JP2002527538A - Glass fiber reinforced prepreg, laminate, electronic circuit board, and fabric assembling method - Google Patents

Abstract

(57) Summary One aspect of the present invention is a prepreg for an electronic support, the prepreg containing the following components: (a) a polymeric matrix material; and (b) a strand comprising glass fibers. Wherein at least a portion of the fabric has a coating compatible with the polymeric matrix material, and the prepreg uses a 0.46 mm (0.018 inch) diameter tungsten carbide drill. As measured after drilling 2000 holes through a stack of three laminates at a hole density of 62 holes per square centimeter (400 holes per square inch) and a chip load of 0.001. , Having a drill tip wear rate of about 32% or less, and each laminate includes eight prepregs. The present invention also provides a laminate incorporating the prepreg. Another aspect of the present invention is a prepreg for an electronic support. The present invention also provides a laminate incorporating the prepreg.

Description

DETAILED DESCRIPTION OF THE INVENTION

(Cross Reference of Related Applications) The present patent application is filed on October 13, 1998, by “Glass Five”.
r-Reinforced Laminates, Electronic Ci
rcuit Boards and Methods for Assembl
B. ing a Fabric ". Novich et al., US patent application Ser.
No./170,578, which is a continuation-in-part application, which was filed in August 1998
"Glass Fiber-Reinforc, filed on March 6 and now abandoned
ed Laminates, Electronic Circuit Boar
ds and Methods for Assembling a Fabr
ic ". Novich et al. Is a continuation-in-part of U.S. patent application Ser.
ss Fiber Strands and Products Include
B. ing the Same. Novich et al., US patent application Ser.
This is a continuation-in-part application of U.S. Pat. This application is also based on October 13, 1998.
"Inorganic Lubricant-Coated G
las Fiber Strands and Products Incl
B. UDING THE SAME. Novich et al., A continuation-in-part of US patent application Ser. No. 09 / 170,780, which was filed in 1998.
Inorganic Lubrican, filed March 3, 2013 and now abandoned
t-Coated Glass Fiber Strands and Pro
B. Ducts Includes the Same. Novic
is a continuation-in-part of US Patent Application Serial No. 09 / 034,525 to H et al. This application is also related to "Glass Fiber Stra, filed October 13, 1998.
nds Coated With Thermally Conductive
Inorganic Solid Particles and Produ
B.cts Included the Same. Is a continuation-in-part of US Patent Application No. 09 / 170,781 to Novich et al.
No. 34,663 is a continuation-in-part application.

[0002] This patent application is filed on October 13, 1998, entitled "Methods fo
r Inhibiting Abrasive Wear of Glass
Fiber Strands ". Novich et al., US Patent Application No. 0
9 / 170,579 (this U.S. patent application is a continuation-in-part of U.S. patent application Ser. No. 09 / 034,078, filed Mar. 3, 1998, now abandoned);
"Impaired Glass" filed on October 13, 1998
Fiber Strands and Products Included
B. under the title of "the Same". Novich et al., US Patent Application Serial No. 09/17.
No. 0,566 (this U.S. patent application is a continuation-in-part of U.S. patent application Ser. No. 09 / 034,077 filed Mar. 3, 1998 and now abandoned);
“Inorganic Particle- filed on October 13, 998
Coated Glass Fiber Strands and Produ
B.cts Included the Same. Novich et al., U.S. patent application Ser. No. 09 / 170,565, which was filed on March 3, 1998.
Which is a continuation-in-part of U.S. patent application Ser.

[0003] This application is related to US Provisional Patent Application No. 60 / 133,0, filed May 7, 1999.
No. 75; U.S. Provisional Patent Application No. 60 / 133,07, filed May 7, 1999
No. 6; and US Provisional Patent Application No. 60/146, filed July 30, 1999.
, 337.

[0004] The present invention relates generally to reinforced laminates for electronic circuit boards and, more particularly, to:
For a laminate comprising a woven glass fiber fabric having a coating, the coating is compatible with the laminate matrix resin and provides the laminate with improved perforation properties.

BACKGROUND OF THE INVENTION Electronic circuit boards are typically formed from laminated layers of resin impregnated fabrics composed of reinforcing fibers (eg, glass fibers), on which the reinforcing fibers are placed. Dimensional stability is provided to the substrate to maintain the integrity of the mounted electronics.
Holes are formed in the laminate by drilling through the layers of the laminate or support and interconnecting circuits located along different planes of the laminate. It has been observed that the hardness of the glass fibers in the laminate and the heat generated during the drilling operation can accelerate the wear of the drill bit. As a result, the drill bit changes drills with only a small number of holes drilled and / or re-sharpens the drilling tip, reducing the overall tool service life. In addition, it has been observed that accelerated wear of the drilling tip also affects the positional accuracy of the hole, particularly the exit end of the hole drilled through the laminate.

Typically, the surface of the glass fibers forming the reinforcing fibers of these laminates is coated with a sizing composition during the fiber forming process to protect these fibers from abrasion during subsequent processing. I do. For example, starch or oil-based sizing compositions can be used to reduce fibers during interfilament weaving of fabrics.
ent) and equipment attrition, which can cause fiber breakage. To reduce attrition, sizing compositions include organic lubricants (eg, alkyl imidazoline derivatives and amide substituted polyethylene imines).
Is added. However, such organic lubricants can degrade during subsequent processing or cause undesired side reactions with other sizing components and matrix material components. In addition, many commonly used sizing components include these glass fibers and laminate matrix materials (eg,
Starch-these are commonly used as film formers in textile sizing and are generally not compatible with this laminate resin matrix material)
Can have an adverse effect on the adhesion between them. To avoid incompatibility between these glass fibers and the matrix material, the coating or sizing composition is typically prepared by pyrolyzing the components of the sizing (heat treatment or deoiling).
Alternatively, it is removed from the fabric prior to lamination by washing with water or other solution. The conventional heat cleaning method uses a temperature of 380 ° C.
With heating for 60 to 80 hours. The washed fabric is then recoated with a silane coupling agent to improve the adhesion between the glass fibers and the matrix resin.

[0007] The strength of these glass fibers, and more specifically the flexural strength of the laminate, can be significantly reduced by these thermal cleaning methods. Thermal cleaning of high silica content glass fibers (e.g., D-glass, S-glass and Q-glass) is particularly undesirable due to strength loss and bleaching.

[0008] Many fiberglass coating compositions that require a thermal or water wash prior to use as a reinforcement in composites or laminates have been disclosed in the art. Japanese Patent Application 9
No. 208,268 discloses starch or synthetic resin and 0.0
01 to 20.0% by weight of inorganic particles (e.g., colloidal silica, calcium carbonate,
Disclosed is a fabric having a yarn formed from glass fibers coated with (kaolin and talc). Prior to forming the laminate, thermal or oil dewatering is required.

US Pat. No. 5,286,562 discloses a textile strand for screen products that can be woven on an air jet loom, comprising at least 45% by weight of wax, lubricant, polyvinylpyrrolidone and organosilane. It has a coating of a coupling agent. U.S. Pat. No. 5,038,555 discloses twisted bundles of glass fibers for screen products, which include epoxy film formers, emulsifiers, lubricants, organofunctional metal coupling agents, polyvinylpyrrolidone, It is coated with an aqueous chemical treatment composition comprising polyethylene and water.

[0010] In order to avoid hot-washed glass fiber cloth, Japanese Patent Application No. 8-119,682 discloses a primary sizing agent for glass fiber, which contains a water-soluble epoxy resin, It has a pH of 5.5 to 7.5, making it easier to remove this sizing agent with water. Similarly, U.S. Pat. No. 5,236,777 discloses that the glass yarn is a primary sizing agent, which is a group consisting of amine-modified epoxy resins, ethylene oxide-added epoxy resins and ethylene oxide-added bisphenol A, silane coupling agents and lubricants. (Having at least one water-soluble film-forming agent selected from), and washing the yarns with water to reduce the amount of primary sizing to 0.1.
Disclosed is a method of making glass cloth to strengthen the resin by lowering the LOI to less than 25% by weight and treating with a secondary sizing agent. Japanese Patent Application No. 9-268,034 discloses a binder for untwisted glass fiber yarns, which comprises a water-soluble urethane compound and / or a water-soluble epoxy product, Modified by an addition reaction).

[0011] US Pat. No. 4,933,381 discloses a resin compatible size composition for glass fibers which comprises an epoxy film former, a nonionic lubricant, a cationic lubricant, a silane. It contains a coupling agent and an acid (eg, acetic acid or citric acid).

Japanese Patent Application No. 8-325,950 discloses a glass fiber sizing agent containing, as essential components, polyvinylpyrrolidone, a water-soluble epoxy resin amine addition product, and a silane coupling agent. No heat removal from the finished glass cloth is required.

[0013] Japanese Patent Application No. 7-102,483 discloses a warp secondary sizing agent for glass fiber for weaving glass cloth, which does not require heat oil removal. The warp secondary sizing agent is primarily composed of polyvinylpyrrolidone and contains additives (eg, high molecular weight polyethylene oxide). As a binding component, a water-soluble epoxy resin can be contained.

An inert lubricant for inhibiting the abrasion of glass fibers, which does not degrade significantly during processing, improves the perforation properties of laminates incorporating the glass fibers, and is compatible with polymeric matrix materials What is sex is desired. However, the use of inorganic materials has primarily focused on fillers that modify the general physical properties of the composite material, rather than fillers that improve the attrition resistance properties of the reinforcing fibers.

US Pat. No. 4,869,954 discloses a sheet-like thermally conductive material comprising a urethane binder, a curing agent and a thermally conductive filler (eg, aluminum oxide, aluminum nitride) , Nitrogen boron, magnesium oxide and zinc oxide and various metals) (column 2, lines 62-65 and column 4, 3
-10). The thermally conductive material includes one or more layers of support material (eg,
Glass fiber cloth).

US Pat. No. 3,312,569 discloses adhesive alumina particles to the surface of these glass fibers, and Japanese Patent Application No. 9-208,268 discloses a method as described above. Immediately after spinning, from glass fibers coated with starch or synthetic resin and inorganic particles (eg, colloidal silica, calcium carbonate, kaolin and talc) to improve resin penetration between glass reinforced fibers during formation of the composite. A fabric having a formed yarn is disclosed. However, the Mohs hardness values of alumina and silica are greater than about 9 and about 7, respectively, ¹ , which can cause the abrasion of soft glass fibers. ¹ R. West (ed.),
Handbook of Chemistry and Physics, CR
C Press (1975), page F-22, and H.C. Katz et al. (Eds.), Ha
ndbook of Fillers and Plastics, (1987
), Page 28, the contents of which are incorporated herein by reference.

US Pat. No. 5,541,238 discloses fibers for reinforcing thermoplastic or thermoset composites, which are produced by vapor deposition or plasma processes.
It is coated with a single layer of ultrafine material (e.g., inorganic oxides, nitrides, carbides, borides, metals and combinations thereof) having an average particle size of 0.005 to 1 micrometer. The requirement of limited space and environment makes the use of vapor deposition or plasma processes under glass bushing manufacturing impractical.

Soviet Patent No. 859400 discloses an impregnating composition for making a laminate of glass fiber cloth, which composition comprises a phenol-formaldehyde resin,
Contains an alcoholic solution of graphite, molybdenum disulfide, polyvinyl butyral and surfactant. Volatile alcohol solvents are not desirable for glass fiber manufacturing applications.

US Pat. No. 5,217,778 discloses a dry process comprising a composite yarn of glass fibers, metal wires and polyacrylonitrile fibers, which are impregnated and coated with a thermosettable cement or binder system. Clutch exterior (facing
). The binder is used to improve the frictional properties of the composite by providing friction particles (e.g., carbon black, graphite, metal oxides, barium sulfate, aluminum silicate, ground rubber particles, ground organic resin, polymerized cashew nut oil,
Clay, silica or cryolite) (column 2, lines 55-66).
.

A fiberglass lubricant coating compatible with various polymeric matrix materials, comprising:
What is needed is a drill that reduces wear on the tip of the drill and improves the positional accuracy of the drilled hole. In addition, it is particularly advantageous if the coating is compatible with modern air-jet weaving equipment to increase productivity and.

SUMMARY OF THE INVENTION One aspect of the present invention is a prepreg for an electronic support, the prepreg comprising: (a) a polymeric matrix material; and (b) a strand comprising glass fibers. A fabric comprising at least a portion of the fabric having a coating compatible with the polymeric matrix material, wherein the prepreg is 0.46 mm (0.018 mm).
Stacking of three stacks using an inch diameter tungsten carbide drill with a hole density of 62 holes per square centimeter (400 holes per square inch) and a chip load of 0.001. (Stack)
Have a drill tip percentage wear of less than or equal to about 32%, as measured after drilling 2000 holes through the stack, and each laminate includes eight prepregs. The present invention also provides a laminate incorporating the prepreg.

Another aspect of the present invention is a prepreg for an electronic support, wherein the prepreg comprises:
A woven woven fabric comprising: (a) a polymeric matrix material; and (b) glass fibers, wherein the woven fabric comprises glass fibers.
At least a portion of the woven fabric has a coating compatible with the polymeric matrix material, and the prepreg is 62 pieces / square centimeter using a 0.46 mm (0.018 inch) diameter tungsten carbide drill. With a hole density of 400 holes per square inch (400 holes per square inch) and a chip load of 0.001, less than about 36 micrometers when measured after drilling 2000 holes through a stack of three laminates. It has a deviation distance.
The present invention also provides a laminate incorporating the prepreg.

DETAILED DESCRIPTION OF THE INVENTION The laminate of the present invention is reinforced with a fabric comprising coated fiber strands, preferably a woven fabric comprising coated glass fiber strands, which has a low coefficient of thermal expansion, good A laminate having excellent bending strength, heat stability, hydrolysis stability, low corrosion and reactivity in the presence of reactive acids and alkalis at high humidity can be provided. These coated fiber strands are compatible with various polymeric matrix materials, thereby eliminating the need to heat or water wash the fiberglass fabric prior to lamination.

Another important advantage of the laminate of the invention is that improved drilling performance, ie low drill tip wear and / or improved drilling, especially when the laminate is used as an electronic support. May indicate hole location accuracy. As used herein, the term "electronic support" refers to active electronic components, passive electronic components, printed circuits, integrated circuits, semiconductor devices, and other hardware associated with such elements (e.g., connectors, A structure that mechanically supports and / or electrically interconnects elements, including, but not limited to, sockets, securing clips, and radiators.

Another advantage of the laminate of the present invention is that it can be made from fiber strands suitable for use in an air jet weaving process. As used herein, the term "air jet weaving" refers to a type of fabric weaving in which fill yarns are inserted into warp yarns injected by blowing compressed air from one or more air jet nozzles. It is.

Referring now to the drawings, where like numerals refer to like elements throughout the drawings, FIG. 1 shows a laminate 10 according to the present invention. The laminate 10 includes a polymeric matrix material 12 (described in more detail below), which comprises a reinforced fabric 14.
Has been enhanced. The fabric 14 can be a woven or non-woven fabric, for example, a knit or mat, which can be formed by any suitable knitting, weaving, or mat manufacturing method.
Formed), but is not limited thereto. Preferably, the fabric 14 is a woven fabric formed by an air jet weaving method, which is well known to those skilled in the art. Laminate 10 may also be a unidirectional laminate, where most of the fibers, yarns or strands of each fabric layer are oriented in the same direction.

Typically, the laminate comprises a plurality of prepregs, each prepreg incorporating a fabric 14 and a partially cured polymeric matrix 12, as described in further detail below. The number of prepregs in the laminate can range from one to about forty. In these figures, only a single prepreg is shown in the laminate 10 for clarity.

Referring now to FIGS. 2 and 3, fabric 14 includes one or more coated fiber strands 16. As used herein, the term "strand" refers to a plurality of individual fibers. The term "fiber" means individual filaments.

