CN101117275B - Glass fiber-reinforced prepregs, laminates, electronic circuit boards and methods for assembling a fabric - Google Patents

Abstract

The present invention provides an at least partially coated fiber strand comprising a plurality of glass fibers having a coating composition on at least a portion of at least one of the glass fibers, the coating composition comprising at least one coating comprising greater than 20 weight percent on a total solids basis of a plurality of particles selected from inorganic particles, organic hollow particles, composite particles, and mixtures of any of the foregoing, wherein the plurality of particles have a Mohs' hardness value which does not exceed the Mohs' hardness value of the glass fibers.

Description

The method of glass fiber-reinforced prepreg, laminate, circuit card and assembling fabric

The application is the dividing an application that be on October 8th, 1999, denomination of invention the applying date for the one Chinese patent application No.99813148.2 of " method of glass fiber-reinforced prepreg, laminate, circuit card and assembling fabric ".

The cross reference of related application

Present patent application is people's such as Novich US number of patent application 09/170,578, the part continuation application of denomination of invention " method of glass fiber-reinforced laminate, circuit card and assembling fabric " (1998.10.13 application); This application is the partial continuous application of resigned at present US number of patent application 09/130,270, denomination of invention " method of glass fiber-reinforced laminate, circuit card and assembling fabric " (1998.8.6 application, B.Novich etc.); It is the part continuation application of US number of patent application 09/034,525, denomination of invention " the glass fiber yarn thigh of inorganic lubricant coating and the product that comprises it " (1998.3.3 application, B.Novich etc. abandon at present).The application still is the part continuation application of US number of patent application 09/170,780, denomination of invention " the glass fiber yarn thigh of inorganic lubricant coating and the product that comprises it " (1998.10.13 application, B.Novich etc.); It is the part continuation application of US number of patent application 09/034,525, denomination of invention " the glass fiber yarn thigh of inorganic lubricant coating and the product that comprises it " (1998.3.3 application, B.Novich etc. abandon at present).The application still is the part continuation application of US number of patent application 09/170,781, denomination of invention " with the glass fiber yarn thigh of heat conductance inorganic solid particles coating and the product that comprises it " (1998.10.13 application, B.Novich etc.); It is the partial continuous application of US number of patent application 09/034,663 (the 1998.3.3 application is abandoned at present).

Present patent application and US number of patent application 09/170,579, denomination of invention " the inhibition methods of glass fiber yarn thigh wearing and tearing " (B.Novich etc., this application is the part continuation application of resigned at present US application number 09/034,078 (1998.3.3 application)); US number of patent application 09/170,566, denomination of invention " the glass fiber yarn thigh of dipping and the product that comprises it " (B.Novich etc., this application is the part continuation application of US application number 09/034,077 (the 1998.3.3 application is abandoned now)); And US number of patent application 09/170; 565, denomination of invention " the glass fiber yarn thigh of inorganic particle coating and the product that comprises it " (B.Novich etc.; This application is the part continuation application of US application number 09/034,056 (the 1998.3.3 application is abandoned at present)) relevant.

The application requires the right of number 60/133,075 (the 1999.5.7 application) of US provisional application, 60/133,076 (1999.5.7 application) and 60/146,337 (1999.7.30 application).

Invention field

Present invention relates in general to be used for the strengthening course casting die of circuit card; Say more specifically to relate to the laminate that contains fiberglass weaving cloth that wherein said spun glass contains compatible with the laminate matrix resin and the coating of improved boring property is provided in laminate.

Background of invention

Circuit card generally is that the laminate layers by the resin impregnation fabric forms, and said fabric is made up of reinforcement property fiber such as spun glass, and it provides dimensional stability to circuit card, to keep the globality of the superincumbent circuit of sealing.Being positioned at different layers casting die planar circuit through on the layer of laminate or carrier, holing, making interconnects.According to observations, the heat that is produced during the hardness of the spun glass in the laminate and the drilling operation can quicken the wearing and tearing of drill bit.As a result, how many holes drill bit will not bore, just need change and bore and/or the apex point of refacing, and total time limit of service of instrument be shorter.In addition, according to finding that drill bit accelerated wear test also influences the tolerance range of hole site, particularly bored the exit end in the hole of laminate.

In general, in the fiber forming process, to give the surface coated Hairstyling composition of the spun glass of form layers casting die reinforcement property fabric, so that the protection fiber does not receive the friction in the course of processing subsequently.For example, use the Hairstyling composition of starch and oil base material to protect fiber, and this friction can cause fibre breakage in the friction that does not receive during the weaving textile between silk with equipment.Having added the substituted polymine of organic lubricant such as alkyl imidazoline derivatives and acid amides in the Hairstyling composition reduces friction.Yet this organic lubricant can be rotten in the course of processing subsequently, perhaps causes the side reaction of not expecting with other typing component and substrate material component.In addition, a lot of commonly used typing components can influence the binding property between spun glass and the laminate substrate material unfriendly, starch for example, and it is commonly used in the weaving setting agent makes membrane-forming agent, incompatible usually with the laminate resin matrix material.For avoiding incompatible between spun glass and the substrate material, generally will be before lamination component (thermal treatment or de-oiling) or water or other solution washing through the thermolysis setting agent remove coating or Hairstyling composition on the woven cloths.Conventional thermal cleaning processing comprises heats cloth 60-80 hour down at 380 ℃.Then, be coated with cloth again, so that improve the binding property between spun glass and the matrix resin through cleaning with silane coupling agent.

The intensity of thermal cleaning processing can the reduction greatly spun glass, the bending strength of the laminate of more specifically saying so.Concerning the spun glass such as D-glass, S-glass and Q-glass of high silicon dioxide content, thermal cleaning is not extremely expected, because can cause loss of strength and decolouring.

Disclose the coating composition that a lot of spun glass are used in the prior art, it needed thermal treatment or water cleaning before the supporting material as composite members or laminate.JP patented claim 9-208; 268 disclose a kind of cloth with yarn of being processed by spun glass, and wherein said spun glass is coated with inorganic solid particles such as colloid silica, lime carbonate, kaolin and the talcum of starch or synthetic resins and 0.001-20.0wt% after spinning immediately.Before the form layers casting die, need carry out heat or water de-oiling.

US patent 5,286,562 discloses a kind of fabric yarn thigh that is used to screen product, and it on the air spray loom is can be woven, and this fabric yarn thigh has the coating of 45wt% wax, lubricant, PVP K120 and organo silane coupling agent at least.US patent 5; 038; 555 disclose the spun glass sth. made by twisting system bundle that is used to screen product, are coated with the moisture chemical treatment composite that contains epoxy membrane-forming agent, emulsifying agent, lubricant, organic functional metal coupling agent, PVP K120, Vilaterm and water on it.

For avoiding the thermal cleaning of glasscloth, JP patented claim 8-119,682 disclose a kind of bottom setting agent that is used for spun glass, and wherein containing water-soluble epoxy resin and pH is 5.5-7.5, and it helps water to remove setting agent.Equally; US patent 5; 236; 777 disclose the working method of the woven fiber glass that a kind of reinforced resin uses, through with the bottom setting agent coated glass yarn that contains at least a water-soluble film forming agent, silane coupling agent and lubricant, said membrane-forming agent be selected from the amine modification epoxy resin, add the epoxy resin of oxyethane and add the dihydroxyphenyl propane of oxyethane; The water washing yarn is lower than 0.25wt%LOI and handles with second kind of setting agent so that the amount of bottom setting agent is reduced to.JP patented claim 9-268,034 discloses the tackiness agent that is used for not twisting glass fiber yarn, wherein contains the aqurous ployurethane compound and/or passes through by the polyvalent alcohol addition reaction soluble epoxide product of modification.

US patent 4,933,381 discloses a kind of resin compatible Hairstyling composition that is used for spun glass, contains epoxy membrane-forming agent, non-ionic lubricant, cationic lubricant, silane coupling agent and such as the acid of acetate or Hydrocerol A.

JP patented claim 8-325,950 disclose a kind of spun glass setting agent, contain PVP K120, water-soluble epoxy resin amine addition product and silane coupling agent as basal component, and it need be from heat extraction on the finished glass cloth.

JP patented claim 7-102,483 disclose the secondary setting agent of warp thread that a kind of spun glass is used, and said spun glass is used for nonwoven glass cloth, and this cloth does not need hot oil removing.The additive such as high molecular weight polyethylene oxide etc. is mainly formed and contained to the secondary setting agent of said warp thread by PVP K120.Can comprise water-soluble epoxy resin as adhesive component.

Boring property and be used to compatible with matrix material of during processing, estimating to never degenerate, can improve the laminate of admixture spun glass prevent that the inert lubricant of spun glass friction from making us expecting.Yet the use of inorganic materials mainly concentrates on the filler that is used to improve mixture General Physics character, rather than improves the wear resistance of reinforcing fiber.

US patent 4; 869,954 disclose a kind of sheet thermal conducting material that is formed by polyurethane tackiness agent, solidifying agent and heat conductance filler such as aluminum oxide, aluminium nitride AlN, SP 1, Natural manganese dioxide and zinc oxide and various metal (referring to the 2nd hurdle 62-65 capable and the 4th hurdle 3-10 is capable).Can comprise one or more layers solid support material in this thermal conducting material, like glasscloth.

US patent 3; 312; 569 disclose a kind of aluminum oxide bonding particle that is used for fiberglass surfacing, and foregoing JP patented claim 9-208, and 268 disclose a kind of cloth with yarn of being processed by spun glass; Wherein said spun glass is coated with starch or synthetic resins with such as the inorganic solid particles of colloid silica, lime carbonate, kaolin and talcum etc. after spinning immediately, so that the resin penetration between resin and the glass reinforcing fiber during improving complex body and forming.Yet, the Mohs ' hardness value of aluminum oxide and silicon-dioxide respectively greater than about 9 with about 7 (referring to R.Weast (volume) Chemistry and physics handbook, (volumes) such as CRC press (1975) F-22 pages or leaves and H.Katz Filler and plastics handbook(1987) the 28th pages, introduce here as a reference), this value can cause the wearing and tearing than the soft glass fiber.

US patent 5; 541; 238 disclose a kind of fiber that is used for reinforcement thermoplasticity or thermoset complex body; Through steam deposition or plasma process coating one deck super-fine material layer, said material for example is inorganic oxide, nitride, carbide, boride, metal and the combination thereof of average particulate diameter 0.005-1 micron with it.Limited space and environment reason make to produce at spun glass uses steam deposition or plasma process unrealistic in mouthful die sleeve.

SU859400 discloses a kind of dip composition that is used to make the glasscloth laminate, and said composition contains alcoholic solution, graphite, molybdenumdisulphide, Vilaterm butyraldehyde and the tensio-active agent of phenol-formaldehyde resin.In the production of spun glass, the volatile alcohol solvent is not expected.

US patent 5,217,778 discloses a kind of dried clutch face glue, and it contains glass fiber yarn, metal wire and polyacrylonitrile fibre complex body, and it is with heat-setting tackiness agent or adhesive composition dipping and coating.Can contain friction particles in the tackiness agent; Like carbon black, graphite, MOX, permanent white, pure aluminium silicate, rubber powder particle, powdery organic resin, polymerization cashew nut oil, clay, silicon-dioxide, sodium aluminum fluoride (capable), to improve the frictional behaviour of complex body referring to the 2nd hurdle 55-66.

