, polyamide, thermoplastic polyurethane, thermoplastic polyester, vinyl polymer, polyimide, polyethersulfone, polyphenylsulfone, polyetherketone, polyphenylene oxide, polyphenylene sulfide, polyacetal, or polycarbohydrate. 3. The reinforced laminate according to claim 2, comprising at least one thermoplastic matrix material selected from the group consisting of nates and mixtures thereof. 6. The method according to claim 1, wherein at least one of the glass fibers is E-glass fiber, D-glass fiber,
The reinforced laminate according to claim 1, wherein the reinforced laminate is selected from the group consisting of glass fibers, S-glass fibers, Q-glass fibers, E-glass derivative fibers and combinations thereof. 7. At least one of said glass fibers is E-glass fiber.
A reinforced laminate according to claim 6. 8. The reinforced laminate according to claim 6, wherein at least one of said glass fibers is an E-glass derivative fiber. 9. The reinforced laminate according to claim 1, wherein the coating on the glass fibers of the fabric comprises inorganic solid lubricant particles. 10. The reinforced laminate according to claim 9, wherein said inorganic solid lubricant particles of said coating have a layered structure. 11. The inorganic solid lubricant particles include at least one particle selected from the group consisting of non-hydratable inorganic solid lubricant particles, hydratable inorganic solid lubricant particles, and mixtures thereof. Item 10. A reinforced laminate according to item 9. 12. The non-hydratable inorganic solid lubricant particles include at least one particle selected from the group consisting of graphite, boron nitride, metal dichalcogenide, cadmium iodide, silver sulfide and mixtures thereof. A reinforced laminate according to claim 11. 13. The reinforced laminate according to claim 12, wherein the non-hydratable inorganic solid lubricant particles include boron nitride particles having a hexagonal structure. 14. The non-hydratable inorganic solid lubricant particles comprising molybdenum disulfide,
13. The reinforced laminate of claim 12, comprising at least one metal dichalcogenide selected from the group consisting of molybdenum diselenide, tantalum disulfide, tantalum diselenide, tungsten disulfide, tungsten diselenide, and mixtures thereof. Board. 15. The non-hydratable inorganic solid lubricant particles are selected from the group consisting of indium, thallium, tin, copper, zinc, gold, silver, calcium carbonate, calcium fluoride, zinc oxide and mixtures thereof. 12. The reinforced laminate according to claim 11, comprising at least one particle. 16. The reinforced laminate according to claim 11, wherein said hydratable inorganic solid lubricant particles comprise a layered silicate. 17. The enhancement of claim 16, wherein the layered silicate comprises at least one layered silicate selected from the group consisting of mica, talc, gypsum, kaolinite, montmorillonite, and mixtures thereof. Laminated board. 18. The reinforced laminate according to claim 11, wherein the hardness value of the inorganic solid lubricant particles is less than or equal to the hardness value of the E-glass fibers. 19. The reinforced laminate of claim 1, wherein the coating on the glass fibers of the fabric comprises a film-forming polymer. 20. The method of claim 1, wherein at least one of the glass fibers is formed from a fiberizable material selected from the group consisting of a non-glassy inorganic material, a natural material, an organic polymer material, and combinations thereof. Reinforced laminate. 21. The reinforced laminate of claim 1, wherein the laminate has a flexural strength in the filling direction of the fabric of greater than about 4.9 × 10 ⁷ kg / m ² (about 70 kpsi). 22. A reinforced laminate for an electronic support, wherein the laminate is at least partially coated with: (a) a polymer matrix material; and (b) a coating compatible with the polymer matrix material. Woven reinforced fabric comprising a yarn containing glass fibers, wherein the coating comprises (1) a polyester; and (2) at least one polymer selected from the group consisting of vinylpyrrolidone polymers, vinyl alcohol polymers and starch. Including, woven reinforced fabric, including, reinforced laminates. 23. The reinforced laminate according to claim 22, wherein said polymer matrix material comprises at least one material selected from the group consisting of a thermoset matrix material and a thermoplastic matrix material. 24. The polymer matrix material comprising: a thermosetting polyester;