The glass fibers 18 can be formed from any type of fiberizable glass composition known to those skilled in the art, including fiberizable glass compositions (eg, “E-glass”,
"A glass", "C glass", "D glass", "Q glass", "R glass", "S glass"
Glass "and E-glass derivatives). As used herein, the term "fibrillable" means a material that can be formed into a substantially continuous filament, fiber, strand or yarn. As used herein, “E glass derivative” contains a small amount of fluorine and / or boron (preferably,
Glass composition (containing no fluorine and / or no boron). Further, as used herein, small amounts mean less than about 1% by weight fluorine and less than about 5% by weight boron. Basalt and mineral wool materials are examples of other fiberizable glass materials useful in the present invention. Preferred glass fibers are formed from E-glass or E-glass derivatives. Such compositions are well-known to those of skill in the art and need not be further described in view of the present disclosure. The glass fibers of the present invention can be formed by any suitable method known in the art for forming glass fibers. For example, glass fibers can be formed in a direct-melt fiber forming operation or an indirect or marble-melt fiber forming operation. In a direct melt fiber forming operation, the raw materials are combined, melted, and homogenized in a glass melting furnace. The molten glass moves from the furnace to the forehearth and enters the fiber former where the molten glass is reduced to continuous glass fibers. In a marble molten glass forming operation, a glass piece or marble having the desired final glass composition is preformed and fed to a bushing,
At this point, they are melted and reduced to continuous glass fibers. if,
If a premelter is used, the marbles are first fed to the premelter and melted, and then the molten glass is fed to a fiber forming device where the marble is fed. The glass is thinned to form continuous fibers. In the present invention, these glass fibers are preferably formed in this direct melt fiber forming operation. For more information on glass compositions and methods of forming glass fibers, see K. K. Loewenstein, The Manufac
turning Technology of Glass Fibers (3rd
Edition, 1993), pages 30-44, 47-60, 115-122 and 12.
6-135, U.S. Pat. Nos. 4,542,106 and 5,789,329, and IPC-EG-140 "Specification for Fin."
ished Fabric Woven from "E" Glass for
Printed Boards ", page 1, The Institute fo
r Interconnecting and Packing Elec
See the literature of Tronic Circuits (June 1997), the contents of which are incorporated herein by reference.

These glass fibers have a nominal (nominal) range of about 3.0 to about 35.0 micrometers, which corresponds to the BU filament designations described above.
A) a filament diameter, preferably having a nominal filament diameter in the range of about 5.0 to about 30.0 micrometers; For fine yarn applications, the average nominal filament diameter preferably ranges from about 5 to about 7 micrometers. The number of fibers per strand can range from about 2 to about 15,000, preferably from about 100 to about 7,000. For more information on nominal filament diameters and glass fiber names, see Loewenstein
, Pages 25-27, the contents of which are incorporated herein by reference.

In addition to glass fibers, the coated fiber strands 16 may further include fibers 20 formed from other fiberizable inorganic materials, fiberizable organic materials, and mixtures and combinations thereof. These inorganic and organic materials can be either man-made or naturally occurring materials. It is understood by those skilled in the art that these fiberizable inorganic and organic materials can also be polymeric materials. As used herein, the term "polymeric material" refers to a material formed from a polymer composed of long chains of atoms bonded together that can be entangled in solution or in the solid state ² means. ² James Mark et al., Inorganic Polymers, Pren.
Tice Hall Polymer Science and Engineering
ering Series, (1992), p. 1, the contents of which are incorporated herein by reference.

Non-limiting examples of suitable non-glass, fiberizable inorganic materials include ceramic materials (eg, silicon carbide, carbon, graphite, mullite, aluminum oxide, and piezoelectric ceramic materials). Non-limiting examples of suitable fiberizable organic materials include cotton, cellulose, natural rubber, flax, ramie, hemp, sisal and wool. Non-limiting examples of suitable fiberizable organic polymeric materials include those formed from polyamides (eg, nylon and aramid), thermoplastic polyesters (eg, polyethylene terephthalate and polybutylene terephthalate), acrylics (eg, , Polyacrylonitrile), polyolefins, polyurethanes and vinyl polymers (eg, polyvinyl alcohol). Non-glass fiberizable materials useful in the present invention and methods of preparing and treating such fibers are described in Encyclopedia of Polymer Science.
and Technology, Vol. 6, (1967), pages 505-712, the contents of which are incorporated herein by reference. It will be appreciated that combinations of blends or copolymers of any of the above materials and fibers formed from any of the above materials can be used in the present invention, if desired.

The present invention will now be described generally herein in the context of glass fiber strands,
Those skilled in the art will appreciate that the strand 16 may further contain one or more of the non-glass fibers described above.

[0034] Although not limiting to the present invention, in the embodiment of the fabric 14 shown in FIG. 2, at least one (preferably all) of the fibers 18 of the strands 16 protect their fiber surfaces from abrasion during processing. To prevent fiber breakage, the fibers 18 are coated with a layer 22 of a coating composition applied to at least a portion of the surface. Preferably, the coating composition is applied to the entire outer surface or perimeter of each of the fibers 18 of the strand 16, as shown in FIG.

The coating composition useful in the present invention is present on these fibers as a sizing, which is preferred, on which a secondary coating has been applied and / or a tertiary An outer coating (if desired) has been applied. As used herein, the terms "size,""sized," or "sizing" refer to the coating composition applied to the fibers immediately after their formation. In alternative embodiments, the terms "size,""sized," or "sizing" may further refer to at least a portion (typically all) of a conventional primary coating composition, a heat treatment, a water treatment or It refers to the coating composition (also known as "finished size") applied to these fibers after removal by chemical treatment. That is, this is the finished size applied to the bare glass fibers incorporated into the fiber shape. The term "secondary coating" refers to applying a sizing composition,
Preferably, it refers to a coating composition that is at least partially dried and then secondarily applied to one or more strands. The coating may be applied to the fiber prior to incorporation into the fabric, for example, by coating the fiber, or may be applied to the fiber after the fiber has been incorporated into the fiber.

[0036] The coating composition useful in the present invention is preferably an aqueous coating composition. Although not preferred for safety reasons, the coating composition can optionally include a volatile organic solvent (eg, alcohol or acetone), but preferably does not.

The coating compositions useful in the present invention contain one or more polymeric materials (eg, thermosetting or thermoplastic materials), which are the polymeric matrix material 12 of the laminate 10. That is, the components of the coating composition promote wet-out and wet-through of the matrix material on these fiber strands and impart appropriate physical properties to the composite. Preferably, these polymeric materials form a substantially continuous film when applied to the surface of the fibers 18. These polymeric materials can be water-soluble, emulsifiable, dispersible and / or curable. As used herein, the phrase "compatible with a polymeric matrix material" means that the components of the coating composition applied to these glass fibers are such that the components of the coating material wet through and through the matrix material on these fiber strands. Promotes wet out,
Gives the composite appropriate physical properties, is chemically compatible with the polymeric matrix material, and has good hydrolytic stability (ie, water migration along the fiber surface / matrix material interface) , Which means that the coating component (or selected coating component) need not be removed before incorporating the coated fibers into the polymeric matrix material. The measure by which the polymeric matrix material penetrates the mat or fabric is called "wet-through." The measure of the flowability of the polymer matrix material through the glass fiber strands in order to obtain essentially complete encapsulation of the entire surface of each glass fiber with the polymer matrix material is called "wet out".

In one embodiment of the present invention, the coating composition applied to the fibers 18 incorporated into the laminate 10 includes one or more polymeric film-forming materials, which are heat-curable Compatible with matrix materials (eg, those used to form laminates for printed circuit boards or printed wiring boards (hereinafter individually or collectively referred to as "electronic circuit boards")) This material includes, for example, FR-4 epoxy resin, which is a multifunctional epoxy resin, and in one particular embodiment of the present invention, a difunctional brominated epoxy resin, and a polyimide. It is. E
electronic Materials Handbook, ASM Int
See international (1989), pages 534-537, the contents of which are incorporated herein by reference.

Non-limiting examples of useful polymeric film-forming materials include thermoplastic polymeric materials (eg, thermoplastic polyesters), vinyl polymers, polyolefins, polyamides (
Examples include aliphatic or aromatic polyamides (eg, aramid), thermoplastic polyurethanes, acrylic polymers and mixtures thereof, which are compatible with thermoset materials. Non-limiting examples of thermoplastic polyesters include:
DESMOPHEN2000 and DESMOPHEN2001KS (both are Bayer of Pittsburgh, Pennsylvania
RD-847A polyester resin (which is commercially available from Borde Corp.)
n Chemicals of Columnus, commercially available from Ohio), and DYNAKOLL SI 100 resin, which is available from Eka Chem
icals AB, commercially available from Sweden). Useful polyamides include VERSAMID products, which are available from General
Mills Chemicals, Inc. It is commercially available from. Useful thermoplastic polyurethanes include WITCOBOND® W-290H, which includes
Witco Chemical Corp. (Chicago, Illinoi
s), and RUCOTHANE® 2011L
Polyurethane latex (Ruco Polymer Corp. o
f (commercially available from Hicksville, New York).

Non-limiting examples of useful thermoset polymeric materials include thermoset polyesters, epoxy materials, vinyl esters, phenols, aminoplasts, thermoset polyurethanes, and mixtures thereof. Is compatible with thermoset matrix materials. Suitable thermoset polyesters include STYPOL polyester (
This is the Cook Composites and Polymers of
(Commercially available from Port Washington, Wisconsin),
And NEOXIL polyester (which are available from DSM BV (Como, It)
aly) commercially available).

Useful epoxy materials contain at least one epoxy or oxirane group in the molecule (eg, a polyglycidyl ether of a polyhydric alcohol or thiol). Examples of suitable epoxy polymers include EPON® 826 and EPON® 880 epoxy resins, which are epoxy-functional polyglycidyl ethers of bisphenol A and are available from Shell Chem.
It is commercially available from Ical Company (Houston, Tex.). In one embodiment of the coating composition, the coating composition is essentially free of epoxy material, ie, contains less than about 5% by weight epoxy material, and more preferably,
Contains less than about 2% by weight epoxy material.

In one non-limiting embodiment of the coating composition, the coating composition comprises one or more polyesters (eg, DESMOPHEN2000 and RD-8
47A), and one or more additional film-forming polymers, which are selected from the group consisting of vinylpyrrolidone polymers (which are preferred), vinyl alcohol polymers and / or starch. Vinylpyrrolidone polymers useful in the present invention include polyvinylpyrrolidone (eg, PVP K-15, PV
PK-30, PVP K-60 and PVP K-90), each of which is available from ISP Chemicals (Wayne, New Jersey).
It is commercially available from. Other suitable vinyl polymers include Resyn 2828 and Resyn 1037 vinyl acetate copolymer emulsions, which include N 2
national Starch and Chemical (Bridgewa
ter, New Jersey). Useful starches include potato, corn, wheat, waxy corn, sago, rice, milo and mixtures thereof, such as KOLLOTEX 1250, which is a low viscosity, low amylose potato-based starch etherified with ethylene oxide. And commercially available from AVEBE (Netherlands). The amount of additional polymer is preferably less than about 20% by weight, more preferably about 0.1% by weight.
To about 5% by weight. Preferably, the coating composition is essentially starch-free, ie, contains less than about 5% starch by weight, and more preferably, starch, which is often incompatible with the matrix material Is not contained.

The coating composition may include a mixture of one or more thermoset polymeric materials and one or more thermoplastic polymeric materials. In one embodiment of the laminate for an electronic circuit board, the polymeric material of the coating composition is RD-847A polyester resin or DYNAKOLL SI 100 resin, PVP K-30 polyvinylpyrrolidone, DESMOPHEN2000 polyester and VERSAMI.
Contains a mixture of D polyamides. In an alternative embodiment suitable for laminates for printed circuit boards, the polymeric material of the aqueous sizing composition comprises PVP K-30 polyvinylpyrrolidone, optionally combined with EPON 826 epoxy resin.

Generally, the amount of polymeric material, based on total solids, is from about 1 to about 90 of the coating composition.
%, Preferably in the range of about 1 to about 80% by weight.

In addition to or in place of the polymeric materials described above, the coating composition preferably includes one or more coupling agents (eg, an organosilane coupling agent, a transition metal coupling agent, a phosphonate Coupling agents, aluminum coupling agents, amino-containing Werner coupling agents and mixtures thereof). These coupling agents typically have dual functionality. Each metal or silicon atom links it to one or more groups, which groups are either capable of reacting with or compatible with the fiber surfaces and / or components of the polymeric matrix. Is. "Compatible" as used herein
The term means that these groups are chemically bonded to the fiber surface and / or components of the coating composition, for example, by polar, wetting or solvating forces. In one non-limiting embodiment, each metal or silicon atom has one
One or more hydrolyzable groups (these enable the coupling agent to react with the glass fiber surface) and one or more functional groups (
These groups allow the coupling agent to react with the components of the polymeric matrix). Examples of hydrolysable groups include:

[0046]

Embedded imageMonohydroxy residue of 1,2- or 1,3-glycol and / or cyclic C _Two ~ C_ThreeA residue, where R¹Is C₁~ C_ThreeAlkyl; R^TwoIs H
Is C₁~ C_FourAlkyl; R^ThreeAnd R^FourIs independently H, C₁~ C_FourAlkyl
Or C₆~ C₈Selected from aryl; and R^FiveIs C_Four~ C₇Alkylene
You. Examples of suitable compatible or functional groups include epoxy groups, glycidoxy groups,
Pt, cyano, allyl, alkyl, uretano, halo, isocyanato
Group, ureido group, imidazolinyl group, vinyl group, acrylate group, methacrylate group
, An amino group or a polyamino group.

[0047] Functional organosilane coupling agents are preferred 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 include A-187γ-glycidoxypropyltrimethoxysilane, A-174γ-methacryloxypropyltrimethoxysilane, A-1100γ-aminopropyltriethoxysilane coupling agent, A-1108 Aminosilane coupling agents and A-1160γ-ureidopropyltriethoxysilane (each of which is described in OSi Specialties, Inc. (Tarrytown, New York).
Commercially available from York). The organosilane coupling agent can be at least partially hydrolyzed with water, or, if desired, hydrolyzed, preferably at a stoichiometric ratio of about 1: 1 prior to application to the fibers. It can be applied in a form that is not. If desired, the pH of the water can be adjusted as is well known in the art.
It can be varied by adding an acid or base to initiate or accelerate the hydrolysis of the coupling agent.

Suitable transition metal coupling agents include titanium, zirconium, yttrium and chromium coupling agents. Suitable titanate and zirconate coupling agents are available from Kenrich Petrochemica
Commercially available from l Company. Suitable chromium complexes are described in E.I. I. duP
It is commercially available from ont de Nemours (Wilmington, Del.). The amino-containing Werner-type coupling agent is a complex compound in which a trivalent nuclear atom (for example, chromium) is coordinated with an organic acid having an amino functional group. Other metal chelates and coordinating coupling agents known to those skilled in the art can also be used herein.

The amount of coupling agent may range from about 1 to about 30%, preferably from about 1 to about 10% by weight of the coating composition, based on total solids.

In a non-limiting embodiment of the coating composition shown in FIG. 3, the coating composition of the present invention contains one or more particles 24, When applied to one fiber 18, it adheres to the outer surface of the fiber 18,
This provides one or more interstitial spaces 30 between adjacent glass fibers 26, 28 of the strand 16. The interstitial space 30 generally corresponds to the average size 32 of the particles 24 located between these adjacent fibers.

The particles 24 of the coating composition are preferably dispersed particles. As used herein, the term "discrete" refers to the fact that these particles do not tend to coalesce or combine to form a film under processing conditions, but instead, generally, It means retaining individual shapes or forms.
In addition, these particles are preferably dimensionally stable. The term "dimensionally stable particles" as used herein means that these particles are generally adjacent fibers 2
Maintain their average particle size and shape under processing conditions (eg, forces generated between adjacent fibers during roving, roving and other processing operations) to maintain the desired interstitial space between 6, 28 It means you are. In other words, the particles preferably do not disintegrate, dissolve or substantially deform in the coating composition under typical glass fiber processing conditions (eg, up to about 25 ° C). Temperature, preferably to a temperature of up to about 100 ° C., more preferably to a temperature of up to about 140 ° C.) to form particles having a maximum dimension less than the selected average particle size.
In addition, the particles 24 may be substantially expanded in size or under glass fiber processing conditions, and more specifically, under composite processing conditions (where the processing temperature may exceed 150 ° C.). Should not be expanded. As used herein, the phrase "should not be substantially expanded in size" refers in relation to these particles to the fact that, during processing, the particles should be more than approximately three times their initial size. This means that it should not be enlarged or increased to a large size. Preferably, the coating composition of the present invention is essentially free of thermally expandable hollow particles. As used herein, "heat-expandable hollow particles" refers to a swelling agent, which expands or expands substantially in size when exposed to a temperature sufficient to volatilize the swelling agent. A hollow particle that is filled or contains it is meant. The term "substantially free" as used herein means that the sizing composition is less than about 20%, more preferably less than about 5%, and most preferably less than about 5% by weight, based on total solids. , Less than 0.001% by weight of thermally expandable hollow particles. In addition, the term "dimensional stability" as used herein includes both crystalline and amorphous materials.