Need a kind of lubricant coating that is used for spun glass, it can be compatible with various matrix material, reduces the wearing and tearing of drill bit and the particularity of improvement bore position.In addition, if this coating is also compatible with modern air spray fabric manufacture equipment to increase throughput, then be particularly advantageous.

Summary of the invention

One aspect of the present invention is a kind of prepreg that is used for charge carrier, and this prepreg comprises (a) matrix material; (b) fabric; This fabric contains the yarn that comprises spun glass; At least a portion of fabric has the coating compatible with matrix material; It is about 32% that the drill bit percentage wear rate of this prepreg is not more than, and drill bit percentage wear rate is on the heap layer of 3 laminate, to bore mensuration after 2000 holes with the carbide bur of 0.46mm (0.018 inch) diameter with the cutting load of the hole density of 62 hole/square centimeters (400 hole/square inch) and 0.001, comprises 8 prepregs in each laminate.The present invention also provides the laminate that is mixed with this prepreg.

The present invention is a kind of prepreg that is used for charge carrier on the other hand, and this prepreg comprises (a) matrix material; (b) braiding reinforced textile; This fabric comprises spun glass; At least a portion of fabric has the coating compatible with matrix material; The offset distance of this prepreg is not more than about 36 microns, and offset distance is on the heap layer of 3 laminate, to bore mensuration after 2000 holes with the carbide bur of 0.46mm (0.018 inch) diameter with the cutting load of the hole density of 62 hole/square centimeters (400 hole/square inch) and 0.001.The present invention also provides the laminate that is mixed with this prepreg.

Brief description

When combining with accompanying drawing to read, the general introduction of front and following detailed description of the preferred embodiments will be more readily understood.In the accompanying drawing:

Fig. 1 is the sectional view of strengthening course casting die of the present invention.

Fig. 2 is the top view of an embodiment with fabric of characteristic of the present invention.

Fig. 3 is the skeleton view of coated fiber yarn thigh of the present invention.

Fig. 4 is the sectional view of another embodiment of strengthening course casting die of the present invention

Fig. 5 is the sectional view of charge carrier of the present invention.

Fig. 6 is the synoptic diagram that in the tissue layer of charge carrier, forms the method in hole.

Fig. 7 is the end view that bores, and main cutting edge is described.

Fig. 8 is the pattern synoptic diagram of boring.

Detailed Description Of The Invention

Laminate of the present invention is by the fabric reinforcement, and said fabric contains coated fibres yarn thigh, and preferably contains the Woven fabric of the glass fiber yarn thigh of coating, and it can provide low thermal expansivity for laminate; Good flexural strength; Thermostability; Stability to hydrolysis; Low-corrosiveness in the presence of high humidity, reactive bronsted lowry acids and bases bronsted lowry and reactive behavior.The glass fiber yarn thigh of this coating is compatible with various matrix material, thereby need be with glasscloth heating or water cleaning before lamination.

Another remarkable advantage of laminate of the present invention is that they show improved boring property, promptly reduces the particularity of bit wear and/or improvement bore position, particularly when laminate is used as charge carrier.Here the structure that said " charge carrier " is meant mechanical support and/or element is electrically connected each other; Said element comprises the hardware that (but being not limited thereto) reactive electro assembly, passive electrical component, printed wiring, unicircuit, semiconductor device and other and these element link, like (but being not limited thereto) junctor, socket, retention clip and scatterer.

Another remarkable advantage of laminate of the present invention is that they can be made by the silvalin thigh that is adapted at using in the air spray weaving process.Here said " air spray is weaved " is meant a type of fabric knitting, wherein through the pressurized air stream from one or more air nozzles yarn (weft yarn) is inserted in the shed open of warp thread.

Referring now to accompanying drawing,, identical numerical markings refers to components identical in the wherein whole accompanying drawing, and Fig. 1 has shown laminate 10 of the present invention.Laminate 10 includes matrix material 12 (below go through), and it is by reinforced textile 14 reinforcement.Fabric 14 can be through any suitable braiding, weave or fill up weaving or supatex fabric that production technique forms, for example (but being not limited thereto) braided fabric or pad.Preferably, fabric 14 is Woven fabrics that known by one of skill in the art air spray weaving process forms.Laminate 10 can also be the unidirectional ply casting die, and the most of fiber in wherein every tissue layer, yarn or yarn thigh are all got same direction.

In general, comprise a plurality of prepregs in the laminate, be mixed with fabric 14 and partly solidified polymeric matrix 12 in each prepreg, will more describe in detail below.The quantity of prepreg can be 1-about 40 in the laminate.For clarity sake, only demonstrate a prepreg in the laminate 10 among the figure.

See Fig. 2 and 3 now, fabric 14 contains one or more coated fibres yarn thighs 16.Here said term " yarn thigh " is meant one or more one fiber.Term " fiber " is meant an individual thread.

But spun glass 18 can be processed by the fibrosis glass composition of any kind well known by persons skilled in the art, comprise by such as " E-glass ", " A-glass ", " C-glass ", " D-glass ", " Q-glass ", " R-glass ", " S-glass " but process with the fibrosis glass composition of E-glass verivate etc.Here said term " but fibrosis " is meant the material that can be processed to successive silk, fiber, yarn thigh or yarn.Here said " E-glass verivate " be meant the glass composition that comprises small amount of fluorine and/or boron, and preferably not fluorine-containing and/or boracic not.In addition, said here being meant on a small quantity less than about 1wt% fluorine with less than about 5wt% bromine.Irish touchstone and mineral wool fibres be other can be used for of the present invention can Fibrotic glass material instance.Preferred spun glass is the spun glass of being processed by E-glass or E-glass verivate.This compsn is to well known to a person skilled in the art and believe to need not further discussion in the present invention.Spun glass of the present invention can form according to any suitable spun glass formation method known in the art.For example, can form operation or form spun glass with direct melt fiber with indirect or crucible melt fiber formation operation.In directly melt fiber formation is operated, unprocessed raw material is merged fusion and homogenize at glass-melting furnace.Let fused glass from smelting furnace, move to fore hearth and get into fiber form in the device, therein fused glass is pulled into the successive spun glass.Form in the operation at crucible melt glass, be pre-formed and have glass blank or the ball that final required glass is formed, and send in mouthful die sleeve, therein with their fusions and pull into the successive spun glass.If the use premelter is then at first sent glass sphere into premelter, fusion is sent fused glass into fiber then and is formed device, therein glass is pulled into the successive fiber.Among the present invention, preferably form operation and form spun glass through direct melt fiber.The visible K.Loewenstein of the Additional Information of relevant glass composition and spun glass formation method The spun glass manufacturing technology(the 3rd edition, 1993) 30-44,47-60,115-122 and 126-135 page or leaf, US patent 4; 542; 106 and 5,789,329 and IPC-EG-140 " by the woven finished product fabric of the E glass standard that is used for printed substrate " page 1; Switching and assembling circuit institute publish (1997.6), and it is introduced here as a reference.

Spun glass can have the about 35.0 microns nominal filament diameter of about 3.0-(be equivalent to name and be called B to U and above silk), and preferably has the about 30.0 microns nominal filament diameter of about 5.0-.Fine yarn is used, and the average nominal filament diameter is preferably about 7 microns of about 5-.The quantity of fiber can be about 15,000 for about 2-in every yarn thigh, preferably about 100-about 7000.About the further information of nominal filament diameter and the name of spun glass, referring to LoewensteinThe the 25th and 27 page, it is introduced here as a reference.

Except that spun glass, coated fibres yarn thigh 16 can also comprise by other can Fibrotic inorganic materials, can Fibrotic organic materials and composition thereof and the fiber 20 that is combined to form.Inorganic and organic materials can be synthetical or naturally occurring material.It will be appreciated by those skilled in the art that can be Fibrotic inorganic and organic materials can also be polymeric materialss.Here said term " polymeric materials " is meant the material that the macromole be made up of the atom long-chain forms, and wherein said macromole links together and can become at solution and tangles or be solid state (James Mark etc. Inorganic polymer, " tyro palace polymer science and engineering series " (1992) page 1, it is introduced here as a reference).

But the non-limiting example of suitable non-glass fibrosis inorganic materials comprises stupalith, for example silit, carbon, graphite, mullite, aluminum oxide and piezoceramic material.But the non-limiting example of suitable fibrosis organic materials comprises cotton, Mierocrystalline cellulose, tree elastomer, flax, ramie, hemp, sisal and wool.But the unrestricted instance of suitable fibrosis organic polymer material comprises the material that is formed by polyamide-based (like nylon and aromatic poly), thermoplastic polyester class (like polyethyleneterephthalate and polybutylene terephthalate), acrylic acid or the like (like polyacrylonitrile), polyolefins, polyurethanes and vinyl polymer class (like polyvinyl alcohol).But can be used for being processed in of non-glass fibrosis material of the present invention and preparation method thereof and these fibers Polymer science and technology encyclopediaIn the 6th volume (1967) the 505-712 pages or leaves detailed description is arranged, it is introduced here as a reference.Should explain that if desired, the combination of the blend of any above-mentioned materials or multipolymer and the fiber processed by any above-mentioned materials all can be used for the present invention.

The present invention will discuss the content of glass fiber yarn thigh now generally, comprise one or more above-mentioned non-glass fibers although it will be apparent to those skilled in the art that yarn thigh 16 can also add.

Be not limited to the present invention; In the embodiment of fabric shown in Figure 2 14; At least one and preferred whole fiber 18 are coated with the coating 22 of coating composition in the yarn thigh 16; Be coated at least a portion surface of fiber 18, do not receive the wearing and tearing in the course of processing and prevent fibre breakage with the protection fiber surface.Preferably, as shown in Figure 3, coating composition is coated in each root fiber 18 entire exterior surface or periphery in the yarn thigh 16.

Be used for coating composition of the present invention can according to required as setting agent (preferably), be coated on the setting agent second coating and/or the 3rd or the form of outer field coating be present in fiber.Here said term " typing ", " be finalized " or " setting agent " is meant and after fiber forms, applies the coating composition of giving fiber immediately.In another embodiment; Term " typing ", " be finalized " or " setting agent " and also refer to after removing the conventional substrate coating composition, give through heating, water or chemical treatment fibre applicator coating composition (be referred to as again " arrangement typing "), the arrangement typing applies promptly for the bare glass fiber that is blended into form of fabric.Term " second coating " is meant after applying the setting agent compsn and preferably at least after the part drying, applies the coating composition of giving one or more yarn thighs once more.Can before fiber is blended into fabric, give fiber, perhaps can after fiber is blended into fabric, apply and give fiber, for example pass through coated textiles this applying coating.

Be used for preferably aqueous coating composition of coating composition of the present invention.Although for security reasons be not preferred, can contain volatile organic solvent on demand in the coating composition, like alcohol or ketone, preferably do not contain this solvent.