24. The reinforced laminate of claim 23, comprising at least one thermoset matrix material selected from the group consisting of vinyl esters, epoxides, phenolic resins, aminoplasts, thermoset polyurethanes, and mixtures thereof. 25. The reinforced laminate of claim 24, wherein the thermoset matrix material comprises an epoxide. 26. The polymer matrix material is made of polyolefin, polyamide, thermoplastic polyurethane, thermoplastic polyester, vinyl polymer, polyimide, polyether sulfone, polyphenyl sulfone, polyether ketone, polyphenylene oxide, polyphenylene sulfide, polyacetal, polycarbo. 24. The reinforced laminate of claim 23, wherein the reinforced laminate is a thermoplastic matrix material selected from the group consisting of nates and mixtures thereof. 27. At least one of said glass fibers is E-glass fiber, D
23. The reinforced laminate according to claim 22, wherein the reinforced laminate is selected from the group consisting of: glass fibers, S-glass fibers, Q-glass fibers, E-glass derivative fibers, and combinations thereof. 28. The reinforced laminate according to claim 27, wherein at least one of said glass fibers is E-glass fiber. 29. The reinforced laminate according to claim 27, wherein at least one of said glass fibers is an E-glass derivative fiber. 30. The reinforced laminate of claim 22, wherein said coating on said glass fibers of said fabric further comprises inorganic solid lubricant particles. 31. The reinforced laminate of claim 30, wherein the inorganic solid lubricant particles of the coating have a layered structure. 32. The inorganic solid lubricant particles include at least one particle selected from the group consisting of non-hydratable inorganic solid lubricant particles, hydratable inorganic solid lubricant particles, and mixtures thereof. Item 30. The reinforced laminate according to item 30. 33. The non-hydratable inorganic solid lubricant particles comprise at least one particle selected from the group consisting of graphite, boron nitride, metal dichalcogenides, cadmium iodide, silver sulfide and mixtures thereof. A reinforced laminate according to claim 32. 34. The reinforced laminate according to claim 33, wherein the non-hydratable inorganic solid lubricant particles include boron nitride particles having a hexagonal structure. 35. The non-hydratable inorganic solid lubricant particles comprise molybdenum disulfide,
34. The reinforced laminate of claim 33, comprising at least one metal dichalcogenide selected from the group consisting of molybdenum diselenide, tantalum disulfide, tantalum diselenide, tungsten disulfide, tungsten diselenide, and mixtures thereof. Board. 36. The non-hydratable inorganic solid lubricant particles comprise indium, thallium, tin, copper, zinc, gold, silver, calcium carbonate, calcium fluoride, zinc oxide,
And at least one particle selected from the group consisting of:
A reinforced laminate according to claim 32. 37. The reinforced laminate of claim 32, wherein said hydratable inorganic solid lubricant particles comprise a layered silicate. 38. The enhancement of claim 37, wherein the layered silicate comprises at least one layered silicate selected from the group consisting of mica, talc, gypsum, kaolinite, montmorillonite, and mixtures thereof. Laminated board. 39. The reinforced laminate according to claim 30, wherein the hardness value of the inorganic solid lubricant particles is less than or equal to the hardness value of the glass fiber. 40. The reinforced laminate of claim 22, wherein the coating on the E-glass fibers of the fabric comprises a film forming polymer. 41. At least one of the glass fibers is made of a non-glass inorganic material,
23. The reinforced laminate of claim 22, formed from a fiberizable material selected from the group consisting of natural materials, organic polymer materials, and combinations thereof. 42. The yarn having a loss on ignition in the range of about 0.01 to about 0.6% by weight and an air jet transport resistance greater than about 100,000 grams per gram of yarn. The air jet transport resistance is about 274 m using a needle air jet nozzle unit with an internal air jet chamber having a diameter of 2 mm and a nozzle outlet tube having a length of 20 cm.