In addition, although not required, particles 24 are preferably non-waxy. The term "non-waxy" means that the material from which these particles are formed is not wax-like. The term "wax-like" as used herein, refers mainly material composed of hydrocarbon chains that are not intertwined with an average carbon chain length of from about 25 to about 100 carbon atoms range ^{3 , 4} .

³ L. H. Sperling Introduction of Physi
cal Polymer Science, John Wiley and S
ons, Inc. (1986), pp. 2-5 (the contents of which are incorporated herein by reference).

⁴ W. Pushaw et al., "Use of Micronized Waxe"
s and Wax Dispersions iin Waterborn
Systems "Polymers, Paint, Colors Jou
rnal, V .; 189, no. 4412, January 1999, pp. 18-21 (the contents of which are incorporated herein by reference).

Preferably, the particles 24 in the coating composition are dispersed, dimensionally stable, and non-waxy particles. In certain non-limiting embodiments of the invention, the average particle size 32 of the particles 24 is at least about 0.1 micrometer, preferably at least about 0.5 micrometer, and about 0.1 micrometer ~
A range of about 5 micrometers, preferably about 0.5 micrometers to about 3.
It is in the range of 0 micrometers. In one embodiment, particles 24 are at least about 1 micrometer, and preferably range from about 1 to about 3 micrometers.
In this non-limiting embodiment, the particles 24 have an average particle size 32, which is generally smaller than the average diameter of the fibers 18 to which the coating composition is applied. Twisted yarn made from a fiber strand 16 having a layer 22 of a residue of the primary sizing composition containing particles 24 having an average particle size 32 as described above, provides a complete fiber strand 16 when impregnated with a polymeric matrix material. Sufficient adjacent fibers 26 to allow air-jet weaving (ie, air-jet transport across the loom), while maintaining the properties and providing adequate "wet-through" and "wet-out" properties.
, 28 can be provided.

In another specific, non-limiting embodiment of the present invention, the average particle size 32 of the particles 24 is at least 3 micrometers, preferably at least about micrometers, and between 3 and about 1000 micrometers. Range, preferably from about 5 to about 10
It is in the range of 00 micrometers, more preferably in the range of about 10 to about 25 micrometers. Preferably, each of the particles 24 has a minimum particle size of at least 3 micrometers, preferably at least about 5 micrometers. In this embodiment, it is also preferred that the average particle size 32 of the particles 24 generally correspond to the average nominal diameter of these glass fibers. Fabrics made of strands coated with particles of the above size, when impregnated with a polymeric matrix material, have a good "
It has been observed to exhibit "wet-through" and "wet-out" properties.

One or more sizing compositions according to the present invention having different average particle sizes 32 may be used to impart desired attributes and processing properties to the fiber strands 16 and subsequently to the products made therefrom. It will be appreciated by those skilled in the art that a mixture of particles 24 can be incorporated. More specifically, different sized particles can be blended in the required amount to provide a fabric that exhibits good wet out and wet through properties as well as fibers having good air jet transport characteristics.

Although not limited by the present invention, the configuration or shape of the particles 24 is generally spherical (eg, beads, microbeads or solid and hollow spheres), as desired.
, Cubes, plates or needles (elongated or fibrous). In addition to it,
Particles 24 can have a hollow, porous or void-free, or a combination thereof structure. In addition, particles 24 can be a combination of these structures (eg,
Hollow center with a porous or solid wall). For more information on suitable particle properties, see Katz et al. (Author), Handbo
Ok of Fillers and Plastics (1987), 9-
See page 10 (the contents of which are incorporated herein by reference).

The glass fibers may be abrasive, due to the roughness of adjacent glass fibers and / or contact with other solids or materials that the glass fibers contact during formation and during subsequent processing (eg, weaving or roving). Subject to abrasive wear. As used herein, "abrasive wear" refers to scraping or cutting off small pieces of the glass fiber surface or breaking the glass fiber. K. Ludem
a, Friction, Wear, Lubrication, (1996),
See page 129, the contents of which are incorporated herein by reference. Abrasive wear of glass fiber strands results in strand breakage during processing and surface defects in products (eg, woven fabrics and composites), which increases waste and increases manufacturing costs.

To minimize abrasive wear, the particles 24 have a hardness value that does not exceed (ie, is equal to or less than) the hardness value of the glass fiber. The hardness value of these particles and glass fibers can be measured by any conventional hardness measurement method (for example, Vickers hardness or Brinell hardness), but preferably, the original (
(Original) Measured according to the Mohs hardness scale, which indicates the relative scratch resistance of the surface of a material. The Mohs hardness value of the glass fibers generally ranges from about 4.5 to about 6.5, and preferably is about 6. R. W
east (Author), Handbook of Chemistry and Ph
ysics, CRC Press (1975), page F-22, the contents of which are incorporated herein by reference. Mohs hardness values of particles suitable for use in the above-described coating compositions preferably range from about 0.5 to about 6. Mohs hardness values for some non-limiting examples of particles suitable for use in the present invention are shown in Table A below.

[0061]

[Table 1] ⁵ K. Ludema, Friction, Wear, Lubricatio
n, (1996 years), page 27 (the contents of which are incorporated by reference herein) ⁶ R. Weast (Author), Handbook of Chemistry
and Physics, CRC Press (1975 years), F-22, pp. ⁷ R. Lewis, Sr. , Hawley's Condensed Ch
Chemical Dictionary, (12th edition, 1993), p. 793 (
The contents of which are incorporated herein by reference.) ⁸ Hawley's Condensed Chemical Dicti
onary, (12th edition, 1993), page 1113 (the contents of which are incorporated herein by reference). ⁹ Hawley's Condensed Chemical Dicti.
onary, (12th edition, 1993), p. 784 (the contents of which are incorporated herein by reference). ¹⁰ Handbook of Chemistry and Physics.
, F-22, ¹¹ Handbook of Chemistry and Physics
, F-22, page ¹² Friction, Wear, Lubrication, 27 pp. ¹³ Friction, Wear, Lubrication, 27 pp. ¹⁴ Friction, Wear, Lubrication, 27 pp. ¹⁵ Friction, Wear, Lubrication, 27 pp. ¹⁶ Handbook of Chemistry and Physics
, F-22, ¹⁷ Handbook of Chemistry and Physics
, F-22, ¹⁸ Handbook of Chemistry and Physics
Pp. F-22, ^19, Handbook of Chemistry and Physics.
Pp. F-22 ²⁰ Handbook of Chemistry and Physics
, F-22, ²¹ Handbook of Chemistry and Physics
, F-22, pp. ²² Handbook of Chemistry and Physics
, F-22.

As mentioned above, the Mohs scale is related to the scratch resistance of a material. Accordingly, the present invention further contemplates particles having a surface hardness that is different from the hardness inside the particle below its surface. More specifically, the surface of the particle is formed in the art such that the hardness under the surface of the particle is higher than the hardness of the glass fiber, and the surface hardness of the particle is equal to or less than the hardness of the glass fiber. It can be modified in any known manner, including, but not limited to, chemically altering its surface properties using techniques known in the art. In another alternative embodiment,
The particles can be coated, clad or encapsulated to form a composite particle having a soft surface (described below).

In general, the particles 24 useful in the present invention can be formed from a material selected from the group consisting of polymeric and non-polymeric inorganic materials, polymeric and non-polymeric organic materials, composites, and mixtures thereof. As used herein, the term "polymeric inorganic material" means a polymeric material having a skeleton repeating unit based on an element other than carbon. For more information, see E. FIG. See Mark et al., Page 5, the contents of which are incorporated herein by reference. Polymeric organic materials include synthetic, semi-synthetic, and natural polymer materials. As used herein, the term "organic material" refers to all carbon compounds except the following compounds: binary compounds such as carbon oxides, carbides, carbon disulfide, etc .; metal cyanides, metals Ternary compounds such as carbonyl, phosgene, carbonyl sulfide, and the like; and metal carbonates (eg, calcium carbonate and sodium carbonate). R. Lewi
s, Sr. , Hawley's Condensed Chemical Di
ctionary, (12th edition, 1993), pp. 761-762, the contents of which are incorporated herein by reference. More generally, organic materials include carbon-containing compounds, where the carbon is typically bonded to itself and hydrogen, and often to other elements as well. But excluding carbon-containing ionic compounds. M. Silverberg, Chemist
ry The Molecular Nature of Matter an
d Change, (1996), p. 586, the contents of which are incorporated herein by reference. The term "inorganic material" generally refers to all materials that are not carbon compounds, except for carbon oxides and carbon disulfide. R. Le
wis, Sr. , Hawley's Condensed Chemical
Dictionary, (12th edition, 1993), p. 636, the contents of which are incorporated herein by reference. As used herein, the term "inorganic material" refers to any material that is not an organic material. As used herein, the term "composite material" refers to a blend of two or more different materials. For more information on particles useful in the present invention, see G.S. Wypych
, Handbook of Fillers, 2nd edition, (1999), 15-.
See page 202, the contents of which are incorporated herein by reference.

Non-polymeric inorganic materials useful in forming particles 24 include ceramic and metallic materials. Suitable ceramic materials include metal nitrides, metal oxides,
Metal carbides, metal sulfides, metal borides, metal silicates, metal carbonates and mixtures thereof.

A non-limiting example of a suitable metal nitride is boron nitride, which is a preferred inorganic material to form 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 silicate and magnesium silicate (eg, vermiculite). Suitable metallic materials include graphite, molybdenum, platinum, palladium, nickel, aluminum, copper, gold, iron, silver and mixtures thereof.

Although not required, preferably, the particles 24 are also a solid lubricant. The term "solid lubricant" as used herein is used between two surfaces to provide protection from damage during relative movement and / or to reduce friction and wear. Means any solid. More preferably, particles 24 are an inorganic solid lubricant. As used herein, the term "inorganic solid lubricant" means that the inorganic particles 24 have a characteristic crystal habit, whereby they are sheared into thin slabs, which easily slip over each other, Means that an anti-friction effect occurs between this glass fiber surface and the adjacent solid surface, at least one of which is moving. (RL
ewis, Sr. , Hawley's Condensed Chemical
Dictionary, (12th edition, 1993), p. 712), the contents of which are incorporated herein by reference. Friction is the resistance of one solid from sliding over another. F. Clauss, Solid
Lubricants and Self-Lubricating Soli
d, (1972), p. 1, the contents of which are incorporated herein by reference.

In one particular embodiment useful in the present invention, these solid lubricant particles have a layered structure, which, as will be described in further detail below, includes its laminae.
It is believed that it contributes to lower instrument wear when drilling holes through. Particles with a layered structure are composed of sheets or plates of atoms in a hexagonal array, which are strongly bonded within the sheets, and the van der Waals bonds between the sheets are weak, with low shear between the sheets. Produces power. A non-limiting example of a layered structure includes a hexagonal crystal structure. Friction, Wear, Lubr
Icitation, page 125, Solid Lubricants and Se
If-Lubricating Solid, pp. 19-22, pp. 42-54, 7
Pages 5 to 77, pages 80 to 81, page 82, pages 90 to 102, pages 113 to 120 and page 128; Campbell "Solid Lubricants"
, Boundary Lubrication; An Appraisal o
f World Literacy, ASME Research Com
mitte on Lubrication (1969), 202-203
See page (the contents of which are incorporated herein by reference). Inorganic particles having a layered fullerene (buckyball) structure are also useful in the present invention.

Non-limiting examples of suitable inorganic solid lubricant particles having a layered structure include: boron nitride, graphite, metal dichalcogenide, 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.

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

[0070] Non-limiting examples of boron nitride particles suitable for use in the present invention include: Polar
Therm® 100 Series (PT 120, PT 140,
PT 160 and PT 180), 300 Series (PT 350) and 600 Series (PT 620, PT 630, PT 640 and PT
670) Boron nitride powder particles, which are available in Advanced Ceram
ics Corporation of Lakewood, Ohio. “PolarTherm® Thermally Con
ductile Fillers for Polymeric Materi
als "(Advanced Ceramics Corporation o
f The content of Lakewood, Ohio's Technical Bulletin (1996) is incorporated herein by reference. These particles are 1 meter K at 25 ° C.
It has a thermal conductivity of about 250-300 watts per inch, a dielectric constant of about 3.9 and a volume resistivity of about 10 ¹⁵ ohm-cm. The 100 Series powder particles are:
Having an average particle size in the range of about 5 to about 14 micrometers, and 300 Series
The particles have an average particle size ranging from about 100 to about 150 micrometers, and the 600 Series particles have an average particle size ranging from about 16 to greater than about 200 micrometers.

The particles 24 can be formed from a non-polymeric organic material. Examples of non-polymeric organic materials useful in the present invention include, but are not limited to, stearates (eg, zinc stearate and aluminum stearate), carbon black and stearamide.

The particles 24 can be formed from an inorganic polymer material. Non-limiting examples of useful inorganic polymeric materials include polyphosphazenes, polysilanes, polysiloxanes, polygeremanes, polymeric sulfur, polymeric selenium, silicones, and mixtures thereof. A specific, non-limiting example of a particle formed from an inorganic polymeric material suitable for use in the present invention is Tospearl ²³ , a particle formed from a cross-linked siloxane, and a Toshiba Silicones Company, L
td. It is commercially available from of Japan.

²³ R. J. Perry "Applications for Cross-
Linked Siloxane Particles "Chemtech,
See February 1999, pages 39-44.

Suitable synthetic organic polymeric materials from which these particles can be formed include, but are not limited to, thermoset materials and thermoplastic materials. Suitable thermoset materials include thermoset polyesters, vinyl esters, epoxy materials, phenolics, aminoplasts, thermoset polyurethanes, and mixtures thereof. A non-limiting example of a preferred synthetic polymer particle formed from an epoxy material is an epoxy microgel particle.

[0075] Suitable thermoplastic materials include thermoplastic polyesters, polycarbonates, polyolefins, acrylic polymers, polyamides, thermoplastic polyurethanes, vinyl polymers and mixtures thereof. Preferred thermoplastic polyesters include, but are not limited to, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Preferred polyolefins include, but are not limited to, polyethylene, polypropylene and polyisobutene. Preferred acrylic polymers include styrene and acrylic copolymers and methacrylate-containing polymers. Non-limiting examples of synthetic polymer particles formed from acrylic polymers include ROPAQUE® HP-1
055 ²⁴ (This is an opaque non-film-forming styrene-acrylic polymer synthetic pigment having a particle size of 1.0 micrometer, a solids content of 26.5% by weight and a void volume of 55%) , ROPAQUE (R) OP-96 ²⁵ (which is 0.55 opaque film non-forming styrene having a solids content of particle size and 30.5 wt% of the micrometer - acrylic polymer synthesized pigment dispersion And ROPAQUE® OP-62LO ²⁶ (also 0.4
Which are opaque non-film-forming styrene-acrylic polymer synthetic pigment dispersions having a particle size of 0 micrometers and a solids content of about 36.5% by weight), each of which is described in Rohm and Haas Company. of Ph
Commercially available from iladelfia, Pennsylvania.

²⁴ Rohm and Haas Company, Philadelphia
a, “ROPAQUE® HP”, October 1994, available from PA.
-1055, Hollow Sphere Pigment for Pap
er and Paperboard Coatings, page 1, which is incorporated herein by reference. ²⁵ Rohm and Haas Company, Philadelphia
a, April 1997 "Architectureal Co. available from PA.
atings-ROPAQUE® OP-96, The All Pu
rpose Pigment refer to the product technical bulletin (one page) of the title "(the contents of which are incorporated by reference herein) ^26, supra.

Suitable semi-synthetic organic polymeric materials from which particles 24 can be formed include celluloses (eg, methylcellulose and cellulose acetate); and modified starches (eg, starch acetate and starch hydroxyethyl ether), It is not limited to these.

Suitable natural polymeric materials from which the particles 24 can be formed include polysaccharides (eg, starch); polypeptides (eg, casein); and natural hydrocarbons (eg, natural rubber and gutta percha), It is not limited to these.

In one embodiment of the present invention, the polymer particles 18 are formed from a hydrophobic polymer material to reduce or limit the absorption of moisture by the coated strand. Non-limiting examples of hydrophobic polymeric materials that are considered useful in the present invention include, but are not limited to, polyethylene, polypropylene, polystyrene and polymethyl methacrylate. Non-limiting examples of polystyrene copolymers include ROPAQU
E.RTM. HP-1055, ROPAQUE.RTM. OP-96, and ROPAQUE.RTM. OP-62LO pigments (each described above).