Can be used for containing in the coating composition of the present invention the compatible polymeric materials of matrix material 12 of one or more and laminate 10; Like thermosetting material or thermoplastic material; Be that the component of coating composition helps substrate material on the silvalin thigh to soak and drenches, and sufficient physicals is provided in composite bed.Preferably, polymeric materials forms common successive film when on the surface that is coated to fiber 18.Polymeric materials can be water miscible, emulsible, dispersible and/or curable.Here said phrase " compatible with matrix material " is meant that the component that is coated to the coating composition on the spun glass helps substrate material on the silvalin thigh drenched and soak; Sufficient physicals is provided in composite bed; With matrix material be the chemistry compatible; Good stability to hydrolysis is provided; Promptly anti-moisture is along fiber surface/substrate material interfacial migration, and before coated fibres being spiked in the matrix material, need not remove coating composition (or the coating composition through selecting).Matrix material penetrates measuring of mat or fabric and is called " drenching ".Matrix material see through the glass fiber yarn thigh with the whole surface that obtains each spun glass by matrix material basically fully the measuring of flowability of encapsulate be called " soaking ".

In one embodiment of the invention; The coating composition of being coated with application for the fiber 18 mix in the laminate 10 contain one or more with such as be used to form printed substrate or PC board (after this with they separately or be commonly referred to as " circuit card ") the thermoset matrix material compatible polymers film forming material of laminate; FR-4 epoxy resin for example, it is a kind of polyfunctional epoxy resin and in concrete embodiment of the present invention, is dual functional brominated epoxy resin; And polyimide.Referring to 1 The electronic material handbook, ASM Internat ional (1989) 534-537 pages or leaves, it is introduced here as a reference.

The non-limiting example of available polymer film-forming material comprises the thermoplastic polymeric material compatible with thermoset matrix material, for example thermoplastic polyester, vinyl polymer, polyolefins, polyamide-based (like aliphatic polyamide or aromatic poly such as Kevlar); Thermoplastic polyurethane, XPA and composition thereof.The thermoplastic polyester limiting examples comprises DESMOPHEN 2000 and DESMOPHEN 2001KS, and both all can be purchased acquisition from the Bayer of Pittsburgh (Pennsylvania); The RD-847A vibrin, it can be purchased acquisition from the Borden Chemicals of Columbus (Ohio); And DYNAKOLL SI100 resin, it can be purchased acquisition from Eka Chemicals AB (Sweden).The available polymeric amide comprises the VERSAMID product, and it can be purchased acquisition from General Mills chemical company.Useful thermoplastic polyurethane comprises

W-290H, its can be from Chicago the Witco chemical company of (Illinois) be purchased acquisition; 2011L polyurethane rubber latex, it can be purchased acquisition from the Ruco Polymer company of Hicksville (New York).

The non-limiting example of available thermoset polymerization material comprises the thermosetting polyester compatible with thermoset matrix material, epoxide, vinyl ester, phenoplast, aminoplastics, heat-curable urethane and composition thereof.Suitable thermosetting polyester can comprise the STYPOL polyester, and it can be purchased acquisition from the Cook Composites and Polymers of Port Washington (Wisconsin); With the NEOXIL polyester, it can be purchased acquisition from the DSM B.V. of Como (Italy).

Contain at least one epoxy group(ing) or ethylene oxide group in its molecule of available epoxide, for example the polyglycidyl ether of polyvalent alcohol or mercaptan.Suitable epoxy polymer instance comprises

826 with

880 epoxy resin; It is can be from Texas, and the shell chemical company of Houston is purchased the epoxy functionalized polyglycidyl ether of the dihydroxyphenyl propane of acquisition.In an embodiment of coating composition, coating composition is substantially free of epoxide, promptly contains the epoxide less than about 5wt%, is more preferably less than about 2wt%.

In an indefiniteness embodiment of coating composition, coating composition contains one or more polyester (like DESMOPHEN2000 and RD-847A) and one or more are selected from the additional film forming polymkeric substance in vinyl pyrrolidone polymer (preferably), vinyl alcohol polymkeric substance and/or the starch.Can be used for vinyl pyrrolidone polymer of the present invention and comprise the PVP K120 such as PVP K-15, PVPK-30, PVP K-60 and PVP K-90, every kind all can be purchased acquisition from the ISP chemical company of Wayne (New Jersey).Other suitable vinyl polymer comprises Resyn2828 and Resyn1037 vinyl acetate copolymer emulsion, and it can be purchased acquisition from the National Starch and Chemical of Bridgewater (New Jersey).Available starch comprises by yam, corn, wheat, Glutinous Semen Maydis, sago, rice, buys starch of sieve Chinese sorghum preparation and composition thereof; Kollotex1250 (starch of the yam base-material of a kind of LV, low amylose starch, ethylene oxide etherification) for example, it can be purchased acquisition from the AVEBE of Holland.The amount of additional polymer is preferably less than about 20wt%, more preferably from about the about 5wt% of 0.1-.Preferably, coating composition is substantially free of starch, promptly contains the starch less than about 5wt%, and more preferably not starch-containing, and said starch often is inconsistent with substrate material.

Coating composition can contain one or more thermoset polymerization materials and one or more thermoplastic polymeric materials' mixture.In an embodiment of printed substrate laminate, the polymeric materials that is used for coating composition contains the mixture of RD-847A vibrin or DYNAKOLL SI100 resin, PVP K-30 PVP K120, DESMOPHEN2000 polyester and VERSAMID polymeric amide.In another embodiment that is fit to the printed substrate laminate, the polymeric materials of moisture Hairstyling composition contains PVP K-30 PVP K120, and it can optionally combine with EPON826 epoxy resin.

As a rule, the amount of polymeric materials is counted the about 90wt% of about 1-of coating composition, the about 80wt% of preferably about 1-with total solids.

Except or replace above-mentioned polymeric materials; Preferably contain one or more coupling agents in the coating composition, such as organo silane coupling agent, transition metal coupling agent, phosphonic acid ester coupling agent, aluminum coupling agent, contain amino Wei Na (Werner) coupling agent and composition thereof.These coupling agents generally have difunctionality.Connect on each metal or the Siliciumatom one or more can with the group of the component reaction or the compatibilized of fiber surface and/or polymeric matrix.Here said term " compatibilized " is meant group by the component of chemical attraction to fiber surface and/or coating composition, for example through polarity, wetting or solvation power.In an indefiniteness embodiment, connect one or more permission coupling agents and the hydrolysable group of fiberglass surfacing reaction and the functional groups of one or more permission coupling agent and polymeric matrix component reaction on each metal or the Siliciumatom.The instance of hydrolysable group comprises:

and

1,2-or 1, the monohydroxy of 3-glycol and/or ring-type C ₂-C ₃Residue, wherein R ¹Be C ₁-C ₃Alkyl; R ²Be H or C ₁-C ₄Alkyl; R ³And R ⁴Be selected from H, C respectively ₁-C ₄Alkyl or C ₆-C ₈Aryl; And R ⁵Be C ₄-C ₇Alkylidene group.The suitable compatibilized or the instance of functional group comprise that epoxy, glycidoxy, sulfydryl, cyanic acid, allyl group, alkyl, urethano, halogen, isocyanato, urea groups, imidazolinyl, vinyl, propylene acid group close, the methacrylic acid group closes, amino or gather amino.

The present invention preferably uses functional organic alkane coupling agent.The instance of useful functional organic alkane coupling agent comprises γ aminopropyl trialkoxy silane, γ isocyanato propyl-triethoxysilicane, vinyl-trialkoxy silane, glycidoxy propyl trialkoxy silane and urea groups propyl trialkoxy silane.Preferred functional organosilane coupling agent comprises the silane coupling agent of A-187 γ glycidoxypropyltrime,hoxysilane, A-174 γ methacryloxypropyl trimethoxy silane, A-1100 γ aminopropyltriethoxywerene werene; A-1108 amino silicane coupling agent and A-1160 γ urea groups propyl-triethoxysilicane (every kind all can be from the OSi Specialties of Tarrytown (New York), and Inc. is purchased acquisition).Before using to fiber, can water with organo silane coupling agent partly hydrolysed at least, preferably with about 1: 1 stoichiometric ratio, or use with unhydrolysed form if desired.If desired, can regulate the pH of water, so that as well known in the art, cause or quicken the hydrolysis of coupling agent through adding acid or alkali.

Suitable transition metal coupling agent comprises titanium, zirconium, yttrium and chromium coupling agent.Suitable titanate coupling agent and zirconate coupling agent can be purchased acquisition from Kenrich Petrochemical company.Suitable chromium complex can be purchased acquisition from the E.I.duPont deNemours of Wilmington (Delaware State).Contain amino Wei Na type coupling agent and be wherein trivalent central atom such as chromium atom and contain the organic acid coordinate complex compound compound of amido functional group.Other metal-chelating well known by persons skilled in the art and corrdination type coupling agent also can be used for the present invention.

The amount of coupling agent can be the about 30wt% of about 1-of coating composition in total solids, and the about 10wt% of preferably about 1-.

Be not restricted to the present invention; In the embodiment depicted in fig. 3; Coating composition of the present invention contains one or more particles 24; It sticks to the outside surface of fiber 18 when apply giving at least one fiber 18 of yarn thigh 16, and at the adjacent glass fiber 26 of yarn thigh 16, one or more clearance spaces 30 are provided between 28.These clearance spaces 30 as a rule are equivalent to the mean sizes 32 of the particle 24 between adjacent fiber.

The particle that the particle 24 of coating composition is preferably discrete.Here said term " disperses " and is meant that particle does not trend towards Colaesce or combine forming film under processing conditions, but keeps its one shape or form usually.And these particles dimensional stabilizing preferably.Here said term " particle of dimensional stabilizing " is meant that particle is under processing conditions; For example in the power of weaving, being produced between the adjacent fiber in slubbing and other process operation; Usually can keep its average particle size particle size and shape, thus the clearance air that keeps adjacent fiber 26, requires between 28.In other words; Particle in the coating composition is under typical spun glass processing conditions; As place cruelly the highest about 25 ℃ and preferably the highest about 100 ℃, more preferably under the highest 140 ℃; Preferably not broken, dissolving or distortion in essence form the particle of overall dimension less than its selected average particle size particle size.In addition, particle 24 says that more specifically processing temperature can surpass under 150 ℃ the complex body processing conditions therein under the spun glass processing conditions, and its size should not increase or expand basically.Here said phrase is meant the expansion of particle size during processing or increases about particulate " size should not increase basically " and should be no more than about 3 times of its original size.Preferably, coating composition of the present invention is substantially free of the hollow bead of heat-swellable.Here said term " hollow bead of heat-swellable " is meant the hollow bead that is filled with or contains whipping agent, when being placed when being enough to make whipping agent evaporable temperature its size to expand cruelly or increasing basically.Here said " being substantially free of " is meant and contains in the Hairstyling composition in the hollow bead of total solids less than about 20wt% heat-swellable, be more preferably less than about 5wt%, and be first-selected less than 0.001wt%.In addition, said here term " dimensional stabilizing " comprises crystalline form and amorphous material.