A yarn feed rate of about 300 yards / minute, and about 310 kilopascals (about 45
23. The reinforced laminate of claim 22, evaluated at an air pressure of pounds per square inch). 43. The laminate, in the filling direction of the fabric, about 3 × 10 ⁷ kg / m ² (about 42.7Kpsi) greater flexural strength, reinforcing laminate according to claim 22. 44. A reinforced laminate for an electronic support, wherein the laminate is at least partially coated with: (a) a polymer matrix material; and (b) a coating compatible with the polymer matrix material. A reinforced laminate comprising: a woven reinforced fabric comprising a yarn containing glass fibers, wherein the coating comprises: (1) a polyester; and (2) a vinylpyrrolidone polymer. 45. At least one of said glass fibers is E-glass fiber, D
45. The reinforced laminate of claim 44, wherein the reinforced laminate is selected from the group consisting of -glass fibers, S-glass fibers, Q-glass fibers, E-glass derivative fibers, and combinations thereof. 46. An electronic circuit board, wherein the electronic circuit board comprises: (a) a laminate for an electronic support comprising: (i) a woven fabric comprising yarns containing glass fibers. The yarn has a loss on ignition in the range of about 0.01 to about 0.6% by weight and an air jet transport resistance greater than about 100,000 grams weight per gram mass of yarn. The drag force is determined using a needle air jet nozzle unit with an internal air jet chamber having a diameter of 2 mm and a nozzle exit tube having a length of 20 cm, a yarn feed rate of about 300 yards / minute, and Assessed at an air pressure of about 310 kilopascals (about 45 pounds per square inch) gauge, where the laminate is oriented in the filling direction of the fabric. , About 3 × 10 ⁷ kilogram / square meter (about 42.7Kpsi) having a greater flexural strength, woven fabric; layer and (ii) a polymeric matrix material applied to at least a portion of the fabric; and (b) An electrical conductive layer disposed adjacent to a selected location on a selected side of the laminate. 47. At least one of said glass fibers is E-glass fiber, D
47. The electronic circuit board of claim 46, wherein the electronic circuit board is selected from the group consisting of -glass fibers, S-glass fibers, Q-glass fibers, E-glass derivative fibers, and combinations thereof. 48. The electronic circuit board according to claim 46, further comprising at least one opening extending through at least a portion of the circuit board. 49. The electronic circuit board according to claim 46, wherein said circuit board is a first, second or third level package. 50. An electronic circuit board, said electronic circuit board comprising: (a) a laminate for an electronic support comprising: (i) glass fibers at least partially coated with a coating. A woven fabric, comprising: (1) a polyester; and (2) at least one polymer selected from the group consisting of vinylpyrrolidone polymers, vinyl alcohol polymers and starch. And (ii) a layer of a polymer matrix material applied to at least a portion of the fabric; and (b) an electrically conductive layer disposed adjacent to a selected portion on a selected side of the laminate. Electronic circuit board. 51. At least one of said glass fibers is E-glass fiber, D
51. The electronic circuit board of claim 50, wherein the electronic circuit board is selected from the group consisting of -glass fibers, S-glass fibers, Q-glass fibers, E-glass derivative fibers, and combinations thereof. 52. The electronic circuit board according to claim 50, further comprising at least one opening extending through at least a portion of the circuit board. 53. The electronic circuit board according to claim 50, wherein the circuit board is a first, second or third level package. 54. An electronic circuit board, wherein the electronic circuit board comprises: (a) a laminate for an electronic support comprising: (i) a first composite layer comprising: (1) a glass fiber; Claims: 1. A woven fabric comprising yarns comprising: a yarn loss in the range of about 0.01 to about 0.6% by weight; and an air jet greater than about 100,000 gram weight per gram mass of yarn. The air jet transfer resistance is about 274 m (about 274 m) using a needle air jet nozzle unit with an internal air jet chamber having a diameter of 2 mm and a nozzle exit tube having a length of 20 cm. Evaluated at a yarn feed rate of 300 yards / minute, and an air pressure of about 310 kilopascals (about 45 pounds per square inch) gauge, where the laminate is: In the filling direction of the fabric,
A woven fabric having a flexural strength of greater than about 3 × 10 ⁷ kilograms per square meter (about 42.7 kpsi); and (2) a layer of a polymer matrix material applied to at least a portion of the fabric; and (ii) the woven fabric. An electronic circuit board, comprising: a second composite layer different from the first composite layer; and (b) an electrically conductive layer disposed adjacent to a selected portion on a selected side of the laminate. 55. The method of claim 55, wherein at least one of said glass fibers is E-glass fiber, D
55. The electronic circuit board of claim 54, wherein the electronic circuit board is selected from the group consisting of -glass fibers, S-glass fibers, Q-glass fibers, E-glass derivative fibers, and combinations thereof. 56. The electronic circuit board according to claim 54, further comprising at least one opening extending through at least a portion of the circuit board. 57. The electronic circuit board according to claim 54, wherein the circuit board is a first, second or third level package. 58. An electronic circuit board, the electronic circuit board comprising: (a) a laminate for an electronic support comprising: (i) a first composite layer comprising: (1) at least partially A woven fabric comprising a yarn containing glass fibers coated with a coating, wherein the coating is at least selected from the group consisting of: (A) a polyester; and (B) a vinylpyrrolidone polymer, a vinyl alcohol polymer and a starch. Including one polymer,
A woven fabric; and (2) a layer of a polymer matrix material applied to at least a portion of the fabric; and (ii) a second composite layer different from the first composite layer; and (b) a selection of the laminate. An electronic circuit board, comprising: an electrically conductive layer disposed adjacent to a selected portion of the side. 59. At least one of said glass fibers is E-glass fiber, D
59. The electronic circuit board of claim 58, wherein the electronic circuit board is selected from the group consisting of: glass fibers, S-glass fibers, Q-glass fibers, E-glass derivative fibers, and combinations thereof. 60. The electronic circuit board according to claim 58, further comprising at least one opening extending through at least a portion of the circuit board. 61. The electronic circuit board according to claim 58, wherein said circuit board is a first, second or third level package. 62. A copper-coated reinforced laminate for an electronic support, the laminate comprising: (a) a polymer matrix material; and (b) one or more woven reinforced fabrics. Each of the layers is about 30% by weight
And 75% by weight of the yarn, the yarn comprising glass fibers at least partially coated with a coating compatible with the polymer matrix material;
Wherein the laminate comprises a woven reinforced fabric having a coefficient of thermal expansion in the z-direction at a temperature of 288 ° C. of less than about 4.5%. 63. The laminate as set forth in claim 1 wherein said laminate is at about 288 ° C.