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

[0081] Composite particles 24 useful in the present invention include particles formed by packaging, encapsulating, or coating particles formed from a primary material with one or more secondary materials. For example, inorganic particles formed from an inorganic material (eg, silicon carbide or aluminum nitride) can be used to form useful composite material particles.
A silica, carbonate or nanoclay coating can be provided. In another example, a silane coupling agent with an alkyl side chain can be reacted with the surface of the inorganic particles formed from the inorganic oxide to provide useful composite particles having a "softer" surface. Other examples include armored, encapsulated or coated particles formed from an organic or polymeric material that is an inorganic or different organic or polymeric material. Non-limiting examples of such composite particles include DUA
There is LITE, which is a synthetic polymer particle coated with calcium carbonate,
Pierce and Sevens Corporation of Buf
falo, New York.

In yet another embodiment of the present invention, particles 24 may be hollow particles formed from a material selected from the group consisting of inorganic, organic, polymeric, composite, and mixtures thereof. . Non-limiting examples of suitable materials from which these hollow particles can be formed are described above. Non-limiting examples of hollow polymeric particles useful in the present invention include ROPAQUE® HP-1055, POPAQUE®
There are OP-96 and POPAQUE® OP-62LO pigments (each described above). For other non-limiting examples of hollow particles that may be useful in the present invention, see Katz et al. (1987), pp. 437-452, the contents of which are incorporated herein by reference. See).

The solid lubricant particles 24 can be present in an aqueous dispersion, suspension or emulsion. If desired, the sizing composition can include other solvents, such as mineral oil or alcohol (preferably less than about 5% by weight). Non-limiting examples of preferred aqueous dispersions of about 25% by weight boron nitride include ORPAC BORON NI
There is TRIDE RELEASE COAT-CONC, which is a ZYP Co
atings, Inc. of Oak Ridge, Tennessee. "ORPAC BORON NITRIDE RELESEC
OAT-CONC ”is a trademark of ZYP Coatings, Inc. , The contents of which are incorporated herein by reference. The boron nitride particles in the product have an average particle size of less than about 3 micrometers and about 1% magnesium-aluminum silicate to bind the boron nitride particles to the substrate to which the dispersion is applied. It contains. Other useful products commercially available from ZYP Coatings include BORON NITRIDE LUBRICOAT® paint, BRAZE STOP and WELD RELEASE products. Non-limiting examples of emulsions and dispersions of synthetic polymer particles formed from acrylic polymers and copolymers include: Rhoplex®
GL-623 ²⁷ (which is an all-acrylic farm (firm) polymer emulsion having 45 wt% solids content and a glass transition temperature of about 98 ° C.); EMUL
SION E-23221 ²⁸ (which has a solids content of 45% by weight and about 105 ° C.
Is a hard methacrylate polymer emulsion having a glass transition temperature of
QUE® OP-96 (described above), supplied as a dispersion having a particle size of 0.55 micrometers and a solids content of 30.5% by weight; R
OPAQUE® OP-62LO (described above), also supplied as an opaque non-film-forming synthetic pigment dispersion having a particle size of 0.40 micrometers and a solids content of about 36.5% by weight And ROPAQUE® HP-1055 (described above), which is supplied as a dispersion having a solids content of about 26.5% by weight; all of which are described in Rohm and Haas
Company of Philadelphia, Pennsylvani
a.

²⁷ Rohm and Haas Company, Philadelphia
a, March 1997 "Rhople available from Pennsylvania.
x (registered trademark) GL-623, Self-Crosslinking Acry
ric Binder of Industrial Nonwovens, the contents of which are incorporated herein by reference. ²⁸ Rohm and Haas Company, Philadelphia
a, "Building Produ" available from Pennsylvania
cts Industrial Coatings-Emulsion E-2
321 "(1990), the contents of which are incorporated herein by reference.

Although not required, particles 24 are preferably non-hydratable inorganic solid lubricant particles. As used herein, "non-hydrat"
The term "able" means that these solid inorganic lubricant particles do not react with water molecules to form hydrates and contain no water of hydration or water of crystallization. "Hydrate" is generated by the reaction of a substance whose H-OH bond is not split with a water molecule. R. Lewis, Sr. , Hawley's Cond
ened Chemical Dictionary, (12th edition, 1993)
Year), pages 609-610 and T.M. Perros, Chemistry, (
1967), 186-187, the contents of which are incorporated herein by reference. Structurally hydratable inorganic materials are described, for example, in J. Am. Mitc
hell, Fundamentals of Soil Behavior (1
976), page 34, FIG. 3.8, which shows the structure of kaolinite; van Olphen, Clay Colloid Chem
As shown in the structure of the 1: 1 and 2: 1 layer minerals shown in FIGS. 18 and 19, respectively, on page 62 (2nd edition, 1977). Contains at least one hydroxyl group in the crystal lattice layer (but is incorporated by reference herein), but contains hydroxyl groups at their surface or at the surface of the unit structure or substance that absorbs water by capillary action do not do)
. A “layer” of a crystal lattice is a combination of sheets, which is a combination of planes of atoms. Minerals in Soil Environments, So
il Science Society of America (1977)
196-199 (the contents of which are incorporated herein by reference). The collection of layers and interlayer materials (eg, cations) is called a unit structure.

A hydrate contains coordinating water, which coordinates with its cations in the hydrated material and whose structure and / or structure water (which is a gap in this structure) And is added to its electrostatic energy without disrupting the charge balance) and cannot be removed. R, Evans, An Introduction
See to Crystal Chemistry, (1948), page 276, the contents of which are incorporated herein by reference.

[0087] Although not preferred, the aqueous sizing composition can contain a hydratable or hydrated inorganic solid lubricant material in addition to the non-hydratable inorganic solid lubricant material described above. Non-limiting examples of such hydratable inorganic solid lubricant materials include the clay mineral phyllosilicic acid, which includes mica (muscovite), talc, montmorillonite, kaolinite and gypsum.

Preferably, the coating composition is substantially free of hydratable inorganic solid lubricant particles or abrasive silica particles or calcium carbonate, ie, on a total solids basis,
Less than about 20% by weight, more preferably less than about 5% by weight, and most preferably less than about 0.5% by weight.
Contains less than 001% by weight of hydratable inorganic lubricant particles, abrasive silica particles or calcium carbonate.

In an alternative embodiment useful in the present invention, particles 24 are formed from an organic polymeric material selected from the group consisting of thermosetting materials, thermoplastic materials, starch, and mixtures thereof. Suitable thermoset materials include thermoset polyesters, vinyl esters, epoxy materials, phenolics, aminoplasts, thermoset polyurethanes, and mixtures thereof (eg, those described below). Suitable thermoplastic materials include vinyl polymers, thermoplastic polyesters, polyolefins, polyamides, thermoplastic polyurethanes, acrylic polymers and mixtures thereof. Preferred organic particles are in the form of microbeads or hollow spheres.

Although not required, in one embodiment useful in the present invention, particles 24 are thermally conductive, ie, having a thermal conductivity of greater than about 30 watts per meter K, preferably 1 It has a thermal conductivity of greater than about 100 watts per metric K, and more preferably a thermal conductivity in the range of about 100 to about 2000 watts per metric K. As used herein, the term "thermal conductivity" refers to the property of a particle 24 that describes its ability to transfer heat through itself. R. Lewis, Sr.
, Hawley's Condensed Chemical Diction
ary, (12th edition, 1993), page 305, the contents of which are incorporated herein by reference.

The thermal conductivity of a solid material can be measured by any method known to those skilled in the art. For example, if the thermal conductivity of the material under test ranges from about 0.001 watts per meter K to about 100 watts per meter K, then the thermal conductivity of the material is about 300K. At temperature, it can be measured using the preferred guarded hotplate method according to ASTM C-177-85, the contents of which are incorporated herein by reference. If the thermal conductivity of the material to be tested ranges from about 20 watts per meter K to about 1200 watts per meter K, then the thermal conductivity of the material is ASTM C-518-91 ( Its contents can be measured using the guarded hot flux sensor method according to (herein incorporated by reference herein). It is believed that materials with higher thermal conductivity dissipate heat generated during the drilling operation from the bore area more quickly, thereby extending the life of the drill tip. The thermal conductivity of the selected materials in Table A is included in Table B.

[0092] Although not required, in other embodiments useful in the present invention, particles 24 are
It is electrically insulating or has a high electrical resistivity, ie, greater than about 1000 microohm-cm. The use of particles with a high electrical resistivity is preferred for normal electronic circuit applications because it prevents loss of electrical signals due to conduction of electrons due to this enhancement. Special applications (eg, microwave circuit boards, radio frequency and electromagnetic interference applications) do not require high electrical resistivity particles.
The electrical resistance of the selected materials in Table A is included in Table B.

It will be understood by those skilled in the art that the particles 24 of the coating composition may contain any combination or mixture of the particles 24 described above. More specifically, particles 24 can include additional particles made from any of the above materials to form particles 24.

[0094] These solid lubricant particles, if present, are present in an amount of about 1 to about 1 on a total solids basis.
%, Preferably about 1 to about 60% by weight of the coating composition. In one embodiment, the coating composition can include from about 2 to about 10% by weight, based on total solids, of boron nitride. In another embodiment of the present invention, wherein a combination of different particles is used. %, More preferably from about 30 to about 50% by weight of the particles 24.

The coating composition may further contain one or more emollients or surfactants, which impart a uniform change to the surface of the fibers and cause the fibers to repel each other. And reduce friction between these fibers to function as a lubricant. Although not required, it is preferred that these softeners are chemically different from the polymeric materials described above. Although the coating composition may contain up to about 60% by weight of a softener, preferably the coating composition is substantially free of softener, ie, contains less than about 10% by weight of a softener. And more preferably,
Contains less than about 5% by weight of a softener. Examples of such softeners include cationic, nonionic or anionic softeners and mixtures thereof, such as amine salts of fatty acids, alkylimidazoline derivatives (eg, CATION X
(This is Rhone Poulenc of Princeton, New
Commercially available from Jersey)), acid solubilized fatty acid amides, condensates of fatty acids with polyethyleneimine and amide substituted polyethyleneimines (eg, EMERY)
(Registered trademark) 6717), Henkel Corporation of Ka
and partially amidated polyethyleneimine commercially available from NKakee, Illinois. For more information on softeners, see A. J. Ha
II, Textile Finishing, Second Edition, (1957), 108
Pp. 115, the contents of which are incorporated herein by reference.

The coating composition can contain one or more emulsifiers (eg, organic and inorganic particles) for emulsifying or dispersing the components of the coating composition. Non-limiting examples of suitable emulsifiers or surfactants include polyoxyalkylene block copolymers, such as PLURONIC® F-108 polyoxypropylene-polyoxyethylene copolymer (BASF Corporation
on of Parsippany, New Jersey), ethoxylated alkylphenols (e.g., IGEPAL CA-630 ethoxylated octylphenoxyethanol, which is GAF Corporation)
on of Wayne, New Jersey), polyoxyethylene octyl phenyl glycol ether, ethylene oxide derivatives of sorbitol esters, polyoxyethylated vegetable oils (eg, ALKAMUL
SEL-719 (commercially available from Rhone-Poulenc)
) And a nonylphenyl surfactant (e.g., MACOL NP-6 (which is
BASF of Parsippany, New Jersey). Generally, the amount of emulsifier can range from about 1 to about 30% by weight of the coating composition, based on total solids.

[0097] The coating composition may further comprise one or more lubricating materials that are chemically different from these polymeric materials and the softening described above to impart the desired processing properties to the fiber strands during weaving. Agents can be included. Suitable lubricating materials can be selected from the group consisting of oils, waxes, greases and mixtures thereof. Non-limiting examples of wax materials useful in the present invention include aqueous soluble, emulsifiable or dispersible wax materials such as vegetable waxes, animal waxes, mineral waxes, synthetic waxes or petroleum waxes. For example, paraffin)). Oils useful in the present invention include natural, semi-synthetic and synthetic oils. Generally, the amount of wax or other lubricating material will range from 0 to about 80%, preferably from about 1 to about 50%, more preferably from about 20 to about 40% by weight of the sizing composition, based on total solids. %, Most preferably from about 25 to about 35% by weight.

[0098] Preferred lubricating materials include polar waxes and oils, more preferably polar and melting points above about 35 ° C (more preferably about 45 ° C).
(High melting point). Such materials have a wet out and a wet out on fiber strands coated with a sizing composition containing such a polar material, as compared to fiber strands coated with a sizing composition containing a non-polar wax and oil. It is thought to improve wet-through. Preferred polar lubricating materials include esters formed from reacting (1) a monocarboxylic acid and (2) a monohydric alcohol.
Non-limiting examples of such fatty acid esters useful in the present invention include cetyl palmitate (which is preferred, for example, KESSCO 653 or STEPANT).
As EX 653, Stepan Company of Maywood,
Commercially available from New Jersey), cetyl myristate (also available as STEPANLUBE 654 from Stepan Company), cetyl laurate, octadecyl laurate, octadecyl myristate, octadecyl palmitate and octadecyl stearate. . Other fatty acid esters that are lubricating materials useful in the present invention include trimethylolpropane triperargonate, natural spermaceti and triglyceride oils, including, for example, soybean oil, linseed oil, epoxidized soybean oil, and epoxide. Oil).

Although not preferred, the coating composition may contain one or more other lubricating materials (eg, non-polar petroleum waxes) in place of or in addition to the lubricating materials described above. Non-limiting examples of non-polar petroleum waxes include MICHEM® LUBE 296 microcrystalline wax, POLYMEKON® S
PP-W microcrystalline wax and PETROLITE 75 microcrystalline wax (
These are, respectively, Michelman Inc. of Cincinnat
i, Ohio and the Petrolite Corporation o
f Tulsa, Oklahoma).

Although not required, if desired, the coating composition can also be used to further improve the lubrication of the coated fiber strands of the present invention while maintaining resin compatibility, such as manufacturing operations such as weaving and knitting. Good performance in such weaving operations is provided by reducing the potential for the formation of fluff, halo and broken filaments therein. As used herein, "resin-reactive diluent" means that the diluent contains functional groups that can chemically react with the same resin for which the coating composition is compatible. The diluent may include one or more functional groups that react with the resin system, preferably functional groups that react with the epoxy resin system, more preferably functional groups that react with the FR-4 epoxy resin system. Lubricant. Non-limiting examples of suitable lubricants include lubricants with amine, alcohol, anhydride, acid or epoxy groups. A non-limiting example of a lubricant with an amine group is a modified polyethylene amine (eg, EMERY 6717), which is available from Henkel C
Partially amidated polyethyleneimine commercially available from the corporation of Kankakee, Illinois. Non-limiting examples of lubricants with alcohol groups include polyethylene glycol (eg, CARBO).
WAX 300), which is a Union Carbide of Dan.
Polyethylene glycol commercially available from Bury, Connecticut. Non-limiting examples of lubricants with acid groups include fatty acids (eg, stearic acid) and salts of stearic acid. Non-limiting examples of lubricants with epoxy groups include epoxidized soybean oil and epoxidized linseed oil (eg, FLEXOL L
OE (which is an epoxidized linseed oil) and FLEXOL EPO (which is an epoxidized soybean oil) (both Union Carbide of
Danbury, Connecticut), and LE
-9300 epoxidized silicone emulsion (Witco Corpora
Tion OSi Specialties, Inc. of Danbury
, Connecticut))). Without limitation in the present invention, the sizing composition can contain the resin-reactive diluent described above in an amount up to about 15% by weight of the sizing composition, based on total solids.

Crosslinking materials (eg, melamine formaldehyde), and plasticizers (eg, phthalates, trimellitates, and adipates) can also be included in the coating composition. The amount of crosslinker or plasticizer, based on total solids, is about 1% of the coating composition.
To about 5% by weight.

[0102] The coating composition will generally include other additives, such as, for example, less than about 5% by weight.
Silicones, fungicides, bactericides and anti-foaming materials). Organic and / or
Alternatively, an inorganic acid or base can also be included in an amount sufficient to provide a coating composition having a pH of about 2 to about 10. A non-limiting example of a suitable silicone emulsion is LE-9300 epoxidized silicone emulsion, which is available from OSi Sp.
ecolies, Inc. of Danbury, Connecticut
It is commercially available from. One example of a suitable fungicide is the BIOMET 66 antimicrobial compound, which is available from M & T Chemicals of Rahway, New
It is commercially available from Jersey. Suitable anti-foaming materials include SAG materials (these are OSi Specialties, Inc. of Danbury, Conn.)
and MAZU DF-136 (available from BASF Corporation of Parsippany, New York).
Commercially available from Jersey). If desired, ammonium hydroxide can be added to the coating composition for stabilization. To facilitate the application of a substantially uniform coating on the strand, the coating composition generally comprises
Water, preferably deionized water, is contained in an amount of about 99% by weight. The weight percentage of solids of the aqueous coating composition generally ranges from about 1 to about 75% by weight.