In addition, although do not require, preferred particulates 24 is non-waxs.Term " non-wax " is meant that forming the particulate material is not waxy.Here said term " wax shape " refers to that mainly the average carbon chain length degree of said hydrocarbon chain is the about 100 carbon atom (L.H.Sperling of about 25-by separating the material that the hydrocarbon chain that twines is formed The physical polymeric scienceForeword, John Wiley and Sons company (1986) 2-5 pages or leaves, it is introduced here as a reference; W.Pushaw etc. " micronization wax and the wax dispenser purposes in water system " Polymkeric substance, paint, pigment magazine, V.189, No.4412, in January, 1999, the 18-21 page or leaf, it is introduced here as a reference).

Preferably, the particle in the coating composition 24 is particles that disperse, dimensional stabilizing, non-wax.In concrete, indefiniteness embodiment of the present invention, the average particle size particle size 32 of particle 24 is at least about 0.1 micron, preferably at least about 0.5 micron, and is the about 5 microns scope of 0.1-, about 3.0 microns of preferably about 0.5-.In one embodiment, particle 24 is at least about 1 micron, and about 3 microns of preferably about 1-.In this indefiniteness embodiment, the average particle size particle size 32 common little mean diameters of wanting the fiber 18 of applying coatings compsn on it of particle 24.According to observations; Have sth. made by twisting system yarn that the silvalin thigh 16 of the bottom Hairstyling composition residue layer 22 of the particle 24 of average particle size particle size 32 as stated processes adjacent fiber 26, enough spaces between 28 can be provided by containing; So that allow air spray to weave (being that airflow passes loom), keep the globality of silvalin thigh 16 simultaneously and acceptable " soaking into " and " soaking " characteristic are provided when flooding with matrix material.

Of the present invention another is concrete, in the indefiniteness embodiment, the average particle size particle size 32 of particle 24 is at least 3 microns, preferably at least about 5 microns, and is the about 1000 microns scope of 3-, about 1000 microns of preferably about 5-, more preferably from about 10-is about 25 microns.Preferably, each particle 24 all has at least 3 microns smallest particles size, preferably at least about 5 microns.The average particle size particle size 32 of going back preferred particulates 24 in this embodiment generally is equivalent to the average nominal diameter of spun glass.According to observations, there is the fabric of the particle coated yarn thigh manufacturing of size as stated when flooding, to show good " soaking into " and " soaking " characteristic by apparatus with matrix material.

The mixture that those skilled in the art will recognize that one or more particles 24 of different average particle size particle size 32 can be spiked in the Hairstyling composition of the present invention, so that give silvalin thigh 16 and required performance and machining feature is provided for subsequently the product by its manufacturing.More specifically say, can measure associating use particles of different sizes on demand, make fiber have good airflow migration performance and make fabric show the good characteristic of soaking and soak into.

Be not restricted to the present invention, the configuration of particle 24 or shape as a rule can be spherical (like pearl, microballon shape or solid hollow ball), cube shaped, flat-section, aciculiform (elongate or fibrous) on demand.In addition, the structure of particle 24 can be hollow, porous or zero-clearance or its combination.In addition, particle 24 can have the combination of these structures, like hollow arbor braid porous or solid walls.About suitable particle characteristic than details referring to (volumes) such as H.Katz Filler and plastics handbook(1987) 9-10 pages or leaves, it is introduced here as a reference.

Be shaped and subsequently the course of processing, as weave or slubbing in, spun glass is worn through solid objects or the coarse contact of material that contacts with near spun glass and/or other spun glass.Here said " wearing and tearing " are meant through making fiberglass surfacing scraping with the particle that is difficult to be enough to damage spun glass, edge or material monolithic wiping or fragment is cut or breakout.Referring to K.Ludema Friction, wearing and tearing, lubricated(1996) the 129th pages, it is introduced here as a reference.The wearing and tearing of glass fiber yarn thigh can cause in the course of processing fracture of yarn thigh and such as the surface imperfection in the product of woven cloths and composite members, waste and manufacturing cost thereby increase.

For reducing wear, particle 24 can not surpass the certain rigidity value, promptly is less than or equal to the hardness value of spun glass.The hardness value of particle and spun glass can be measured through the hardness measurement method of any routine, for example Vickers or Brinell hardness, but preferably measure according to primary Mohs ' scale of hardness, it has pointed out the relative scraping resistance of material surface.Mohs ' the hardness value of spun glass is generally about 4.5-about 6.5, preferred about 6.Referring to R.Weast (volume) Chemistry With the physics handbookCRC press (1975) F-22 pages or leaves, it is introduced here as a reference.The aforesaid particulate Mohs ' hardness value that is suitable for this coating composition is preferably about 0.5-about 6.Following Table A has provided the Mohs ' hardness value of the particulate non-limiting example of a lot of the present invention of being fit to uses.

Table A

Particulate material	Mohs ' hardness (original scale)
		SP 1	About 2 5
Graphite	About 0.5-1 6
		Molybdenumdisulphide	About 1 7
Talcum	About 1-1.5 8
		Mica	About 2.8-3.2 9
Kaolinite	About 2.0-2.5 10
		Gypsum	About 1.6-2 11
Calcite (lime carbonate)	About 3 12
		Calcium Fluoride (Fluorspan)	About 4 13
Zinc oxide	About 4.5 14
		Aluminium	About 2.5 15
Copper	About 2.5-3 16
		Iron	About 4-5 17
Gold	About 2.5-3 18
		Nickel	About 5 19
Palladium	About 4.8 20
		Platinum	About 4.3 21
Silver	About 2.5-4 22

5 K.Ludema Friction, wearing and tearing, lubricated(1996) the 27th pages, introduce here as a reference.

6 R.Weast (volume) Chemistry and physics handbookCRC press (1975) F-22 pages or leaves.

7 R.Lewis, Sr. Hawley ' s condensation chemical dictionary(the 12nd edition 1993) the 793rd page introduced here as a reference.

8 Hawley ' s condensation chemical dictionary(the 12nd edition 1993) the 1113rd page introduced here as a reference.

9 Hawley ' s condensation chemical dictionary(the 12nd edition 1993) the 784th page introduced here as a reference.

10 Chemistry and physics handbookF-22 page or leaf 11 chemistry and physics handbook F-22 pages or leaves

12 Friction, wearing and tearing, lubricatedRub for the 27th page 13, wear and tear, lubricate the 27th page

14 Friction, wearing and tearing, lubricatedThe 27th page

15 Friction, wearing and tearing, lubricatedThe 27th page

16 Chemistry and physics handbookThe F-22 page or leaf

17 Chemistry and physics handbookThe F-22 page or leaf

18 Chemistry and physics handbookThe F-22 page or leaf

19 Chemistry and physics handbookThe F-22 page or leaf

20 Chemistry and physics handbookThe F-22 page or leaf

21 Chemistry and physics handbookThe F-22 page or leaf

22 Chemistry and physics handbookThe F-22 page or leaf

As stated, Mohn ' s scale of hardness relates to the scratch resistance of material.Therefore the present invention comprises that also its surface hardness is different from the particle of its surface underneath granule interior hardness.More specifically say; The particulate surface can be improved by any way well known in the art; Comprise (but being not limited thereto) use its surface property of technological chemically changed known in the art; So that the particulate surface hardness is not more than the hardness of spun glass, the pellet hardness below the surface is greater than the hardness of spun glass simultaneously.Perhaps, can coating, covering or encapsulated particles, form the composite particles (discuss the back) that has than pressure release surface

As a rule, can be used for particle 24 of the present invention can be formed by polymerization and non-polymer-inorganic material, polymerization and non-polymerization organic materials, matrix material and composition thereof.Here said term " polymer-inorganic material " refers to that its main chain repeating unit is the polymeric materials that is the basis with non-carbon.About more information can referring to J.E.Mark etc.Page 5, it is introduced here as a reference.The polymerization organic materials comprises synthetic polymeric material, semi-synthetic polymeric materials and natural polymerization material.Here said " organic materials " refers to such as binary compounds such as carbonoxide, carbide, dithiocarbonic anhydride; Such as metal cyanides; Ternary compounds such as metal carbonyls, carbonyl chloride, carbonyl sulfide and such as all carbon cpds except the carbonic acid metal salts such as lime carbonate and yellow soda ash.Referring to R.LewisSr. Hawley ' s condensation chemical dictionary(the 12nd edition, 1993) 761-762 page or leaf, it is introduced here as a reference.More generally, organic materials comprises carbon compound, wherein general self bonding of carbon and and hydrogen bonding, and often also with other element bonding, and do not comprise carbonaceous ionic compound.Referring to the M.silberberg chemistry The molecular property of material And variation(1996) the 586th pages, introduce here as a reference.Term " inorganic materials " is often referred to all material of non-carbon cpd, except carbonoxide and the dithiocarbonic anhydride.Referring to R.Lewis Sr. Hawley ' s condensation chemical dictionary(the 12nd edition, 1993) the 636th page, it is introduced here as a reference.Here said term " inorganic materials " refers to any material of non-organic materials.Here said term " matrix material " refers to two or more combinations of different materials.About can be used for particulate more information of the present invention referring to G.Wypych The filler handbookThe 2nd edition (1999) 15-202 pages or leaves are introduced here as a reference.

The non-polymer-inorganic material that can be used for forming particle 24 comprises stupalith and metallic substance.Suitable stupalith comprises metal nitride, MOX, metallic carbide, metallic sulfide, metal boride, metal silicate, metal carbonate and composition thereof.

The non-limiting example of suitable metal nitride is a SP 1, and it is to form to be applicable to the preferred inorganic materials of particulate of the present invention.The non-limiting example of useful MOX is a zinc oxide.Suitable metallic sulfide comprises molybdenumdisulphide, tantalum disulfide, tungsten disulfide and zinc sulphide.Useful metal silicate comprises pure aluminium silicate and Magnesium Silicate q-agent, for example vermiculite.Suitable metallic substance comprises graphite, molybdenum, platinum, palladium, nickel, aluminium, copper, gold, iron, silver and composition thereof.

Although do not require, preferred particulates 24 solid lubricants.Here said " solid lubricant " refers between two surfaces to use any solid to prevent the damage in the process of relatively moving and/or reduces friction and wear and tear.Particle 24 is more preferably inorganic solid lubricant.Here said " inorganic solid lubricant " refers to that inorganic particle 24 has characteristic crystalline form character; This character causes them to be sheared the thin flat plate that slides easily each other, thus fiberglass surfacing and near solid surface between produce the lubricant effect (wherein at least one moves) of friction resistant.(referring to R.Lewis, Sr. Hawley ' s condensation chemical dictionary(the 12nd edition 1993) the 712nd page, it is introduced here as a reference.) friction be that a solid is at another resistance that slides above solid.Referring to F.Clauss, The solid of solid lubricant and self-lubrication(1972) page 1, it is introduced here as a reference.

Be used for a specific embodiments of the present invention, solid lubricant particle has laminate structure, it is believed that this laminate structure can reduce the wearing and tearing of instrument when boring on laminate, below will more go through.Particle with laminate structure is made up of the sheet or the plate of the atom of hexagonal array, is strong bonding and be that weak van der Waals' bond closes between sheet and the sheet in the sheet, and the low shearing resistance between the sheet is provided.The laminate structure limiting examples is a hexagonal crystal structure.Referring to Friction, wearing and tearing, lubricatedThe 125th page; Solid The solid of lubricant and self-lubrication19-22,42-54,75-77,80-81,82,90-102,113-120 and 128 pages; And W.Campbell " solid lubricant " Boundary lubrication: the evaluation of world's documentASME Research Committee onLubrication (1969) 202-203 pages or leaves, it is introduced here as a reference.Inorganic particle with stratiform soccerballene (buckyball) structure also can be used for the present invention.