. 63. The laminate of claim 62 having a coefficient of thermal expansion in the range of 5%. 64. At least one of said glass fibers is E-glass fiber, D
63. The laminate of claim 62, wherein the laminate is selected from the group consisting of -glass fibers, S-glass fibers, Q-glass fibers, E-glass derivative fibers, and combinations thereof. 65. The laminate of claim 62, further comprising at least one opening extending through at least a portion of the circuit board. 66. The laminate according to claim 62, wherein the circuit board is a first, second or third level package. 67. The laminate of claim 62, wherein the laminate comprises eight layers of a 7628 woven fabric. 68. A method of assembling a fabric by knitting a first yarn with a second yarn to form a fabric, the improvement comprising: a coating wherein the first yarn is compatible with a polymer matrix material. At least partially coated glass fibers, wherein the coating is at least selected from the group consisting of: (1) a polyester; and (2) a vinylpyrrolidone polymer, a vinyl alcohol polymer, a starch, and mixtures thereof. Containing one polymer. 69. At least one of said glass fibers is E-glass fiber, D
69. The method of claim 68, wherein the method is selected from the group consisting of: glass fibers, S-glass fibers, Q-glass fibers, E-glass derivative fibers, and combinations thereof. 70. A woven fabric and a laminate of the polymer matrix material by at least partially coating the woven fabric with a polymer matrix material, forming a coated fabric, and applying heat to the coated fabric. A method of forming, wherein the woven fabric comprises a yarn containing glass fibers, wherein the improvements include: the glass fibers are at least partially coated with a coating compatible with the polymer matrix material. Wherein the yarn is from about 0.01 to about 0
. Loss on ignition in the range of 6% by weight, and about 100,00 per gram weight of yarn.
Air jet transfer resistance greater than 0 grams weight, using a needle air jet nozzle unit with an internal air jet chamber having a diameter of 2 mm and a nozzle exit tube having a length of 20 cm And a yarn feed rate of about 300 yards / minute and about 310
Rated at an air pressure of kilopascal (approximately 45 pounds per square inch) gauge,
And the laminate has a flexural strength greater than about 3 × 10 ⁷ kilograms per square meter (about 42.7 kpsi) in the filling direction of the fabric;
Including, methods. 71. At least one of said glass fibers is E-glass fiber, D
71. The method of claim 70, wherein the method is selected from the group consisting of: glass fibers, S-glass fibers, Q-glass fibers, E-glass derivative fibers, and combinations thereof. 72. A woven fabric and a laminate of the polymer matrix material by at least partially coating the woven fabric with a polymer matrix material, forming a coating fabric, and applying heat to the coating fabric. A method of forming, wherein the woven fabric comprises yarns containing glass fibers, wherein the improvements include: wherein the glass fibers are at least partially coated with a coating compatible with a polymer matrix material. Wherein the coating comprises: (1) a polyester; and (2) at least one polymer selected from the group consisting of a vinylpyrrolidone polymer, a vinyl alcohol polymer and a starch. 73. At least one of said glass fibers is E-glass fiber, D
73. The method of claim 72, wherein the method is selected from the group consisting of glass fibers, S-glass fibers, Q-glass fibers, E-glass derivative fibers, and combinations thereof.