The coating composition is preferably virtually free of glass material. As used herein, the term "essentially free of glass material" means that the coating composition
It means that it contains less than 20% by volume, preferably less than about 5% by volume, more preferably no glass material, of the glass matrix material for forming the glass composite. Examples of such glass matrix materials include:
Black glass ceramic materials or aluminosilicate matrix materials (eg, those well known to those skilled in the art) may be mentioned.

In one non-limiting embodiment of the electronic circuit board fabric of the present invention, the glass fibers of the coated fiber strand are coated with a primary layer of a dry residue of an aqueous sizing composition, The sizing composition is PolarTherm® 1
60 boron nitride powder and / or ORPAC BORON NITRIDE
RELEASECOAT-CONC dispersion, PVP K-30 polyvinylpyrrolidone, A-174 acrylic functional organic silane coupling agent, A-187 epoxy functional organic silane coupling agent, ALKAMULS EL-719 polyoxyethylated vegetable oil, EMERY (registered) TM) 6717 partially amidated polyethyleneimine, RD-847A polyester, DESMOPHEN 2000 polyester, PLURONICS F-108 polyoxypropylene-polyoxyethylene copolymer, ICONOL NP-6 alkoxylated nonylphenol and SAG 10 antifoam material.

In another embodiment of the electronic circuit board fabric of the present invention, the glass fibers of the coated fiber strand of the present invention are coated with a primary layer of a dry residue of the aqueous sizing composition, The composition was PolarTherm® 160
Boron nitride powder and / or ORPAC BORON NITRIDE RE
LEASECOAT-CONC dispersion, RD-847A polyester, PVP
K-30 polyvinylpyrrolidone, DESMOPHEN 2000 polyester,
A-174 Acrylic-functional organosilane coupling agent, A-187 epoxy-functional organosilane coupling agent, PLURONICS F-108 polyoxypropylene-polyoxyethylene copolymer, VERSAMID 140 polyamide and MACOL NP-6 nonylphenol I do.

In yet another embodiment for weaving a laminated printed circuit board fabric, the glass fibers of the coated fiber strands of the present invention have a primary layer of a dry residue of an aqueous primary sizing composition, and The composition was ROPAQUE® HP
-1055 and / or ROPAQUE® OC-96 styrene-acrylic copolymer hollow spheres, PVP K-30 polyvinylpyrrolidone, A-174
Acrylic-functional organosilane coupling agents and A-187 epoxy-functional organosilane coupling agents, EMERY® 6717 partially amidated polyethyleneimine, STEPANTEX 653 cetyl palmitate, TMAZ 81 ethylene oxide derivative of sorbitol ester, MACOL OP- Contains 10 ethoxylated alkylphenols and MAZU DF-136 anti-foam material. In addition, this embodiment optionally further includes PolarTher.
m® 160 boron nitride powder and / or ORPAC BORON
NITRIDE RELEASECOAT-CONC dispersion can be included.

[0107] Coating compositions useful in the present invention can be prepared by any suitable method (eg, conventional mixing well known to those skilled in the art). Preferably, the above components are diluted with water to have the desired percent solids by weight and mixed together. The powdered particles can be premixed with water or added to the polymeric material before mixing with the other components of the coating.

The coating layer is applied to the fibers in a number of ways, for example, by contacting the filament with a roller or belt applicator, spraying or other means. The coated fibers are preferably dried at room or elevated temperature. A dryer removes excess moisture from these fibers and cures any curable coating composition components, if present. The temperature and time at which these glass fibers are dried depend on variables such as 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 dried,
It is present as a dry sizing residue on these fibers in an amount between about 0.1% and about 25% by weight. The burning loss of these fibers is generally about 1.0% by weight.
Less than about 0.5% by weight, more preferably less than about 0.01% by weight.
約 0.45% by weight. As used herein, the term "burnout loss" means the weight percent of dry coating composition present on the surface of the fiber strand, as determined by the following equation: LOI = in _{100 × [(W dry -W bare} ) / W dry] wherein, W _dry the residual fiber strand + coating composition after drying for about 60 minutes at about 220 ° F in an oven (about 104 ° C.) The weight of the thing, and W _bare
The weight of the exposed fiber strands after removing the coating composition residue by heating the fiber strands in an oven at about 1150 ° F. (about 621 ° C.) for about 20 minutes.

On the coating composition layer described above, for example, by dipping the coating strand in a bath containing the secondary coating composition, by spraying the secondary coating composition onto the coating strand, or by coating By contacting the strand with the applicator described above, the secondary coating composition layer can be applied in an amount effective to coat or impregnate a portion of the coated strand. The coating strand can be passed through a die to remove excess coating composition from the strand, and / or for a time sufficient to at least partially dry or cure the secondary coating composition. Can be dried like The method and apparatus for applying the secondary coating composition to the strand is determined, in part, by the shape of the strand material. The strand is preferably dried after applying the secondary coating composition, in a manner well known in the art.

[0110] Suitable secondary coating compositions can contain one or more film-forming materials, lubricants and other additives, such as those described above. The secondary coating is preferably different from the sizing composition, ie, it contains (1) at least one component that is chemically different from the components of the sizing composition;
Or (2) contains at least one component in an amount different from the amount of the same component contained in the sizing composition. Non-limiting examples of suitable secondary coating compositions containing polyurethanes are described in U.S. Pat.
762, 751, the contents of which are incorporated herein by reference.

In an alternative embodiment of the present invention, the glass fibers of the fiber strands are coated with a primary coating of a dry residue of a sizing composition that can contain any of the conventional sizing compositions or sizing components in the amounts described above. it can. Examples of suitable sizing compositions are Loewenstein, pages 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). (Incorporated herein by reference). The secondary coating composition layer useful in the present invention and disclosed herein is applied to at least a portion, and preferably the entire outer surface, of this primary coating. The secondary coating composition can contain one or more of the particles described above and / or the particles shown in Table B below. It is noted that some of these particles have a higher Mohs hardness than expected for this glass fiber (i.e., about 4.5 to about 6). However, because these particles are the part of the secondary coating composition that does not directly contact the surface of the glass fiber, these high hardness values do not adversely affect the glass fiber and are acceptable.

[0112]

[Table 2] ²⁹ G. Slack, "Nonmetallic Crystals wit
h High Thermal Conductivity, "J. Am. Phys.
Chem. Solids (1973) Vol. 34, p. 322 (the contents of which are incorporated by reference herein) ³⁰ A. Weimer (eds.), Carbide, Nitride and B
oride Materials Synthesis and Procedures
sing, (1997 years), 654 pp. ³¹ Friction, Wear, Lubrication, 27 pp. ³² G. Slack, "Nonmetallic Crystals wit
h High Thermal Conductivity, "J. Am. Phys.
Chem. Solids (1973) Vol. 34, p. 325 (the contents of which are incorporated by reference herein) ³³ R. Lewis, Sr. , Hawley's Condensed Ch
Chemical Dictionary, (12th edition, 1993), p. 164 (
The contents of which are incorporated herein by reference.) ³⁴ G. Slack, "Nonmetallic Crystals wit
h High Thermal Conductivity, "J. Am. Phys.
Chem. Solids (1973) Vol. 34, p. 333 (the contents of which are incorporated by reference herein) ³⁵ G. Slack, "Nonmetallic Crystals wit
h High Thermal Conductivity, "J. Am. Phys.
Chem. Solids (1973) Vol. 34, p. 329 (the contents of which are incorporated by reference herein) ³⁶ A. Weimer (eds.), Carbide, Nitride and B
oride Materials Synthesis and Procedures
sing, (1997), p. 654, ³⁷ Fiction, Wear, Lubrication, p. 27, ³⁸ G. Slack, "Nonmetallic Crystals wit
h High Thermal Conductivity, "J. Am. Phys.
Chem. Solids (1973) Vol. 34, p. 333 ³⁹ G. Slack, "Nonmetallic Crystals wit
h High Thermal Conductivity, "J. Am. Phys.
Chem. Solids (1973) Vol. 34, p. 321 (the contents of which are incorporated herein by reference). ⁴⁰ Microelectronics Packaging Handbo
ok, 36 pp. (the contents of which are incorporated by reference herein) ⁴¹ A. Weimer (eds.), Carbide, Nitride and B
oride Materials Synthesis and Procedures
sing, (1997), p. 653, the contents of which are incorporated herein by reference. ⁴² Friction, Wear, Lubrication, p. 27, ⁴³ Microelectronics Packaging Handbod.
ok, 36 pp. (the contents of which are incorporated by reference herein) ⁴⁴ A. Weimer (eds.), Carbide, Nitride and B
oride Materials Synthesis and Procedures
sing, (1997), p. 654, ⁴⁵ Fiction, Wear, Lubrication, p. 27, ⁴⁶ Microelectronics Packaging Handbo.
ok, page 905, the contents of which are incorporated herein by reference. ⁴⁷ Hawley's Condensed Chemical Dicti.
onary, (12th edition, 1993), p. 141 (the contents of which are incorporated herein by reference) ⁴⁸ Friction, Wear, Lubrication, p. 27 ⁴⁹ Handbook of Chemistry and Physics and Physics
, CRC Press (1975), pp. 12-54, ⁵⁰ Handbook of Chemistry and Physics.
, CRC Press (71st edition, 1990), pp. 12-63 (the contents of
(Incorporated herein by reference)

[0113]

[Table 3] ⁵¹ Handbook of Chemistry and Physics
, CRC Press (71st edition, 1990), pp. 4-158 (contents of
(Incorporated herein by reference) ⁵² Microelectronics Packaging Handbo
Ok, p. 36 ⁵³ Handbook of Chemistry and Physics
, CRC Press (71st edition, 1990), pp. 12-63 (the contents of
⁵⁴ Handbook of Chemistry and Physics.
, F-22, ⁵⁵ Microelectronics Packaging Handbo
Ok, page 174 ⁵⁶ Handbook of Chemistry and Physics
, F-166 pp (the contents of which are incorporated by reference ^{herein) 57 Friction, Wear, Lubrication,} 27 pp. ⁵⁸ G. Slack, "Nonmetallic Crystals wit
h High Thermal Conductivity, "J. Am. Phys.
Chem. Solids (1973) Vol. 34, p. 322 (the contents of which are incorporated by reference herein) ⁵⁹ W. Callister, Materials Science and
Engineering An Introduction, (2nd edition, 19
1991), p. 637, the contents of which are incorporated herein by reference. ⁶⁰ Handbook of Chemistry and Physics
, F-22, ⁶¹ Microelectronics Packaging Handbo
OK, 174 pages ⁶² Microelectronics Packaging Handbo
ok, p. 37, ⁶³ "Web Elements" http: // www. shef. ac.
uk / ~ chem / web-elents / nofr-image-l / har
dness-minerals-l. html (February 26, 1998) ⁶⁴ Microelectronics Packaging Handbo
OK, 174 pages ⁶⁵ Microelectronics Packaging Handbo
ok, p. 37 ⁶⁶ Handbook of Chemistry and Physics
, F-22 ⁶⁷ Microelectronics Packaging Handbo
ok, p. 37, ⁶⁸ Microelectronics Packaging Handbo
ok, p. 37 ⁶⁹ Handbook of Chemistry and Physics
, F-22, ⁷⁰ Microelectronics Packaging Handbo
Ok, p. 37, ⁷¹ Microelectronics Packaging Handbo
ok, p. 37, ⁷² "Web Elements" http: // www. shef. ac.
uk / ~ chem / web-elents / nofr-image-1 / har
dness-minerals-l. html (February 26, 1998) ⁷³ Microelectronics Packaging Handbo
OK, 174 pages ⁷⁴ Microelectronics Packaging Handbo
ok, p. 37 ⁷⁵ Handbook of Chemistry and Physics
, F-22, ⁷⁶ Microelectronics Packaging Handbo
ok, 174 pages ⁷⁷ Microelectronics Packaging Handbo
Ok, p. 37, ⁷⁸ Friction, Wear, Lubrication, p. 27, ⁷⁹ Microelectronics Packaging Handbod.
ok, p. 37 ⁸⁰ Microelectronics Packaging Handbo
ok, p. 37 ⁸¹ Handbook of Chemistry and Physics
, F-22, ⁸² Microelectronics Packaging Handbo
ok, 174 pages ⁸³ Microelectronics Packaging Handbo
Ok, p. 37, ⁸⁴ Handbook of Chemistry and Physics
, Page F-22

[0114]

[Table 4] ⁸⁵ Microelectronics Packaging Handbo
ok, 174 pages ⁸⁶ Microelectronics Packaging Handbo
ok, p. 37 ⁸⁷ Handbook of Chemistry and Physics
, F-22, ⁸⁸ Microelectronics Packaging Handbo
Ok, p. 174 ⁸⁹ Handbook of Chemistry and Physics
⁹⁰ Pressbook of Chemistry and Physics, CRC Press (1975), p. D-171, the contents of which are incorporated herein by reference.
, F-22, ⁹¹ Microelectronics Packaging Handbo
OK, 174 pages ⁹² Microelectronics Packaging Handbo
ok, p. 37 ⁹³ Handbook of Chemistry and Physics
F-22, molybdenum disulfide and molybdenum oxide are other inorganic particles useful in the secondary or tertiary coatings useful in the present invention. One skilled in the art will understand that mixtures of any of the above inorganic particles can be used in the present invention.

[0115] In an alternative embodiment, the particles of the secondary coating composition contain hydrophilic inorganic particles that absorb and retain water in the interstitial spaces of the hydrophilic particles. These hydrophilic inorganic particles can absorb water or swell when contacted with water, or participate in a chemical reaction with this water, forming, for example, a viscous gel-like solution, This prevents or prevents water from further entering the gap in the communication cable that uses the coated fiberglass strand for reinforcement. The term "absorb" as used herein means that the water penetrates the internal structure or interstices of the hydrophilic material and is substantially retained therein. Hawley's Condensed Ch
See Chemical Dictionary, page 3, the contents of which are incorporated herein by reference. "Swell" means that the size or volume of these hydrophilic particles is increased. Webster's New Coll
See egigate Dictionary (1977), p. 1178, the contents of which are incorporated herein by reference. Preferably, these hydrophilic particles swell after contact with water at least 1.5 times their initial dry weight, more preferably about 2 to about 6 times their initial weight. Non-limiting examples of swelling hydrophilic inorganic solid lubricant particles include smectites (eg, vermiculite and montmorillonite), absorbent zeolites, and inorganic absorbent gels. Preferably, these hydrophilic particles are applied in powder form on a sticky sizing material or other sticky secondary coating material. The amount of hydrophilic inorganic particles in this embodiment of the secondary coating composition may range from about 1 to about 99% by weight, based on total solids, preferably
It can range from about 20 to about 90% by weight.

[0116] The amount of inorganic particles in the secondary coating composition may range from about 1 to about 99% by weight, preferably from about 20 to about 90% by weight, based on total solids. The percentage of solids in the aqueous secondary coating composition generally ranges from about 5 to about 75% by weight.

In another alternative embodiment of the present invention, a layer of the tertiary coating composition is applied to at least a part, preferably the entire surface, of the secondary coating, ie such fiber strands are of primary sizing It has a coating layer, a secondary coating composition layer, and a tertiary coating outer layer. The tertiary coating is preferably different from the sizing composition and the secondary coating composition, i.e., the tertiary coating composition is (1) chemically compatible with the components of the sizing composition and the secondary coating composition. Or (2) at least one component in an amount different from the amount of the same component contained in the sizing composition or the secondary coating composition. . This tertiary coating may be applied to these glass fibers or strands before or after incorporation into the fabric using methods such as, but not limited to, spraying and dipping as described above and well known in the art. You.

In this embodiment, the secondary coating composition contains one or more of the above-mentioned polymeric materials (eg, polyurethane) and the tertiary coating composition comprises powdered thermally conductive inorganic particles (Eg, PolarTherm® boron nitride particles)
Or hollow particles (eg, ROPAQUE® pigments), which are mentioned above. Preferably, the powdered coating is applied by passing the strands coated with the liquid secondary coating composition through a fluidized bed or sprayer to adhere the powdered particles to the tacky secondary coating composition. Alternatively, these strands may be applied to the fabric 114 before the tertiary coating 140 is applied, as shown in FIG.
Can be assembled. The weight percent of the powdered thermally conductive inorganic particles attached to the coated strand can range from about 0.1 to about 75% by weight of the total weight of the dried strand. The tertiary coating may also include one or more polymeric materials as described above (eg, acrylic polymers, epoxides or polyolefins, conventional stabilizers known in the art of such coatings, and Other modifiers) can be included, preferably in dry powder form.