The suitable inorganic solid lubricant particulate non-limiting example with laminate structure comprises that SP 1, graphite, metal dithionite belong to element thing (dichalcogeni des), mica, talcum, gypsum, kaolinite, calcite, cadmium iodide, silver sulfide and composition thereof.Preferred inorganic solid lubricant particle comprises that SP 1, graphite, metal dithionite belong to element thing and composition thereof.Suitable metal dithionite belongs to the element thing and comprises molybdenumdisulphide, joins selenizing molybdenum, tantalum disulfide, couplet selenizing tantalum, tungsten disulfide, couplet selenizing tungsten and composition thereof.

Non-limiting example with inorganic solid lubricant material that is adapted at using in the coating composition of the present invention of hexagonal crystal structure is a SP 1.The particle that forms by SP 1, zinc sulphide and smectite with the complex body of matrix material such as nylon 6,6 in good whiteness also is provided.

The non-limiting example that is suitable for boron nitride particle of the present invention is

100 series (PT120, PT140, PT160 and PT180), 300 series (PT350) and 600 series (PT620, PT630, PT640 and PT670) boron nitride powder particle, and it can be purchased acquisition from the Advanced Ceramics company of Lakewood (Ohio).The technical bulletin of " be used for polymeric materials

heat conductance filler " Lakewood (Ohio) Advanced Ceramics company, it is introduced here as a reference.These particulate thermal conductivities are down about 250-300 watt of/meter ° K at 25 ℃, specific inductivity be about 3.9 and volume resistance be about 10 ¹⁵Ohm-cm.The average particle size particle size of 100 serial powder particles is about 14 microns of about 5-, and 300 serial particulate average particle size particle size are that about 16-is greater than about 200 microns for about 100-about 150 microns and 600 serial particulate average particle size particle size.

Particle 24 can be formed by non-polymeric organic materials.The instance that is fit to non-polymerization organic materials of the present invention comprises (but being not limited thereto) stearate (like Zinic stearas and StAl), carbon black and stearylamide.

Particle 24 can be formed by inorganic polymeric materials.The limiting examples of useful inorganic polymeric materials comprises group of polyphosphazenes, polysilanes, ZGK 5, polygeremanes, polymerised sulphur, polymerization selenium, silicone and composition thereof.A kind of particulate instance that is formed by inorganic polymeric materials of the present invention that is suitable for of concrete indefiniteness is that Tospearl is (referring to R.J.Perry " application of crosslinking silicone particulate " Chemtech; 1999.2; The 39-44 page), for the particle that forms by crosslinked siloxanes and can be purchased acquisition from Japanese Toshiba Silicones ltd.

The synthetic organic polymer material that suitable formation particle is used comprises (but being not limited thereto) thermosetting material and thermoplastic material.Suitable thermosetting material comprises thermosetting polyester, vinyl ester, epoxide, phenoplast, aminoplastics, heat-curable urethane and composition thereof.A kind of concrete non-limiting example of the preferred synthetic polymer particle that is formed by epoxide is the epoxy micro-gel particles.

Suitable thermoplastic material comprises thermoplastic polyester class, polycarbonate-based, polyolefins, XPA class, polyamide-based, thermoplastic polyurethanes, vinyl polymer class and composition thereof.Preferred thermoplastic polyester class comprises (but being not limited thereto) polyethylene terephthalate, polybutylene terephthalate and PEN.Preferred polyolefins comprises (but being not limited thereto) Vilaterm, Vestolen PP 7052 and polyisobutene.Preferred XPA class comprises vinylbenzene and acrylic acid multipolymer and the polymkeric substance that contains methacrylic ester.The non-limiting example of the synthetic polymer particle that forms by PEMULEN TR2 be

HP-1055 (be "

HP-1055; be used for the hollow ball shape pigment of paper and pressboard coating " product feature singly; 1994.10; Can be from Rohm and Haas company (Philadelphia; PA) obtain; Page 1 is introduced here as a reference), it is a kind of opaque non-film-forming styrene acrylic polymers synthetic dyestuff; Its particle size is 1.0 microns, and solid content is that 26.5wt% and void volume are 55%; OP-96 (referring to title is " trade sales coating-

OP-96; all-round pigment " the product technology communique; 1997.4; Can be from Rohmand Haas company (Philadelphia; PA) obtain; Page 1 is introduced here as a reference), it is a kind of opaque non-film-forming styrene acrylic polymers synthetic dyestuff dispersion liquid; Its particle size is 0.55 micron; Solid content is 30.5wt% and

OP-62LO (seeing Ibid), also is a kind of opaque non-film-forming styrene acrylic polymers synthetic dyestuff dispersion liquid, and its particle size is that 0.40 micron and solid content are about 36.5wt%; All can be purchased acquisition from Rohmand Haas company (Pennsyivania, Philadelphia).

The suitable semi-synthetic organic polymer material that can be used to form particle 24 comprises (but being not limited thereto) cellulose family, for example methylcellulose gum and rhodia; And treated starch, like starch acetate and h and E starch.

The suitable natural polymerization material that can be used to form particle 24 comprises (but being not limited thereto) polyose, like starch; The polypeptide class is like casein; And natural hydro carbons, like tree elastomer and gutta.

In one embodiment of the invention, polymer beads 18 is formed by hydrophobic polymeric material, so that reduce or restriction is applied the moisture that the yarn thigh absorbs.It is believed that the non-limiting example that can be used for hydrophobic polymeric material of the present invention comprises (but being not limited thereto) Vilaterm, Vestolen PP 7052, PS and polymethylmethacrylate.Polystyrene copolymer Non-limiting examples include

HP-1055,

OP-96 and

OP-62LO pigment (as discussed above).

In another embodiment of the invention, polymer beads 18 is greater than about 25 ℃ and be preferably greater than about 50 ℃ polymeric materials and form by second-order transition temperature (Tg) and/or fusing point.

Can be used for composite particles 24 of the present invention and comprise the formed particle of particle that forms by the bed material material through with coated, encapsulate of one or more second materials or coating.For example, can or receive clay (nanoclay) applying coating, be formed with the composite particles of usefulness with silicon-dioxide, carbonate by the inorganic particle that the inorganic materials such as silit or aluminium nitride AlN etc. forms.In another example, can the surface reaction of the silane coupling agent with alkyl group side chain with the inorganic particle that is formed by inorganic oxide be formed the useful composite particles with " softer " surface.That other instance comprises is coated with inorganic materials or different organic or polymeric materials, encapsulate or coating be by particle organic or that polymeric materials forms.A kind of concrete non-limiting example of this composite particles is DUALITE, and it is the synthesized polymer particle of lime carbonate coating, can be purchased acquisition from the Pierce and Sevens company of Buffalo (New York).

In another embodiment of the invention, particle 24 can be the hollow bead that is formed by the material that is selected from inorganic materials, organic materials, polymeric materials, matrix material and composition thereof.Can be used to form hollow bead suitable material non-limiting example as stated.Can be used in the present invention, the hollow polymeric particles of non-limiting examples are

HP-1055,

OP- 96 and

OP-62LO pigment (as discussed above) .Other limiting examples that can be used for hollow bead of the present invention can be introduced here as a reference referring to (volume) (1987) 437-452 pages or leaves such as H.Katz.

Solid lubricant particle 24 can dispersion liquid, suspension-s or emulsion form in water exist.If desired, can contain other solvent such as MO or alcohol (preferably less than about 5wt%) in the Hairstyling composition.The non-limiting example of preferred about 25wt% boron nitride particle aqueous dispersions is ORPAC BORON NITRIDE RELEASECOAT-CONC, and it can be from the ZYP Coatings of Oak Ri dge (Tennessee State), and Inc. is purchased acquisition." ORPAC BORON NITRIDERELEASECOAT-CONC ", the technical bulletin of ZYP Coatings company is introduced here as a reference.The average particle size particle size of the boron nitride particle in this product is less than about 3 microns, and contains 1% the pure aluminium silicate-magnesium of having an appointment, and needs to apply in the substrate of dispersion liquid so that boron nitride particle is attached to.Other can comprise BORON NITRIDE

paint, BRAZE STOP and WELD RELEASE product from the useful prods that ZYP Coat ings is purchased acquisition.Specifically; The synthesized polymer particulate emulsion that is formed by XPA and multipolymer and the non-limiting example of dispersion liquid comprise: GL-623 (be " GL-623; the type of the crosslinkable acrylic voluntarily tackiness agent of industrial non-woven fabric " product feature single; 1997.3; Can be from Rohm and Haas company (Philadelphia; PA) obtain; Introduce here as a reference), it is a kind of full acrylic film polymer emulsion, its solid content is that 45wt% and second-order transition temperature are about 98 ℃; EMULSION E-2321 is (single for the product feature of " setting up product industrial coating-emulsion E-2321 " referring to title; 1990; Can be from Rohm and Haas company (Philadelphia PA) obtains, and introduces here as a reference); It is a kind of hard methacrylate polymers emulsion, and its solid content is that 45wt% and second-order transition temperature are about 105 ℃;

OP-96 (as above discussing); It provides as dispersion liquid, and wherein particle size is that 0.55 micron and solid content are 30.5wt%;

OP-62LO (as stated); It also is a kind of opaque non-film-forming synthetic dyestuff dispersion liquid; Particle size is 0.40 micron, and solid content is about 36.5wt%; HP-1055 (as above discussing); It provides as dispersion liquid, and wherein solid content is about 26.5wt%; All all can be purchased acquisition from Rohm and Haas company (Pennsyivania, Philadelphia).

Although do not require, preferred particulates 24 be can not hydration the inorganic solid lubricant particle.Here said " can not hydration " be meant that the solid inorganic lubricant particle does not form hydrate with water molecule reaction and do not contain the water or the crystal water of hydration." hydrate " produces through water molecules and substance reaction, and wherein the H-OH key does not rupture.Referring to R.Lewis, Sr. Hawley ' s condensation chemical Dictionary(the 12nd edition 1993) 609-610 page or leaf and T.Perros Chemistry(1967) 186-187 pages or leaves, it is introduced here as a reference.Say on the structure, but the inorganic materials of hydration comprises at least one hydroxyl (but at modular construction or absorb moisture in its surface or absorb in the surface plane of material of moisture not hydroxyl through capillary action), for example J.Mitchell in the layer of crystal lattice The ultimate principle of soil propertyKaolinic structure and H.van Olphen shown in (1976) the 34th pages of Fig. 3 .8 The clay colloid chemistry1: 1 and the structure of 2: 1 layers of mineral shown in (the 2nd edition, 1977) the 62nd page of Figure 18 and 19, it is introduced here as a reference.Crystal lattice " layer " be the combination of crystal face, and crystal face is the combination of lattice plane. Referring to edatope In mineralSoil Loss scientific institution (1977) 196-199 pages or leaves are introduced here as a reference.The cooperation of layer and interlayer material (like positively charged ion) is called modular construction.

Contain coordinated water in the hydrate, the positively charged ion in its coordinated water condensation material and do not destroy structure and/or water of constitution just can not be removed it, it does not break charge balance in occupation of the gap in the structure to increase electrostatic energy.Referring to R.Evans Crystal chemistry is crossed the threshold(1948) the 276th pages, it is introduced here as a reference.

Not preferred, but moisture Hairstyling composition is except that the above-mentioned inorganic solid lubricant material that also contains hydration or hydration can not the inorganic solid lubricant material of hydration.But the non-limiting example of this hydrated inorganic solid lubrication agent material is a clay mineral leaf silicates, comprises mica (like white mica), talcum, smectite, kaolinite and gypsum.

Preferably; But coating composition is substantially free of inorganic solid lubricant particle or the abrasive silica particle or the lime carbonate of hydration; But promptly contain hydrated inorganic lubricant particle, abrasive silica particle or lime carbonate less than about 20wt% in total solids; Be more preferably less than about 5wt%, first-selected less than 0.001wt%.

Be used for another embodiment of the invention, particle 24 can be formed by the organic polymer material that is selected from thermosetting material, thermoplastic material, starch and composition thereof.Suitable thermosetting material comprises thermosetting polyester class, vinyl ester, epoxide, phenoplast, aminoplastics, heat-curable urethane class and composition thereof, for example discusses as follows.Suitable thermoplastic material comprises vinyl polymer, thermoplastic polyester class, polyolefins, polyamide-based, thermoplastic polyurethanes, XPA class and composition thereof.Preferred organic granular is the form with microballon or hollow ball.

Although do not require, be used for one embodiment of the invention, particle 24 is heat conductances, promptly has the thermal conductivity greater than about 30 watts of/meter K, is preferably greater than about 100 watts of/meter K, more preferably from about about 2000 watts of/meter K of 100-.Here said " thermal conductivity " refers to describe the characteristic that particle 24 can conduct heat through self.Referring to R.Lewis, Sr. Hawley ' s condensation chemical Dictionary(the 12nd edition 1993) the 305th page introduced here as a reference.

The thermal conductivity of solid particulate can be measured by any method known to those skilled in the art.For example, if the thermal conductivity of measured material is about 100 watts of/meter K of about 0.001-, then the thermal conductivity of material can use preferred protective hot flat band method to measure under about 300K temperature according to ASTM C-177-85 (it is introduced as a reference) here.If the thermal conductivity of measured material is about 1200 watts of/meter K of about 20-, then the thermal conductivity of material can use protective hot flux sensor method to measure according to ASTM C-518-91 (it is introduced as a reference) here.It is believed that the material with higher heat-conductivity can make the heat of the bore region that is produced during the boring scatter and disappear quickly, makes bit life prolong.The thermal conductivity that has comprised the Table A selected materials among the table B.

Although do not require, be used for another embodiment of the invention, particle 24 be electrical isolation or have high resistivity, promptly have resistivity greater than about 1000 micro-ohms-cm.The preferred particle that uses high resistivity for the custom circuit plate is used is so that suppress electrical signal because electronic conduction is crossed the loss that supporting material causes.Concerning special application, for example be used for microwave, radio frequency interference and EMI and use, do not need the particle of high resistivity.The resistivity that has comprised the Table A selected materials among the table B.

The particle 24 that those skilled in the art can understand coating composition can comprise any combination or the mixture of above-mentioned particle 24.Say that more specifically particle 24 can comprise the particle of the interpolation of being processed by the above-mentioned any material that is used to form particle 24.

Solid lubricant particle if exist, can account for the about 1wt% of about 1-of coating composition, in total solids, and the about 60wt% of preferably about 1-.In one embodiment, can contain SP 1 in the coating composition in the about 10wt% of the about 2-of total solids.In another embodiment of using the variable grain combination of the present invention, contain particle 24 in the coating composition in the about 60wt% of the about 20-of total solids, and the about 55wt% of preferably about 35-, the more preferably from about about 50wt% of 30-.

Can also contain tenderizer or tensio-active agent that one or more can bring equal electric charge to fiber surface in the coating composition, fiber is repelled each other and reduce the friction between the fiber, so that the effect of super fatting agent.Although do not require, preferred tenderizer is chemically different with above-mentioned polymeric materials.Can contain the tenderizer of maximum about 60wt% in the coating composition, the preferred coatings compsn is substantially free of tenderizer, promptly contains the tenderizer less than about 10wt%, more preferably contains the tenderizer less than about 5wt%.The instance of this tenderizer comprises positively charged ion, nonionic or negatively charged ion tenderizer and composition thereof, like the amine salt of lipid acid; Alkyl imidazoline derivatives such as CATIONX, it can be purchased acquisition from the Rhone Poulenc of Princeton (New Jersey); Acid dissolved fatty acid amide; The substituted polymine of the condenses of lipid acid and polymine and acid amides; Like 6717; The amidated polymine of a kind of part can be purchased acquisition from Henkel Corp. of Kankakee (Illinois State).More information about tenderizer can be referring to A.J.Hall Textile finishingThe 2nd edition (1957) 108-115 pages or leaves are introduced here as a reference.

Coating composition can contain one or more and be used for emulsification or dispersion paints composition component such as organic and emulsifying agent inorganic particle.The non-limiting example of examples of suitable emulsifiers or tensio-active agent comprises polyoxyalkylene group block copolymer (like PLURONICTMF--108 polyoxypropylene-polyoxyethylene copolymer, it can be purchased acquisition from BASF AG of Parsippany (New Jersey)); Ethoxylated alkylphenol (like IGEPAL CA-630 ethoxylation octyl phenoxyethanol, it can be purchased acquisition from the GAF company of Wayne (New Jersey)); T 46155 octyl phenyl glycol ethers; The epoxyethane derivative of sorbitol ester; Polyoxy ethylization vegetables oil (like ALKAMULS EL-719, it can be purchased acquisition from Rhone-Poulenc) and NP tensio-active agent (like MACOLNP-6, it can be purchased acquisition from the BASF of Parsippany (New Jersey)).As a rule, the amount of emulsifying agent can be the about 30wt% of about 1-of coating composition in total solids.

Can also contain one or more oilness materials chemically different with tenderizer in the coating composition, so that be provided at processing characteristics required in the weaving process for the silvalin thigh with above-mentioned polymeric materials.Suitable oilness material can be selected from oils, wax class, lubricated lipid and composition thereof.But the non-limiting example that can be used for wax class material of the present invention comprises water dissolvable emulsification or dispersible wax material, like plant, animal, mineral, synthetic or petroleum wax class, for example petroleum wax.Can be used for oil of the present invention and comprise natural oil, semi-synthetic oil and synthetic oil.As a rule, the amount of wax or other oilness material can be the about 80wt% of O-of Hairstyling composition in total solids, the about 50wt% of preferably about 1-, the about 40wt% of 20-more preferably from about, the about 35wt% of first-selected about 25-.

Preferred oilness material comprises wax class and the oils with polar character, more preferably comprises having polarity and fusing point greater than about 35 ℃ and more preferably greater than about 45 ℃ high crystalline state wax class.Contain wax with polar character with coating and compare with the silvalin thigh of the Hairstyling composition of oil, this material it is believed that and can improve soaking and soak on polar resin contains this polar material in coating the silvalin thigh of Hairstyling composition.Preferably having polar oilness material comprises by (1) monocarboxylic acid ester that reaction forms with (2) monohydroxy-alcohol.This non-limiting example that can be used for fatty ester of the present invention comprises the palmitinic acid cetyl ester.It is preferred (KESSCO653 or the STEPANTEX653 that for example can obtain), tetradecanoic acid cetyl ester (STEPANLUBE654 that also obtains), LAURIC ACID 99 MIN cetyl ester, LAURIC ACID 99 MIN stearyl, tetradecanoic acid stearyl, palmitinic acid stearyl and Triple Pressed Stearic Acid stearyl from Stepan company from the Stepan company of Maywood (New Jersey).Other can be used for fatty ester of the present invention, the oilness material comprises trimethylolpropane tris pelargonic esternonate, natural spermaceti and triglyceride oil, like (but being not limited thereto) VT 18, Toenol 1140, epoxidised soybean oil and epoxy linseed oil.

Although not preferred, coating composition can contain one or more other oilness materials, like nonpolar petroleum wax, replaces perhaps except that above-mentioned oilness material.The non-limiting example of nonpolar petroleum wax comprises

LUBE296 Microcrystalline Wax,

SPP-W Microcrystalline Wax and PETROLITE75 Microcrystalline Wax, and it can be purchased acquisition from the Michelman company of Cincinnati (Ohio) and the Petrolite company of Tulsa (Oklahoma) respectively.

Although do not require; Can also contain the resin reactive thinner in the coating composition if desired so as to improve coated fiber yarn thigh of the present invention oilness and through reduce possibly providing of fluffing in the manufacturing operation process, halo and fracture of wire good weave and weave processibility, keep resin compatible simultaneously.Here said " resin reactive thinner " refer to contain in the thinner can with the functional group of resin chemical reaction, said resin is same resin with the resin that is compatible to coating composition.Thinner can be a lubricant, and it has the functional groups of one or more and resin system reaction, preferably with the functional group of epoxy-resin systems reaction, more preferably with the functional group of FR-4 epoxy-resin systems reaction.The non-limiting example of suitable lubricant comprise have amine groups, the lubricant of alcohol groups, anhydride group, acid groups or epoxide group.Non-limiting example with lubricant of amine groups is a modified poly ethylene amine, and like EMERY6717, the amidated polymine of a kind of part can be purchased acquisition from Henkel Corp. of Kankakee (Illinois State).Non-limiting example with lubricant of alcohol groups is a polyoxyethylene glycol, and like CARBOWAX300, it is a kind of polyoxyethylene glycol that can be purchased acquisition from the Union Carbide of Danbury (Connecticut).Non-limiting example with lubricant of acid groups is a lipid acid, like Triple Pressed Stearic Acid and stearic salt.Non-limiting example with lubricant of epoxide group comprises epoxidised soybean oil and epoxy linseed oil; Like FLEXOL LOE epoxy linseed oil and FLEXOL EPO epoxidised soybean oil, all can be purchased acquisition from the Union Carbide of Danbury (Connecticut); And LE-9300 epoxidation organic silicon emulsion, it can be from the WitooCorporation OSi Specialties of Danbury (Connecticut), and Inc. is purchased acquisition.Although be not restricted to the present invention, can contain the above-mentioned resin reactive thinner of maximum about 15wt% of Hairstyling composition in the Hairstyling composition in total solids.

Cross-linked material such as melamine formaldehyde (MF) and softening agent such as phthalic ester, benzenetricarboxylic acid ester and adipic acid ester also can be contained in the coating composition.The amount of linking agent or softening agent is counted the about 5wt% of about 1-of coating composition with total solids.