Although the foregoing discussion is generally directed to applying the coating composition of the present invention directly to glass fibers after fiber formation and subsequently incorporating the fibers into a fabric, the present invention also provides One of ordinary skill in the art will appreciate that the coating compositions of the present invention include embodiments that are applied to a fabric after it has been manufactured using various methods well known in the art. Depending on the processing of the fabric, the coating composition of the present invention can either be applied directly to the glass fibers in the fabric or can be applied to the glass fibers and / or other coatings already on the fabric. Can be For example, these glass fibers may be formed and woven into a fabric prior to regular starch-oil sizing (st
arch-oil sizing). The fabric can then be treated to remove the starch-oil sizing. The coating compositions useful in the present invention and disclosed herein are then known in a known manner, such as, but not limited to, spraying or dipping a cloth into a bath of the sizing composition. Can be applied directly to the fabric. The fabric can then be dried before further processing, leaving a residue of the composition on the fibers and strands of the fabric. This sizing removal is accomplished using methods well known in the art (eg, heat treating or cleaning the fabric). In this case, the coating composition
The surface of the fabric fibers is directly coated. If one does not remove a portion of the sizing composition originally applied to these glass fibers after formation, the coating composition of the present invention may be applied to the sizing composition rather than applied directly to the fiber surface. It is applied to the rest.

In another embodiment of the present invention, selected components of the coating composition of the present invention are applied to as-formed glass fibers, and the remainder of the coating composition is applied to the fabric after making the fabric. Applied to. In a manner similar to that described above, some or all of these selected components can be removed from the fibers prior to coating the glass fibers and fabric with the remaining components. As a result, these remaining components either coat the surface of the fibers of the fabric directly or cover selected components that have not been removed from the fiber surface.

The woven fabric 14 is used as a reinforcement to reinforce the polymeric matrix material 12, and is preferably a composite or laminate 10 (for use in electronic circuit boards).
For example, those shown in FIG. 1) are formed. The warp and weft (ie, fill) strands of the fabric 14 may be untwisted (also referred to as non-twisted or zero-twisted) or may employ any conventional twisting method known to those skilled in the art (eg,
This strand can be twisted prior to weaving by using a twisting frame to provide about 0.5 to about 3 turns of twist per inch). In addition, cloth 1
4 can include various combinations of both twisted and untwisted warp and weft strands.

The reinforced fabric 14 comprises from about 5 to about 100 warp strands per centimeter (about 13 to about 254 warp strands per inch), preferably from about 6 to about 50 warp strands per centimeter. Weft yarn strands (about 15 to about 127 weft strands per inch) may be included. The weave structure can be a conventional plain weave, but any other weave style known to those skilled in the art (eg, twill or satin weave) can be used.

The fabric 14 is preferably a “Fabrics Around the Wor”
ld ", Clark-Schwebel, Inc. of Anderson, S
in a manner suitable for use in laminates for printed circuit boards, as disclosed in the Technical Bulletin of South Carolina (1995), the contents of which are incorporated herein by reference. Woven. A non-limiting example of a fabric style that uses E225 E glass fiber is Style 2116, which includes 5
722 with 118 warp yarns and 114 weft yarns per centimeter (60 warp yarns and 58 weft yarns per inch)
Use 1 × 0 (E225 1/0) warp and weft yarns and 0.09
It has a nominal fabric thickness of 4 mm (0.037 inches) and a fabric weight of 103.8 g / m ² (3.06 ounces per square yard). A non-limiting example of a fabric style using G75 E glass fiber is Style 7628, which includes 5
It has 87 warp yarns and 61 weft yarns per centimeter (44 warp yarns and 31 weft yarns per inch), 9681 x
0 (G75 1/0) warp and weft yarns and use 0.173 mm
It has a nominal fabric thickness of (0.0068 inches) and a fabric weight of 203.4 g / m ² (6.00 ounces per square yard). A non-limiting example of a fabric style using D450E glass fiber is Style 1080, which is 118 warp yarns and 93 weft yarns per 5 cm (60 warp yarns per inch and 60 warp yarns per inch). 47 weft yarns), 5 11 1 × 0
(D450 1/0) warp and weft yarns and use 0.053 mm
It has a nominal fabric thickness of (0.0021 inches) and a fabric weight of 46.8 g / m ² (1.38 ounces per square yard). A non-limiting example of a fabric style using D900E glass fiber is Style 106, which is 110 warp yarns and 110 weft yarns per 5 cm (56 warp yarns per inch and 56 warp yarns per inch). 55.5 1 × 0 with 56 weft yarns)
(D900 1/0) warp and weft yarns and 0.033 mm
It has a nominal fabric thickness of (0.013 inches) and a fabric weight of 24.4 g / m ² (0.72 ounces per square yard). Another non-limiting example of a fabric style using D900E glass fiber is Style 108, which is 118 warp yarns and 93 weft yarns per 5 centimeter (118 warp yarns per inch). 60 and 47 weft yarns) and 55.5 1 × 0
(D900 1/2) warp and weft yarns and 0.061 mm
It has a nominal fabric thickness of (0.0024 inches) and a fabric weight of 47.5 g / m ² (1.40 ounces per square yard). Another non-limiting example of a fabric style that uses E225 and D450E glass fibers is Style 2113, which includes 118 warp yarns and 110 weft yarns per 5 centimeter (60 yarns per inch). Warp yarns and 56 weft yarns), a warp yarn of 7221 × 10 (E225 1/0) and 511 × 0 (D4
50/0) weft yarn and has a nominal fabric thickness of 0.031 mm (0.0031 inches) and a fabric weight of 78.0 g / m ² (2.30 ounces per square yard). Another non-limiting example of a fabric style that uses both G50 and G75E fiberglass yarns is Style 7535, which has 87 warp yarns and 57 fill yarns per 5 centimeter (1).
44 warp yarns and 29 fill yarns per inch) and 96
8 1 × 0 (G75 1/0) warp yarn and 999 1 × 0 (G50
1/0) fill yarn and has a nominal fabric thickness of 0.201 mm (0.0079 inches) and a fabric weight of 232.3 g / m ² (6.85 ounces per square yard). Specifications for these and other useful fabric styles can be found in IPC-EG-140 "Specification for Finish"
ed Fabric Woven from "E" Glass for Pr
integrated Boards "(The Institute for Inte
rconnecting and Packaging Electronic
Circuits (June 1997)).
It is incorporated herein by reference. Although the fabric styles use twisted yarns, it is contemplated that these or other fabric styles using zero twisted yarns or rovings with or instead of twisted yarns can be made in accordance with the present invention. Further, some or all of the warp yarns of the fabric can have fibers coated with a first resin compatible sizing composition, and some or all of the fill yarns have a different second yarn than the first composition. It is contemplated that the second composition may have fibers coated with a resin-compatible coating, ie, (1) contains at least one component that is chemically different from the components of the first sizing composition. Or (2) an amount different from the amount of the same component contained in the first sizing composition by at least 1
Contains seed ingredients.

Suitable reinforced woven fabrics 14 useful in the present invention can be any conventional looms known to those skilled in the art (eg, shuttle loom or rapier looms).
er room)), but is preferably formed using an air jet loom. In weaving fabrics using the air jet method, the air jet loom inserts the fill yarn into the warp shed and blasts compressed air from one or more air jets.
Drives the yarn over the width of the fabric. Preferred air jet looms are available from Tsudakoma of Japan in Model No. 1
03, 103I and 1033, and Sulzer®
uti Model No. L-5000, L-5100 and L-5200 (
These are available from Sulzer Brothers Ltd. of Zurich, S
commercially available from Witzerland). Sulzer RutiL
-5000, L-5100 and L-5200 Product Bullet
ins of Sulzer Ruti Ltd. Swisserland, the contents of which are incorporated herein by reference.

Referring now to FIG. 1, fabric 14 is laminated by coating and / or impregnating one or more layers of fabric 14 with polymeric thermoplastic or thermoset matrix material 12. Used to form body 10. The laminate 10 is suitable for use as an electronic support.

The matrix materials useful in the present invention include thermosetting materials, such as thermosetting polyesters, vinyl esters, epoxides, which contain at least one epoxy or oxirane group in the molecule, eg, , Polyglycidyl ethers of polyhydric alcohols or thiols), phenols, aminoplasts, thermosetting polyurethanes, derivatives and mixtures thereof. Preferred matrix materials for forming laminates for electronic circuit boards include FR-4 epoxy resins, polyimides, and liquid crystalline polymers, the compositions of which are well known to those skilled in the art. If further information relating to such compositions is needed, 1 Electronic
Materials Handbook (R), ASM International
Tional (1989), pp. 534-537.

[0127] Non-limiting examples of suitable thermoplastic polymeric 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,
Examples include polyvinyl chloride and polycarbonate.

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

In the composite material, other components that can be included with the polymeric matrix material and the reinforcing material include colorants or pigments, lubricants or processing aids, ultraviolet (UV)
) Stabilizers, antioxidants, other fillers and extenders.

The cloth 14 is made of, for example, R.P. Tummala (ed.), Microelectro
nicks Packaging Handbook, (1989), 895-
Fabric 14 can be coated and impregnated by soaking fabric 14 in a bath of polymeric matrix material 12, as described on page 896, the contents of which are incorporated herein by reference. The polymeric matrix material 12 and the fabric 14 can be formed into the composite or laminate 10 by a variety of methods depending on factors such as the type of polymeric matrix material used. For example, for thermoset matrix materials, the laminate may be compression molded or injection molded, pultrusi molded.
on), by hand lay-up, or by sheet molding followed by compression or injection molding. The thermoset polymeric matrix material is cured, for example, by including a crosslinking agent in the matrix material and / or by applying heat. Suitable crosslinking agents useful for crosslinking the polymeric matrix material are described above. The temperature and cure time for the thermoset polymer matrix material depends on factors such as the type of polymer matrix material used, other additives in the matrix system and the thickness of the composite material (only a few are listed). ) Relies on.

For thermoplastic matrix materials, suitable methods for forming the composite include direct molding or extrusion compounding followed by injection molding. A method and apparatus for forming this composite material by the above method is described in I.S. Rubi
n, Handbook of Plastic Materials and
Technology (1990), pp. 955-1065, 1179-1.
At pages 215 and 1225-1271, the contents of which are incorporated herein by reference.

In one embodiment, shown in FIG. 5, but not limited to the present invention, the composite or laminate 210 contains a fabric 214 impregnated with a compatible matrix material 212. The impregnated fabric can then be squeezed between a set of metering rolls or bars to leave a measured amount of matrix material and dried to form an electronic support in the form of a semi-cured substrate or prepreg. . Along a portion of the side 252 of the prepreg, a conductive layer 250 is disposed in a manner described herein below, and the prepreg is cured to form a laminate 210, which is a conductive layer. Function as an electronic support 254 including In other embodiments of the present invention, more typically, in the electronic support industry, two or more prepregs are combined with one or more conductive layers, laminated together, and provided to those skilled in the art. Cured in a known manner to form an electronic support. For example, without limiting the invention,
The stack of prepregs is laminated by pressing the stack at elevated temperatures and pressures, for example, between polished steel plates, for a predetermined time to cure the polymeric material and form a laminate of the desired thickness. Is done. One of these prepregs
In one or more parts, the obtained electronic support is a laminate having at least one conductive layer along a part of the exposed surface (hereinafter, referred to as a “cladding laminate”). A conductive layer can be provided either before or after lamination and curing.

[0133] Circuits can then be formed from the conductive layers of the single or multi-layer electronic support using methods well known in the art for making electronic supports in the form of electronic circuit boards.

If desired, these electronic supports may include any known in the art to allow electrical interconnection between circuits and / or components on opposite sides of the electronic support. A convenient manner, including, but not limited to, mechanical drilling and laser drilling, creates an opening or hole (also referred to as a "bias"). More specifically, referring to FIG. 6, the opening 360 extends through at least one layer 362 of the fabric 312 of the electronic support 354 of the present invention. The fabric 312 includes a coated fiber strand, which, as taught herein, contains at least one glass fiber having a layer that is compatible with various polymeric matrix materials. In forming the opening 360, the electronic support 354 is located in a registry with the opening forming device (eg, a drill bit 364 or a laser tip). The opening 360 is provided with a drill 364.
Or at least one layer 3 of the fabric 312 by perforating using a laser.
It is formed through a portion 366 of 62. After forming these openings, a layer of conductive material is deposited on the walls of the openings, or the openings are filled with a conductive material to cover one of the surfaces of the electronic support 354. Facilitates the necessary electrical interconnections and / or heat dissipation between layers or more conductive layers (not shown in FIG. 6).

This conductive layer is shown, for example, as layer 250 in FIG. 5, but can be formed by any method known to those skilled in the art. For example, but not by way of limitation, the conductive layer is formed by laminating a thin sheet or foil of a metal material on at least a portion of a side surface of a semi-cured or cured prepreg or laminate. . Instead, the conductive layer is formed using well known methods, including, but not limited to, electroplating, electroless plating or sputtering.
It is formed by vapor deposition on at least a portion of the side surface of the semi-cured or cured prepreg or laminate. Metallic materials suitable for use as the conductive layer include:
Examples include, but are not limited to, copper (preferred), silver, aluminum, gold, tin, tin-lead alloy, palladium, and combinations thereof.

In another embodiment of the invention, the electronic support comprises one or more electronic circuit boards (described above), one or more clad laminates (described above) and / or one or more clad laminates (described above). This is the shape of a multilayer electronic circuit board produced by laminating the above prepreg (described above). If desired, the electronic support can incorporate additional conductive layers, for example, along a portion of the exposed surface of the multilayer electronic circuit board. Furthermore, if necessary, additional circuits can be formed from these conductive layers in the manner described above. It should be understood that, depending on the relative positions of the layers of the multilayer electronic circuit board, the board can have both internal and external circuits. As previously mentioned, additional openings may be formed partially or completely through the substrate to allow electrical interconnection between these layers at selected locations. The resulting structure has a portion of the opening extending completely through the structure, a portion of the opening extending only partially through the structure, and the structure It should be understood that there may be some openings in the body.

Preferably, the thickness of the laminate forming the electronic support 254 is about 0.051
mm (0.002 inch), and more preferably about 0.13 mm (0 mm).
. 005 inches) to about 2.5 mm (about 0.1 inch). For an eight-ply laminate of 7628 style fabric, the thickness is typically about 1.32 mm (0.0
52 inches). The number of layers of fabric 14 in laminate 10 can vary based on the desired thickness of the laminate.

The resin content of the laminate ranges from about 35 to about 80% by weight, more preferably
It can range from about 40 to about 75% by weight. The amount of fabric in this laminate is about 20-
It may range from about 65% by weight, more preferably from about 25 to about 60% by weight.

For a laminate formed from woven E-glass using a FR-4 epoxy resin matrix material, which has a minimum glass transition temperature of about 110 ° C., the cross-machine or width-wise The desired minimum flexural strength (in general, perpendicular to the longitudinal axis of the fabric) is IPC-4101 "Specification fo
r Base Materials for Rigid and Multi
layer Printed Boards, "p. 29, The Inst
itute for Interconnecting and Packag
According to the literature of ing Electronic Circuits (December 1997) greater than 3 × 10 ⁷ kg / m ² , preferably about 3.52 × 10 ⁷ k
g / m ² (about 50 Kpsi), more preferably about 4.9 × 10 ⁷ k
g / m ² (about 70 Kpsi). The contents of IPC-4101 are incorporated herein by reference in their entirety. In its length direction, this length direction (
This is approximately parallel to the longitudinal axis of the fabric).
It is larger than 10 ⁷ kg / m ² , more preferably larger than 4.23 × 10 ⁷ kg / m ² . The flexural strength is measured according to ASTM D-790 and IPC-TM-650.
Test Methods Manual of the Institute
for Interconnecting and Packing E
electronics (December 1994), the contents of which are incorporated herein by reference, and the metal cladding is measured by IPC-
By etching according to the 3.8.2.4 part of 4101, it is completely removed. Advantages of the electronic support of the present invention include high bending strength (tensile strength and compressive strength)
And a high modulus, which can reduce the deformation of the circuit board including the laminate.