Can contain other additive in the coating composition, like organo-siloxane polymkeric substance, mycocide, bactericide, skimmer, usually with amount less than about 5wt%.Can also contain and present in an amount at least sufficient to make organic and/or mineral acid or the alkali of coating composition pH for about 2-about 10.The limiting examples of suitable organosiloxane polymer emulsion is a LE-9300 epoxidation organosiloxane polymer emulsion, and it can be purchased acquisition from the OSi Specialties company of Danbury (Connecticut).The instance of suitable bactericide is the Biomet66 Fungicidal compounds, and it can be purchased acquisition from the M&T Chemicals of Rahway (New Jersey).Suitable froth breaking material is the SAG material, and it can be purchased acquisition from the OSi Specialties company of Danbury (Connecticut); And MAZU DF-136, it can be purchased acquisition from BASF AG of Parsippany (New Jersey).If desired, can add volatile caustic to coating composition and be used for stabilization.Preferably containing the water (preferred deionized water) that presents in an amount at least sufficient to help coating even coating on the yarn thigh in the coating composition, as a rule is the amount with the about 99wt% of about 25-.Solid weight per-cent is generally the about 75wt% of about 1-in the aqueous coating composition.

Coating composition preferably is substantially free of glass material.Here said " being substantially free of glass material " is meant that coating composition contains the glass host material that is used to form the glass composite members less than 20% volume, preferably less than about 5% volume, more preferably do not contain glass material.The instance of this glass host material comprises welding glass ceramic matrix material or silico-aluminate substrate material, for example well known to a person skilled in the art glass material.

An indefiniteness embodiment at the fabric that is used for circuit card of the present invention; On the spun glass of coated fiber yarn thigh, apply the bottom of moisture Hairstyling composition dried residue, wherein said Hairstyling composition contains

160 boron nitride powders and/or ORPACBORON NITRIDE RELEASECOAT-CONC dispersion liquid, PVP K-30 PVP K120, the functional organo silane coupling agent of A-174 vinylformic acid, epoxy functionalized organo silane coupling agent, ALKAMULS EL-719 polyoxy ethylization vegetables oil,

6717 part amidation polymines, RD-847A polyester, DESMOPHEN2000 polyester, PLURONICS F-108 polyoxypropylene-polyoxyethylene copolymer, ICONOL NP-6 alkoxylate nonylphenol and the SAG10 froth breaking material of A-187.

Another indefiniteness embodiment at the fabric that is used for circuit card of the present invention; On the spun glass of coated fiber yarn thigh of the present invention, apply the bottom of moisture Hairstyling composition dried residue, wherein said Hairstyling composition contains

160 boron nitride powders and/or ORPACBORON NITRIDE RELEASECOAT-CONC dispersion liquid, RD-847A polyester, PVP K-30 PVP K120, DESMOPHEN2000 polyester, the functional organo silane coupling agent of A-174 vinylformic acid, epoxy functionalized organo silane coupling agent, PLURONICS F-108 polyoxypropylene-polyoxyethylene copolymer, VERSAMID140 polymeric amide and the MACOL NP-6 nonylphenol of A-187.

Another embodiment at the Woven fabric that is used for laminated printed circuit boards; The bottom that has moisture bottom Hairstyling composition dried residue on the spun glass of coated fiber yarn thigh of the present invention, wherein said Hairstyling composition contain

HP-1055 like/or epoxyethane derivative, MACOLOP-10 ethoxylated alkyl phenols and the MAZU DF-136 froth breaking material of the epoxy functionalized organo silane coupling agent of

OC-96 styrene-propene acid copolymer hollow ball, PVP K-30 PVP K120, the functional organo silane coupling agent of A-174 vinylformic acid and A-187,

6717 part amidation polymines, STEPANTEX653 palmitinic acid cetyl ester, TMAZ81 sorbitol ester.In addition, can also optionally contain

160 boron nitride powders and/or ORPACBORON NITRIDE RELEASECOAT-CONC dispersion liquid in this embodiment.

Being used for coating composition of the present invention can prepare through any suitable method, for example well known to a person skilled in the art conventional hybrid system.Preferably, above-mentioned component dilute with water is formed have required weight percent solid substance and mix.Can powdered granule and water pre-mixing perhaps, be added to wherein polymeric materials before mixing with other coating composition.

Much mode is given the fibre applicator dope layer, for example through silk is contacted, sprays or other approach with roll-type or belt coating machine.Preferably with coated fibres at room temperature or high temperature down dry.Moisture eliminator is removed the excessive moisture in the fiber and is solidified any curable components in coating compositions (if existence).The used temperature and time of dry glass fiber depends on the multiple factors such as type of percentage composition, the component in the coating composition and the spun glass of solid substance in the coating composition.After super-dry, coating composition generally exists as the dryness finalization resistates on fiber with the amount of the about 25wt% of about 0.1-.The ignition loss of fiber is generally less than about 1.0wt%, preferably less than about 0.5wt%.The about 0.45wt% of more preferably about 0.01-.Here said term " ignition loss " refers to be present in the weight percentage of the lip-deep dry paint compsn of silvalin thigh, confirms according to following equality:

LOI=100 * [(W _Dry-W _Exposed)/W _Dry]

W wherein _DryBe that the silvalin thigh adds coating composition weight of resistates after dry about 60 minutes in about 220 ℉ (about 104 ℃) baking oven, W _ExposedBe to remove the coating composition resistates weight of uncovered fibres yarn thigh afterwards in about 20 minutes through the silvalin thigh is heated in about 1150 ℉ (about 621 ℃) baking oven.

Can be at the coating second coating composition layer above the coating composition layer as stated; Glue spread can effectively be coated with or flood the yarn thigh part that is applied; For example be immersed in the bath that contains second coating composition, second coating composition be sprayed onto on the yarn thigh of coating or and contact with aforesaid coating machine through yarn thigh with coating through yarn thigh with coating.Can let the yarn thigh of coating pass mould, so that remove unnecessary coating composition and/or dry as described above time enough from the yarn thigh, part is dry or solidify second coating composition at least to make it.Applying the used method and apparatus of second coating composition for the yarn thigh is partly determined by the configuration of yarn thigh material.Preferably with method well known in the art that the yarn thigh is dry after applying second coating composition.

Can contain one or more aforesaid film forming materials, lubricant and other additive in the second suitable coating composition.Second coating composition is preferably different with Hairstyling composition, and promptly different component at least a and the Hairstyling composition component chemical is contained in its (1); Or at least a but component that consumption different identical with the contained component of Hairstyling composition contained in (2).The non-limiting example of the second suitable coating composition comprises urethane, like US patent 4,762,750 and 4,762, and 751 disclosed urethane, it is introduced here as a reference.

In another preferred embodiment of the present invention, can apply conventional Hairstyling composition on the spun glass of silvalin thigh or contain the dried residue undercoat of Hairstyling composition of any typing component of above-mentioned content.The instance of suitable Hairstyling composition is seen Loewenstein237-291 page or leaf (the 3rd edition, 1993) and US patent 4,390,647 and 4,795,678, each piece all is incorporated herein by reference.Be used at least a portion that the second coating composition layer described herein of the present invention is coated to priming paint, preferably at whole superficies.Second coating composition can comprise the particle of one or more types shown in aforesaid and/or the following table B.Should be noted that the hardness of these particulate Mohs hardness, promptly about 4.5-about 6 greater than spun glass.Yet because these particles are parts of second coating composition, second coating composition does not directly contact with the surface of spun glass, so the particle of these higher hardness can influence spun glass sharply and be acceptable.

Table B

Solid inorganic material	Heat conductance (W/m K, 300K)	Resistivity (micro-ohm-centimetre)	Mohs hardness (original scale)
				SP 1	About 200 29	1.7×10 19?30	About 2 31
Boron phosphide BP	About 350 32	-	About 9.5 33
				Aluminium phosphide	About 130 34	-	-
Aluminium nitride AlN	About 200 35	Greater than 10 19?36	About 9 37
				Gan	About 170 38	-	-
Gallium phosphide	About 100 39	-	-
				Silit	About 270 40	4×10 5-1×10 6?41	Greater than 9 42
Silicon nitride	About 30 43	10 1910 20?44	About 9 45
				Beryllium oxide	About 240 46	-	About 9 47
Zinc oxide	About 26	-	About 4.5 48
				Zinc sulphide	About 25 49	2.7×10 5-1.2×10 12?50	About 3.5-4 51

" 29G.Slack the nonmetal crystal of high heat conductance " physical chemistry solid magazine (J.Phys.Chem.Solids)(1973) 34 volume p322 are incorporated herein by reference.(1997) the 654th pages of the synthetic and processing of (30A.Weimer volume) carbide, nitride and boride material

31 Friction, wearing and tearing, lubricatedThe 27th page

" 32G.Slack the nonmetal crystal of high heat conductance " physical chemistry solid magazine (J.Phys.Chem.Solids)(1973) 34 volume p325 are incorporated herein by reference.

33R.Lewis, Sr. Hawley ' s condensation chemical dictionary(the 12nd edition 1993) the 164th page introduced here as a reference.

" 34G.Slack the nonmetal crystal of high heat conductance " physical chemistry solid magazine (J.Phys.Chem.Solids)(1973) 34 volume p333 are incorporated herein by reference.

" 35G.Slack the nonmetal crystal of high heat conductance " physical chemistry solid magazine (J.Phys.Chem.Solids)(1973) 34 volume p329 are incorporated herein by reference

(1997) the 654th pages of the synthetic and processing of (36A.Weimer volume) carbide, nitride and boride material

37 Friction, wearing and tearing, lubricatedThe 27th page

" 38G.Slack the nonmetal crystal of high heat conductance " J.Phys.Chem.Solids(1973) 34 volume p333,

" 39G.Slack the nonmetal crystal of high heat conductance " J.Phys.Chem.Solids(1973) 34 volume p321 are incorporated herein by reference

40 Microelectronics assembling handbookThe 36th page, be incorporated herein by reference

41A.Weimer (1997) the 653rd pages of the synthetic and processing of (volume) carbide, nitride and boride material are incorporated herein by reference

42 Friction, wearing and tearing, lubricatedThe 27th page

43 Microelectronics assembling handbookThe 36th page, it is for reference to introduce this paper

(1997) the 654th pages of the synthetic and processing of (44A.Weimer volume) carbide, nitride and boride material

45 Friction, wearing and tearing, lubricatedThe 27th page

46 Microelectronics assembling handbookThe 905th page is incorporated herein by reference

47 Hawley ' s condensation chemical dictionary(the 12nd edition 1993) the 141st page introduced here as a reference.

48 Friction, wearing and tearing, lubricatedThe 27th page

49 Chemistry and physics handbookCRC press (1975) 12-54 pages or leaves

50 Chemistry and physics handbookCRC press (the 71st edition, 1990) 12-63 page or leaf is introduced here as a reference

Table B (continuing)

Solid inorganic material	Heat conductance (W/m K, 300K)	Resistivity (micro-ohm-centimetre)	Mohs hardness (original scale)
				Diamond	About 2300 52	2.7×10 8?53	10 54
Silicon	About 84 55	About 10.0 56	About 7 57
				Graphite	Maximum 2000 58	100 59	About 0.5-1 60
Molybdenum	About 138 61	About 5.2 62	About 5.5 63
				Platinum	About 69 64	About 10.6 65	About 4.3 66
Palladium	About 70 67	About 10.8 68	About 4.8 69
				Tungsten	About 200 70	About 5.5 71	About 7.5 72
Nickel	About 92 73	About 6.8 74	About 5 75
				Aluminium	About 205 76	About 4.3 77	About 2.5 78
Chromium	About 66 79	About 20 80	About 9.0 81
				Copper	About 398 82	About 1.7 83	About 2.5-3 84
Gold	About 297 85	About 2.2 86	About 2.5-3 87
				Iron	About 74.5 88	About 9 89	About 4-5 90
Silver	About 418 91	About 1.6 92	About 2.5-4 93

51 Chemistry and physics handbookCRC press (the 71st edition, 1990) 4-158 page or leaf is introduced here as a reference

52 Microelectronics assembling handbookThe 36th page

53 Chemistry and physics handbookCRC press (the 71st edition, 1990) 12-63 page or leaf is introduced here as a reference

54 Chemistry and physics handbookThe F-22 page or leaf

55 Microelectronics assembling handbookThe 174th page

56 Chemistry and physics handbookThe F-166 page or leaf is introduced here as a reference

57 Friction, wearing and tearing, lubricatedThe 27th page

" 58G.Slack the nonmetal crystal of high heat conductance " physical chemistry solid magazine (J.Phys.Chem.Solids)(1973) 34 volume p322 are incorporated herein by reference.