The electronic support of the present invention is in the form of a copper-clad FR-4 epoxy laminate, preferably IPC Test Method 2.4.41, the contents of which are incorporated herein by reference. ), The coefficient of thermal expansion in the z-direction ("z" of the laminate (""
Z-CTE "), i.e., at 50C to 288C across the thickness of the laminate. Each such laminate preferably contains eight layers of a 7628 style fabric, but 106, 108, 1080, 2113, 2116 or 7535 style fabrics can be used instead. In addition, the laminate can incorporate combinations of these fabric styles. Laminates having a low coefficient of thermal expansion are generally less susceptible to expansion and contraction and can minimize substrate distortion.

The present invention further relates to at least one composite layer made in accordance with the teachings herein and in a manner different from the composite layers taught herein (eg, conventional glass fiber The fabrication of multilayer laminates and electronic circuit boards comprising at least one composite material layer (made using composite technology) is contemplated. More specifically, as is well known to those skilled in the art, traditionally, the filaments in continuous fiberglass strands used in weaving fabrics are made up of starch / oil sizing (partially or completely dextrin Treated with dextrinized starch or amylose, hydrogenated vegetable oils, cationic wetting agents, emulsifiers and water, including Loewenstein, pp. 237-244 (3rd edition, 1993), the contents of which are incorporated herein by reference. , Incorporated herein by reference)
, But is not limited thereto. The warp yarns made from these strands are then solution prior to weaving (eg, US Pat.
No. 530,876, treated with the poly (vinyl alcohol) disclosed in column 3, line 67 to column 4, line 11, the contents of which are incorporated herein by reference. Protect the strands from abrasion during the weaving process. This operation is commonly called slashing. The poly (vinyl alcohol), as well as the starch / oil size, are generally not compatible with the polymeric matrix materials used by composite manufacturers, and the fabric must be filled with the glass fibers before impregnating the woven fabric. Must be cleaned to remove essentially all organic material from the surface of the substrate. This can be achieved, for example, by rubbing the fabric, and more generally by heat treating the fabric in a manner well known in the art. As a result of this washing operation, there is no suitable interface between the polymer matrix material used to impregnate the fabric and the washed glass fiber surface, so that the glass fiber surface , A coupling agent must be applied. This operation is sometimes called finishing by those skilled in the art. The coupling agents most commonly used in finishing operations include silanes, including E.C.
P. Plueddemann, Silane Coupling Agents
(1982), pages 146-147, the contents of which are incorporated herein by reference, but not limited thereto. See also Lowenstein, pages 249-256 (3rd edition, 1993). After treatment with the silane, the fabric is impregnated with a compatible polymeric matrix material, squeezed between a set of metering rolls, and dried to form the semi-cured prepreg described above. It should be understood that depending on the nature of the sizing, the washing operation and / or matrix resin used in the composite, the slashing and / or finishing steps can be eliminated. One or more prepregs incorporated by conventional glass fiber composite technology may be combined with one or more prepregs incorporated by the present invention in combination with the electronic support described above (
In particular, a multilayer laminate or an electronic circuit board) can be formed. For more information on the fabrication of electronic circuit boards, see 1 Electronic Material.
s Handbook (registered trademark), ASM International (1
989), pp. 113-115, R.A. Tummala (ed.), Microelectronic
s Packing Handbook, (1989), 858-861.
Pages 895-909, M.P. W. Jawitz, Printed
Circuit Board Handbook (1997), 9.1-9.
42, and C.I. F. Coombs, Jr. (Ed.), Printed C
See ircuits Handbook, (3rd edition, 1988), pages 6.1-6.7, the contents of which are incorporated herein by reference.

The composite material and the laminate forming the electronic support of the present invention include, for example, Tumma
la, as disclosed on pages 25-43, the contents of which are incorporated herein by reference.
Second and / or third level packaging).
In addition, the present invention can also be used for other packaging levels.

The present invention will now be described by way of the following specific, non-limiting examples.

Example 1 Electric grade laminates made from prepregs incorporating yarns with different sizing compositions into a fabric were tested to determine their perforation properties (more specifically, (i
) The drill tip wear of the drill used to drill holes through these laminates and (ii) the positional accuracy of the holes drilled through these laminates) were evaluated. Control A and Sample B were laminates incorporating 7628 style fabric, as described above. The fabric in Control A was a hot washed and silane finished fabric, available from Clark Schwebel and identified as 7628-718. The fabric in Sample B was woven from a yarn containing glass fibers coated with a resin compatible sizing taught herein and shown in Table 1. The glass fibers woven in Sample B had a combustion loss of 0.35%.

[0145]

[Table 5] ⁹⁴ RD-847A polyester resin (this is Borden Chemical
ls (commercially available from Columbus, Ohio) ⁹⁵ DESMOPHEN 2000 polyethylene adipate diol, which is
Bayer (commercially available from Pittsburgh, Pennsylvania)) ⁹⁶ PVP K-30 polyvinylpyrrolidone, which is available from ISP Chemica
ls (commercially available from Wayne, New Jersey) ⁹⁷ A-187 γ-glycidoxypropyltrimethoxysilane, which is available from OS
i Specialties, Inc. (Tarrytown, New York
kA) ⁹⁸ A-174 γ-methacryloxypropyltrimethoxysilane, which is
OSi Specialties, Inc. (Tarrytown, New Y
ork) commercially available from) ⁹⁹ PLURONIC (TM) F-108 polyoxypropylene - polyoxyethylene copolymer (which, BASF Corporation (Parsi
¹⁰⁰ VERSAMID 140 polyamide, which is commercially available from General Mills Chemicals, Inc. ¹⁰¹ MACOL NP-6 nonylphenol surfactant, which is commercially available from BASF (New Jersey)
Commercially available from Parsippany, New Jersey) ¹⁰² PolarTherm ^™ PT 160 Boron Nitride Powder Particles
advanced Ceramics Corporation (Lakewood
d, Ohio) ¹⁰³ ORPAC BORON NITRIDE RELEASE COAT-C
ONC (this is ZYP Coatings, Inc. (Oak Ridge)
Hand lay-up procedure (commercially available from Shell Chemical Co.), which uses a paintbrush to apply a standard FR-4 epoxy resin (EPON 1120-A80 resin available from Shell Chemical Co.) to these fabrics. Prepreg was prepared. Immediately "dry" the resin saturated fabric, 17
163 ° C (3 ° C) until the desired gel time of 124 seconds at 1 ° C (340 ° F) is reached.
25 ° F) and placed in a B-stages in a ventilated hot air oven for about 3 to about 3.25 minutes. These prepregs were placed in a 46 cm x 46 cm (1
An 8 inch x 18 inch section was cut and weighed to determine the resin content. In the subsequent lamination procedure, only prepregs having a resin content of 44% ± 2% were used.

The prepregs are stacked at an eight layer height and placed at 177 ° C. (350 ° F.) and 3 ° C.
Wabash at 45 Newtons / cm ² (500 psi) for 70 minutes
Press molding. All of these laminates were molded without a copper foil layer. These laminates exhibited different levels of air intake. It is believed that this condition was attributed to the lack of vacuum assistance during lamination and the temperature gradient.

(Instrument Wear Analysis) To evaluate the wear of the drill tip, a first series of tests was performed. This tip wear is represented by the “drill tip wear rate”, which was calculated using the following equation: Drill tip wear rate = 100 × (P _i −P _f ) / P _i where P _i = width of the primary cutting edge after perforating the initial width P _f = allocated holes of the primary cutting edge. Referring to FIG. 7, the width 470 of the primary cutting edge 472 of the drill 474 was measured at the peripheral edge of the drill tip.

The perforation was performed using a single head drilling machine. This perforation is performed at 0.
203 mm (0.008 inch) thick aluminum inlet and 1.88 mm (0
. (074 inches) thick paper core with phenolic coated backup
Performed on three stacks of laminates (described above). Drilling three laminates at once is generally the standard practice in the industry. The drill tip wear rate was measured for two drill diameters: 0.35 mm (0.013
8 inches) and 0.46 mm (0.018 inches). Both drills are series 508 tungsten carbide drills (Tulon Co., Garden
ia, available from California). The tip load during drilling was constant at 0.001 for each instrument. As used herein, "tip load" refers to the ratio of the drill insertion speed measured in inches per minute to the spindle speed (rpm) measured in revolutions per minute. 0.35m
For a m drill, the spindle speed was 100,000 rpm and the insertion speed was 100 inches (254 cm) per minute. 0.46
mm drill, the spindle speed is 80,000 rpm,
The insertion speed was 80 inches (203 cm) per minute. The retraction speed of 2.54 m (1000 inches) per minute and the upper drill head limit of 1.65 mm (0.065 inches) were kept constant for both instrument diameters. As used herein, "drill head limit" means the distance that the drill tip has been pulled above the top surface of the stack.

The drill tip wear rate was measured using the 500 hole drilling pattern shown in FIG. 8 (a 0.235 inch × 4 inch block of 0.635 cm × 10.16 cm (0.25 inch × 4 inch)).
Section 580), followed by 100 holes (10 × 10 hole pattern).
(Section 582) followed by 391 holes drilled with 9 holes in a 3x3 hole pattern (Section 584). 62 holes per square centimeter (4 per square inch)
(00 holes). This pattern was repeated three more times for a total of 2000 holes. The perforations for tests 1 and 2 were determined by Unilin
e was performed using a 2000 single head drilling machine, and drilling for Test 3 was performed using a CNC-7 single head drilling machine. Both machines are E
sterline Technologies, Bellevue, Washi
available from ngton.

Table 2 shows the drill tip wear rate for Control A and Sample B for 0.35 mm and 0.46 mm diameter drills after drilling 2000 holes in the pattern described above. . Each test started with a new drill bit.

[0151]

[Table 6] As can be seen in Table 2, sample B of Tables 1 and 2 contains glass fiber filaments coated with a sizing as taught herein, which is compatible with the laminate matrix resin. After drilling 2000 holes, has a significantly lower rate of drill tip wear than Control A, which contains glass fiber filaments that must be hot cleaned before coating with a silane containing finish sizing. Indicated. Table 3 shows only a slight improvement in the drill tip wear rate, which is due to the fact that the CNC-7 drilling machine used in this test is older and is not as drilling as the Uniline 2000 drilling machine used in tests 1 and 2. It is thought to be due to the fact that control was lost.

Position Accuracy A common metric used to evaluate the perforation performance of the laminate is the hole accuracy. This test measures the deviation of the distance of the actual hole position from its planned position. The measurements were made on the lower surface of the lower stack of the stack of three stacks where the drill exited the stack. The reason is that this hole position was planned (
That is, it is expected to have the largest difference from the "true") hole location. This difference was assessed by the "deviation distance", that is, the distance from the true true center of the hole drilled on the surface of the laminate to the planned true center of the hole. This deviation distance is obtained after repeating the above-described 500 hole procedure four times, ie, each instrument has a total of 2
Measurements were taken after drilling 000 holes. This deviation distance is the last drilled 100
The individual hole pattern, ie, the section 582 that was last drilled, was measured. These holes are made in a Tulon Co. of the type described above. 0.46 mm (0.01
Drilled using an 8 inch) diameter Series 508 drill. The spindle speed for this drill, as used in this instrument wear test, was 80,000 rpm
ms, and the insertion speed was 80 inches per minute for a tip load of 0.001. This test was repeated eight times for each Control A and Sample B, each test using a new drill Started with.

Table 3 shows the results of the position accuracy test for Control A and Sample B after drilling 2000 holes.

[0154]

[Table 7] As can be seen, sample B exhibited a shorter deviation distance than control A, which is particularly important when using this laminate as an electronic support incorporating a large number of holes and circuits. This is consistent with the drill tip wear rate shown in Table 2 above. More specifically, a laminate exhibiting a low drill tip wear rate is also expected to exhibit a short deviation distance because the drill tip is sharp after multiple drillings.

Example 2 In Example 2, a drill tool wear rate test was further performed. Electrical grade laminate controls C and samples D, E and F incorporating the 7628 style fabric described above were tested for drill tool wear rates. The fabric for Control C was Clark-Schweb.
el, Inc. 7628-718 fabric. Fill yarns containing glass fibers coated with the resin compatible sizing as shown in Table 4 and fabrics in samples D, E and F, and different polymeric matrix material compatible coating compositions Woven from warp having glass fibers coated with article ¹⁰⁴ .

¹⁰⁴ This warp yarn was obtained from PPG Industries, Inc. Is a commercially available glass fiber yarn product of PPG Industries, Inc. G-75 glass fiber yarn coated with 1383 Binder.

[0157]

[Table 8] ¹⁰⁵ PVP K-30 polyvinylpyrrolidone (this is available from ISP Chemical
als (commercially available from Wayne, New Jersey).

¹⁰⁶ STEPANTEX 653 (this is the Stepan Company (
Maywood, NJ) ¹⁰⁷ A-187 γ-glycidoxypropyltrimethoxysilane (which is
Si Specialties, Inc. ¹⁰⁸ A-174 γ-methacryloxypropyltrimethoxysilane (commercially available from OSi Specialties, Inc. (Tarrytown, NY)) ¹⁰⁹ EMERY® 6717 Partially amidated polyethyleneimine (commercially available from Henkel Corporation, Kankakee, Ill.) ¹¹⁰ MACOL OP-10 ethoxylated alkylphenol (which is a BAS
F Corp. (Commercially available from Parsippany, NJ). TMAZ-81 ethylene oxide derivative of ¹¹¹ sorbitol ester, which is commercially available from BASF Corp. (Parsippany, NJ).
.

[0159] ¹¹² MAZU DF-136 defoamer (this is BASF Corporation
on (commercially available from Parsippany, NJ). ¹¹³ SAG 10 antifoam material (this is OSi Specialties, I
nc. (Commercially available from Danbury, Connecticut) ¹¹⁴ ROPAQUE® HP-1055, which is a 1.0 micron particle dispersion and is available from Rohm and Haas Company (Phila).
¹¹⁵ ROPAQUE® OP-96, which is a 0.55 micron particle dispersion and is available from Rohm and Haas Company (Philad).
commercially available from Elphia, PA) ¹¹⁶ ORPAC BORON NITRIDE RELEASE COAT-C
ONC Boron Nitride Dispersion (this is available from ZYP Coatings, Inc. (Oa
k Ridge, TN) ¹¹⁷ PolarTherm® PT 160 boron nitride powder, which is an Advanced Ceramics Corporation (Lakew)
ood, commercially available from OH)) ¹¹⁸ RD-847A polyester resin (which, Borden Chemic
als of Columbus, has been being) ¹¹⁹ DESMOPHEN 2000 polyethylene adipate diol (which is commercially available from Ohio, Bayer of Pittsburgh, available from Pennsylvania) ¹²⁰ PLURONIC ^TM F-108 polyoxypropylene - polyoxyethylene copolymer (which Is the BASF Corporation of Parsi
ppany, commercially available from New Jersey) ¹²¹ ALKAMULS EL-719 polyoxyethylated vegetable oil (R
hone-Poulenc) ¹²² ICONOL NP-6 alkoxylated nonylphenol (BA
SF Corp. of Parsippany, New Jersey).

The fabrics were subsequently coated with an FR-4 epoxy resin having a Tg of about 140 ° C. (Nelco International Corporation)
(Named 4000-2 resin by no of Anaheim, CA)
Was used to form a prepreg. The sizing compositions were not removed from the fabric prior to prepreg formation. By stacking (as shown below) eight layers of this prepreg material and four layers of 1 ounce copper, they are brought to a temperature of about 355 ° F. (about 179 ° C.) and a pressure of about 300 pounds per square inch. (
A laminate was made by laminating at a pressure of about 2.1 megapascals) for about 150 minutes (total cycle time). The thickness of these laminates with copper is
About 0.052 inch (about 0.132 cm) to about 0.065 inch (0.165c
m). In forming these laminates, eight prepregs were stacked with copper layers in the following arrangement: one 1 oz / ft ² brilliant copper layer three prepreg layers one oz / ft ² RTF (Reverse treatment foil) Copper layer 2 prepreg layers 1 oz / ft ² RTF copper layer 3 prepreg layers 1 oz / ft ² brilliant copper layer Finished laminate is 40.6 cm × 50.8 cm ( 16 inches x 20 inches).

This perforation was performed using a Uniline 200 single head drilling machine. This perforation was performed on three stacks of the laminate (described above) using a 0.010 inch (0.254 mm) thick aluminum inlet and a 0.1 inch (2.54 mm) thick aluminum clad particle board backup. In, it was executed. The drill tool wear rate is a 0.380 mm (0.0135 inch) tool diameter series 80 tungsten carbide drill (Tulon Co., Gardenia).
, Available from Co., CA). Tip load during drilling is 95,
It was constant at 0.001 with a spindle speed of 000 rpm and an insertion speed of 95 inches (241 cm) per minute. The drill retraction speed is 90 inches (2.29 m) per minute, and the upper drill head limit is 0.05
The upper drill head limit was 9 inches (1.5 mm).

The drill tip wear rate was tested based on 1500 and 2500 hole drilling patterns. The holes in each section were drilled at a hole density of 28 holes per square centimeter (about 178 holes per square inch).

Table 5 shows the percentage of drill tip wear for Control C and Samples D, E and F after drilling 1500 and 2500 holes. Each set of holes was started with a new drill bit, and each stack of stacks had 10 1500 hole populations and 10 2500 hole populations. Three stacks of each fabric type laminate were perforated so that the drill tip wear rate for 30 drillings was measured for each sample.

[0164]

[Table 9] As can be seen in Table 5, samples D, E and F containing glass fiber filaments coated with a sizing as taught herein, which is compatible with the laminate matrix resin After drilling 1500 holes showed a significantly lower wear rate than Control A, which contains glass fiber filaments that must be hot washed before coating with a silane containing finish sizing. . After drilling 2500 holes, the amount of drill tool wear rate for samples D, E and F is still lower than control C, but not so significant. this is,
As expected, most of this instrument wear occurs in holes drilled earlier rather than the last hole drilled in a group.

Based on the foregoing, but not limited by the present invention, prepregs made of fiberglass fabric coated with a polymer matrix compatible sizing as taught herein are 400 prepregs per square inch. Hole density and 0.46m
2,000 holes through a stack of three stacks (each stack contains eight prepregs) at a chip load of 0.001 using a tungsten carbide drill with a diameter of 0.018 inches (m). About 32% or less, as determined after drilling
More preferably, it has a drill tip wear rate of about 30% or less, most preferably about 25% or less.

In addition, based on the foregoing, but not limited by the present invention, a prepreg made of fiberglass fabric coated with a polymer matrix compatible sizing as taught herein, may be 1 square inch. At a hole density of 400 holes per inch and a chip load of 0.001 using a tungsten carbide drill of 0.46 mm (0.018 inch) diameter, three stacks (each stack has eight prepregs) About 36 micrometers or less, more preferably about 33 micrometers or less, as determined after drilling 2000 holes through the stack of
Most preferably, it has a deviation distance of about 31 micrometers or less.

Without being bound by any particular theory, the presence of a solid lubricant in the glass fiber coating composition disclosed herein (in one particular embodiment, the presence of the boron nitride ) Is believed to contribute to the improved perforation properties of the laminates of the present invention. More specifically, the solid lubricant contributes to reduced drill wear and improved positional accuracy of the drilled holes.

The improved perforation properties in laminates made from glass fibers coated with a resin compatible sizing as taught herein provide several advantages. First, long drill life means that each drill bit can drill more holes before being sharpened or discarded. In addition, the positional accuracy of the holes drilled through the laminate of the present invention is greater than the positional accuracy of the conventional laminate, so that the accuracy achieved by stacking three laminates of the conventional laminate is the same as that of the conventional laminate. It is expected that more than three laminates can be stacked for perforation at the same time with the same accuracy. Both of these advantages result in a more cost effective drilling operation. Furthermore, the positional accuracy of the holes drilled in these laminates is improved so that the quality of the electronic support incorporating the laminate is improved.

Those skilled in the art will appreciate that modifications can be made to the embodiments described above without departing from the broader inventive concept. Therefore, it is to be understood that this invention is not limited to the particular embodiments disclosed, but is intended to include modifications within the spirit and scope of the invention as defined by the appended claims. You.

[Brief description of the drawings]

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

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

FIG. 2 is a plan view of one embodiment of a fabric incorporating features of 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 alternative embodiment of a reinforced laminate according to the present invention.

FIG. 5 is a sectional view of an electronic support according to the present invention.

FIG. 6 is a schematic diagram of a method of forming an opening in a fabric layer of an electronic support.

FIG. 7 is an end view of a drill illustrating a primary cutting edge.

FIG. 8 is a schematic diagram of a drill hole pattern.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08L 101: 00 D06M 15/507 Z D06M 101: 00 11/00 Z (31) Priority number 60 / 133,075 (32) Priority date May 7, 1999 (5.7.1999) (33) Country of priority claim United States (US) (31) Priority claim number 60 / 146,337 (32) Priority Date July 30, 1999 (July 30, 1999) (33) Priority 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, TZ, 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, US, UZ, VN, YU, ZW (72) Robertson, Walter Jay. United States Pennsylvania 15202, Pittsburgh, Shannopin Drive 28 (72) Inventor Verpari, Vedaziri United States of America Pennsylvania 15146, Monroeville, Old Himaker Road 230 (72) Inventor Ramon-Khillinski, Cami United States of America Pennsylvania 15212, Pittsburgh, Monterey Street 1218 (72) Inventors Lawton, Ernest L. United States North Carolina 27012, Clemmons, Kill Cache Drive 3432 F-term (reference) 4F072 AB09 AB28 AC08 AD04 AD08 AD13 AD23 AD37 AD41 AD42 AD43 AD44 AD45 AD46 AE11 AG03 AG12 AG16 AJ04 4L031 AA26 AB32 AB34 BA21 BA33 4L033 AA11 AC05 AB13 AC CA45 4L048 AA03 AA48 AA49 AA53 AB07 AC09 AC10 AC14 CA01 CA02 CA06 DA41

Claims (56)

[Claims] 1. A prepreg for an electronic support, wherein the prepreg comprises: (a) a polymeric matrix material; and (b) a fabric comprising a strand comprising glass fibers, at least a portion of the fabric. Has a coating that is compatible with the polymeric matrix material and the prepreg
. Using a tungsten carbide drill 46 mm (0.018 inch) in diameter,
With a hole density of 62 holes per square centimeter (400 holes per square inch) and a chip load of 0.001, 20 through a stack of three laminates
A fabric having a drill tip wear rate of less than or equal to about 32% as measured after drilling 00 holes, wherein each laminate comprises eight of the prepregs. 2. The drill tip wear rate is less than about 30%.
The prepreg according to the above. 3. The drill tip wear rate is less than about 25%.
The prepreg according to the above. 4. The thermoset matrix wherein the polymeric matrix material is selected from the group consisting of thermoset polyesters, vinyl esters, epoxides, phenols, aminoplasts, thermoset polyurethanes and mixtures thereof. The prepreg according to claim 1, comprising a material. 5. The method according to claim 1, wherein the polymer matrix material is polyolefin, polyamide, thermoplastic polyurethane, thermoplastic polyester, vinyl polymer, polyimide, polyether sulfone, polyphenyl sulfone, polyether ketone, polyphenylene oxide, polyphenylene sulfide, polyacetal, The prepreg according to claim 4, comprising at least one thermoplastic matrix material selected from the group consisting of polycarbonate and mixtures thereof. 6. The method of claim 1, wherein at least one of the glass fibers is selected from the group consisting of E glass fibers, D glass fibers, S glass fibers, Q glass fibers, E glass derivative fibers, and combinations thereof. Prepreg. 7. The prepreg according to claim 1, wherein the coating comprises solid lubricant particles. 8. The solid lubricant particles comprising graphite, boron nitride, metal dichalcogenide, cadmium iodide, silver sulfide, indium, thallium, tin, copper,
From the group consisting of zinc, gold, silver, calcium carbonate, calcium fluoride, zinc oxide, molybdenum disulfide, molybdenum diselenide, tantalum disulfide, tantalum diselenide, tungsten disulfide, tungsten diselenide and mixtures thereof The prepreg of claim 7, comprising at least one non-hydratable inorganic solid lubricant particle selected. 9. The prepreg according to claim 8, wherein the non-hydratable inorganic solid lubricant particles include boron nitride particles having a hexagonal structure. 10. The prepreg according to claim 7, wherein the hardness value of the solid lubricant particles is equal to or less than the hardness value of the E glass fiber. 11. The laminate comprises eight layers of a woven style selected from the group consisting of style 106, style 108, style 1080, style 2113, style 2116, style 7535 and style 7628 and combinations thereof. The prepreg according to claim 1. 12. The coating as claimed in claim 12, wherein the coating comprises (1) a polyester; (2) at least one polymer selected from the group consisting of vinylpyrrolidone polymers, vinyl alcohol polymers and starch; and boron nitride particles. 2. The prepreg according to 1. 13. The coating comprises a plurality of dispersed dimensionally stable particles formed from a material selected from the group consisting of organic materials, polymeric materials, composite materials, and mixtures thereof, wherein the particles comprise: The prepreg of claim 1, wherein the prepreg provides an interstitial space between at least one fiber and at least one adjacent fiber, wherein the particles have an average particle size of about 0.1 to about 5 micrometers. 14. The method of claim 1, wherein at least one of the particles comprises a polymer material selected from the group consisting of an inorganic polymer material, a synthetic organic polymer material, a semi-synthetic organic polymer material, and a natural organic polymer material. 14. The prepreg according to 13. 15. The at least one particle comprises a thermoplastic organic polymeric material selected from the group consisting of acrylic polymers, vinyl polymers, thermoplastic polyesters, polyolefins, polyamides, thermoplastic polyurethanes and mixtures thereof. The prepreg according to claim 14. 16. The prepreg according to claim 15, wherein the at least one particle is formed from an acrylic copolymer that is a copolymer of styrene and acrylic. 17. The method of claim 17, wherein the particles are first particles, and the resin-compatible coating composition further comprises a plurality of additional dispersed, dimensionally stable particles different from the first particles. 17. The prepreg of claim 16, wherein the particles are selected from the group consisting of metals, graphite, oxides, carbides, nitrides, borides, sulfides, silicates and carbonates. 18. The method of claim 13, wherein the coating comprises a lubricant selected from the group consisting of cetyl palmitate, cetyl laurate, octadecyl laurate, octadecyl myristate, octadecyl palmitate, octadecyl stearate and paraffin. The prepreg described. 19. The prepreg of claim 13, wherein said particles comprise boron nitride particles and hollow particles formed from a copolymer of styrene and acrylic. 20. The prepreg of claim 1, wherein at least one of the glass fibers is at least partially coated with the coating. 21. The prepreg according to claim 1, wherein the fabric is selected from the group consisting of a woven fabric, a nonwoven fabric, a knit and a mat. 22. The prepreg has a hole density of 62 holes per square centimeter (400 holes per square inch) and a 0.48 mm (0.018 inch) diameter tungsten carbide drill. With a chip load of 001, measured after drilling 2000 holes through a stack of three stacks, having a deviation distance of about 36 micrometers or less, each of the stacks includes eight of the prepregs The prepreg according to claim 1. 23. The prepreg of claim 1, wherein at least a portion of the fabric comprises twisted glass fiber yarn. 24. The prepreg of claim 1, wherein at least a portion of the fabric comprises untwisted glass fibers. 25. The prepreg according to claim 1, wherein the at least one glass fiber is manufactured using a direct molten glass fiber forming method. 26. The prepreg of claim 1, wherein the at least one glass fiber is manufactured using a marble molten glass fiber forming method. 27. The prepreg according to claim 1, wherein said fabric is a non-woven fabric. 28. The prepreg according to claim 1, wherein the fabric is a woven fabric. 29. The prepreg according to claim 28, wherein the fabric is woven on an air jet loom. 30. The prepreg of claim 29, wherein the at least one glass fiber is manufactured using a direct melt glass fiber forming method, and wherein at least a portion of the fabric comprises twisted glass fiber yarn. 31. The prepreg of claim 28, wherein the fabric is woven on a rapier loom. 32. The prepreg of claim 31, wherein the at least one glass fiber is made using a direct melt glass fiber forming method, and wherein at least a portion of the fabric comprises twisted glass fiber yarn. 33. The prepreg of claim 31, wherein the at least one glass fiber is made using a marble molten glass fiber forming method, and wherein at least a portion of the fabric comprises untwisted glass fibers. 34. A laminate incorporating the prepreg according to claim 1. 35. A prepreg for an electronic support, the prepreg comprising: (a) a polymeric matrix material; and (b) a reinforced woven fabric comprising glass fibers, at least a portion of the woven fabric. Has a coating that is compatible with the polymer matrix material and the prepreg is 0.46 mm (
Using a 0.018 inch diameter tungsten carbide drill, the hole density of 62 holes per square centimeter (400 holes per square inch) and 0.0
A reinforced woven fabric having a deviation distance of no more than about 36 micrometers when measured after drilling 2000 holes through a stack of three laminates at a chip load of 01. 36. The prepreg of claim 35, wherein said deviation distance is no greater than about 33 micrometers. 37. The prepreg of claim 36, wherein said deviation distance is no greater than about 31 micrometers. 38. The polymer matrix material is a thermosetting polyester,
36. The prepreg of claim 35, comprising at least one thermoset matrix material selected from the group consisting of vinyl esters, epoxides, phenols, aminoplasts, thermoset polyurethanes, and mixtures thereof. 39. The polymer matrix material is polyolefin, polyamide, thermoplastic polyurethane, thermoplastic polyester, vinyl polymer, polyimide, polyether sulfone, polyphenyl sulfone, polyether ketone, polyphenylene oxide, polyphenylene sulfide, polyacetal, 39. The prepreg of claim 38, comprising at least one thermoplastic matrix material selected from the group consisting of polycarbonate and mixtures thereof. 40. The method of claim 35, wherein at least one of said glass fibers is selected from the group consisting of E glass fibers, D glass fibers, S glass fibers, Q glass fibers, E glass derivative fibers, and combinations thereof. Prepreg. 41. The prepreg of claim 35, wherein said coating comprises solid lubricant particles. 42. The solid lubricant particles may be made of graphite, boron nitride, metal dichalcogenide, cadmium iodide, silver sulfide, indium, thallium, tin, copper, zinc, gold, silver, calcium carbonate, calcium fluoride, oxide At least one non-hydratable inorganic solid lubricant selected from the group consisting of zinc, molybdenum disulfide, molybdenum diselenide, tantalum disulfide, tantalum diselenide, tungsten disulphide, tungsten diselenide and mixtures thereof 42. The prepreg of claim 41 comprising agent particles. 43. The prepreg according to claim 42, wherein the non-hydratable inorganic solid lubricant particles include boron nitride particles having a hexagonal structure. 44. The prepreg according to claim 41, wherein the hardness value of the solid lubricant particles is equal to or less than the hardness value of the E glass fiber. 45. The laminate comprises eight layers of a woven style selected from the group consisting of style 106, style 108, style 1080, style 2113, style 2116, style 7535 and style 7628 and combinations thereof. The prepreg according to claim 35. 46. The coating according to claim 46, wherein the coating comprises: (1) a polyester; (2) at least one polymer selected from the group consisting of vinylpyrrolidone polymers, vinyl alcohol polymers and starch; and boron nitride particles. 35. The prepreg according to 35. 47. The coating comprises a plurality of dispersed dimensionally stable particles formed from a material selected from the group consisting of organic materials, polymeric materials, composite materials, and mixtures thereof, wherein the particles comprise: 36. The prepreg of claim 35, which provides an interstitial space between at least one fiber and at least one adjacent fiber, wherein the particles have an average particle size of about 0.1 to about 5 micrometers. 48. At least one of said particles comprises a polymeric material selected from the group consisting of inorganic polymeric materials, synthetic organic polymeric materials, semi-synthetic organic polymeric materials and natural organic polymeric materials. 47. The prepreg according to 47. 49. The at least one particle comprises a thermoplastic organic polymeric material selected from the group consisting of acrylic polymers, vinyl polymers, thermoplastic polyesters, polyolefins, polyamides, thermoplastic polyurethanes, and mixtures thereof. The prepreg according to claim 48. 50. The prepreg of claim 49, wherein said at least one particle is formed from an acrylic copolymer that is a copolymer of styrene and acrylic. 51. The particle is a first particle, and the resin-compatible coating composition further comprises a plurality of additional dispersed dimensionally stable particles different from the first particle; 51. The prepreg of claim 50, wherein the particles are selected from the group consisting of metals, graphite, oxides, carbides, nitrides, borides, sulfides, silicates, and carbonates. 52. The method of claim 47, wherein the coating comprises a lubricant selected from the group consisting of cetyl palmitate, cetyl laurate, octadecyl laurate, octadecyl myristate, octadecyl palmitate, octadecyl stearate, and paraffin. The prepreg described. 53. The prepreg of claim 47, wherein said particles comprise boron nitride particles and hollow particles formed from a copolymer of styrene and acrylic. 54. The prepreg of claim 35, wherein at least one of the glass fibers is at least partially coated with the coating. 55. The prepreg of claim 35, wherein the fabric is selected from the group consisting of a woven, a nonwoven, a knit, and a mat. 56. A laminate incorporating the prepreg according to claim 35.