59 referring to W.Callister Materials science and Engineering Notice(the 2nd edition, 1991) the 637th page introduced here as a reference

60 Chemistry and physics handbookThe F-22 page or leaf

61 Microelectronics assembling handbookThe 174th page

62 Microelectronics assembling handbookThe 37th page

63 according to " network element " http://www.shef.ac.uk/ ~ chem/web-elents/nofr-image-1/hardness-minerals-l.html (1998.2.26)

64 Microelectronics assembling handbookThe 174th page

65 Microelectronics assembling handbookThe 37th page

66 Chemistry and physics handbookThe F-22 page or leaf

67 Microelectronics assembling handbookThe 37th page

68 Microelectronics assembling handbookThe 37th page

69 Chemistry and physics handbookThe F-22 page or leaf

70 Microelectronics assembling handbookThe 37th page

71 Microelectronics assembling handbookThe 37th page

72 according to " network element " http://www.shef.ac.uk/ ~ chem/web-elents/nofr-image-1/hardness-minerals-l.html (1998.2.26)

73 Microelectronics assembling handbookThe 174th page

74 Microelectronics assembling handbookThe 37th page

75 Chemistry and physics handbookThe F-22 page or leaf

76 Microelectronics assembling handbookThe 174th page

77 Microelectronics assembling handbookThe 37th page

78 Friction, wearing and tearing, lubricatedThe 27th page

79 Microelectronics assembling handbookThe 37th page

80 Microelectronics assembling handbookThe 37th page

81 Chemistry and physics handbookThe F-22 page or leaf

82 Microelectronics assembling handbookThe 174th page

83 Microelectronics assembling handbookThe 37th page

84 Chemistry and physics handbookThe F-22 page or leaf

85 Microelectronics assembling handbookThe 174th page

86 Microelectronics assembling handbookThe 37th page

87 Chemistry and physics handbookThe F-22 page or leaf

88 Microelectronics assembling handbookThe 174th page

89 Chemistry and physics handbookCRC press (1975) D-171 pages or leaves are incorporated herein by reference

90 Chemistry and physics handbookThe F-22 page or leaf

91 Microelectronics assembling handbookThe 174th page

92 Microelectronics assembling handbookThe 37th page

93 Chemistry and physics handbookThe F-22 page or leaf

Molybdenumdisulphide and Natural manganese dioxide are other inorganic particles that can be used as the present invention second or the 3rd coating.Any mixture that those skilled in the art can understand above-mentioned inorganic particle can be used for the present invention.

In another embodiment, the particle of second coating composition comprises hydrophilic inorganic particle, the moisture in this particle absorption and the reservation hydrophilic granules gap.Hydrophilic inorganic particle is when absorbing moisture with contact with moisture or when participating in the chemical reaction with moisture or expanding; Form for example adhesive gel-like solution, blocking-up or suppress in the gap that moisture further gets into the communication cable that uses the reinforcement of coated glass silvalin thigh.Here said " absorption " is meant that water infiltrates among internal structure or the gap of water wetted material and is retained in wherein basically.Referring to Hawley ' s condensation chemical DictionaryPage 3 is introduced here as a reference." expansion " refers to that the size of hydrophilic granules or volume enlarge.Referring to Webster ' s redbrick dictionary(1977) the 1178th pages, it is introduced here as a reference.Preferably, hydrophilic granules is at least one times and sesqui contacting after to its original dry weight with water, and more preferably about 2-of its original weight is about 6 times.Expansive hydrophilic inorganic solid lubricant particulate non-limiting example comprises smectite, for example vermiculite, smectite; Absorptivity zeolite and inorganic absorptivity gel.Preferably, these hydrophilic granules with form of powder be coated in viscosity typing or other viscosity second coating material above.In this embodiment of second coating composition, the amount of hydrophilic inorganic particle can be the about 99wt% of about 1-in total solids, the about 90wt% of preferably about 20-.

The amount of inorganic particle can serve as the about 99wt% of about 1-in total solids in second coating composition, the about 90wt% of preferably about 20-.Solid per-cent is generally the about 75wt% of about 5-in moisture second coating composition.

In another embodiment of the invention; Can be at least a portion surface of second coating and preferably on whole surface, apply the 3rd coating composition layer, promptly this silvalin thigh has the skin of typing priming paint layer, the second coating composition layer and the 3rd coating.The 3rd coating preferably is different from the Hairstyling composition and second coating composition, and promptly the 3rd coating composition (1) contains different component at least a and the typing and the component chemical of second coating composition; Or (2) are contained at least a with typing or the contained component of second coating composition is identical but component that consumption is different.Before or after being blended into fabric, use such as (but being not limited thereto) foregoing spraying and dip-coating and technology known in the art apply the 3rd coating for spun glass and yarn thigh.

In this embodiment; Contain one or more aforesaid polymeric materialss in second coating composition; Urethane for example; And contain powdery heat conductance inorganic particle in the 3rd coating composition; For example aforesaid boron nitride particle, or hollow bead, for example aforesaid

pigment.Preferably, the coating of powder-type coating is through letting the yarn thigh that is coated with liquid second coating composition pass fluidized-bed or spraying equipment, so that powdered granule is sticked on viscosity second coating composition.Perhaps, as shown in Figure 4, can the yarn thigh be assembled into fabric 114, apply the layer 140 of the 3rd coating then.Stick to the powdery on the coating yarn thigh, the weight percent of heat conductance inorganic particle can be the about 75wt% of about 0.1-of dry yarn thigh gross weight.Can also contain one or more aforesaid polymeric materialss in the 3rd coating, like XPA class, epoxides or polyolefins; Conventional stablizer and other modifying agent of this coating known in the art are preferably with the form of dry powder.

After fiber forms, directly be coated in coating composition of the present invention on the spun glass although the discussion of front relates on the whole; Subsequently fiber is blended into fabric, but those skilled in the art are to be understood that the present invention also is included in use various technology well known in the art and processes the embodiment that fabric applies coating composition of the present invention afterwards.According to the processing of fabric, coating composition of the present invention can directly apply to the spun glass in the fabric or apply gives the another kind of coating on spun glass and/or fabric already.For example, can be after forming and being woven to fabric, with conventional starch-oily setting agent coated glass fiber.Then, handle fabric to remove destarching-oily setting agent.Afterwards, can use technique known will be used for the direct coated fabrics of the disclosed coating composition of this paper of the present invention, for example (but being not limited thereto) sprays or fabric is immersed in the bath of Hairstyling composition.Then can with fabric further processing so that make on fiber that the composition residues thing stays fabric and the yarn thigh before with fabric drying.The removal of this setting agent can use technology well known in the art to accomplish, for example thermal treatment or laundering of textile fabrics.In this example, coating composition directly is coated on the surface of fabric fibre.If the original any part that forms the Hairstyling composition on the spun glass of back that is coated in is not removed, then coating composition of the present invention is coated in the rest part of Hairstyling composition, rather than directly is coated in fiber surface.

In another embodiment of the invention, after forming, immediately the selection component of coating composition of the present invention is applied to spun glass, and treat after fabric is processed all the other components of coating composition to be applied to fabric.With the mode of discussing above similar, can remove some or whole selection components from spun glass before with all the other component coated fibers and fabric.As a result, all the other components directly are coated on the surface of fabric fibre, perhaps are coated on to select component not by the part of removing from fiber surface.

With the strengthening agent of Woven fabric 14 as reinforcement property matrix material 12, as shown in Figure 1 to form composite members or laminate 10, preferably in circuit card, use.Twist thread before technology (for example using the frame of twisting thread to twist with the fingers into the yarn thigh of about 3 circles of the about 0.5-of per inch) weaves in known any routine by one of skill in the art, can the warp thread and the weft strands of fabric 14 not twisted (being also referred to as untwisting or non-twist) or twisted.In addition, fabric 14 can contain twisting and the various combinations that do not add twist warp and weft strands.

Reinforcement property fabric 14 every centimetre can comprise the about 100 warp thread thighs of about 5-(the about 254 warp thread thighs of the about 13-of per inch), and preferred every centimetre of weft strands has about 50 weft strands of about 6-(about 127 weft strands of the about 15-of per inch).Woven structure plain weave is regularly made, and also can use to well known to a person skilled in the art any other weaving form, and for example twill weave or satin weave are weaved.

Preferably; The pattern that uses with the laminate that is adapted at being used for printed substrate comes Woven fabric 14; For example disclosed in " world's fabric ", the technical bulletin (1995) of the Clark-Schwebel company of Anderson (South Carolina) is introduced here as a reference.Using the instance of the indefiniteness fabric patterns of E225E-spun glass is Style2116, and its per 5 centimetres have 118 warp thread and 114 weft yarns (60 warp thread of per inch and 58 weft yarns); Use 7221x0 (E2251/0) warp thread and weft yarn; Have nominal fabric thickness 0.094mm (0.037 inch) and fabric weight 103.8g/cm ²(3.06 ounce per square yard).Using the instance of the indefiniteness fabric patterns of G75E-spun glass is Style7628, and its per 5 centimetres have 87 warp thread and 61 weft yarns (44 warp thread of per inch and 31 weft yarns); Use 9681x0 (G751/0) warp thread and weft yarn; Have nominal fabric thickness 0.173mm (0.0068 inch) and fabric weight 203.4g/m ²(6.00 ounce per square yard).Using the instance of the indefiniteness fabric patterns of D450E-spun glass is Style1080, and its per 5 centimetres have 118 warp thread and 93 weft yarns (60 warp thread of per inch and 47 weft yarns); Use 5111x0 (D4501/0) warp thread and weft yarn; Have nominal fabric thickness 0.053mm (0.0021 inch) and fabric weight 46.8g/m ²(1.38 ounce per square yard).Using the instance of the indefiniteness fabric patterns of D900E-spun glass is Style106, and its per 5 centimetres have 110 warp thread and 110 weft yarns (56 warp thread of per inch and 56 weft yarns); Use 55.51x0 (D9001/0) warp thread and weft yarn; Have nominal fabric thickness 0.033mm (0.013 inch) and fabric weight 24.4g/m ²(0.72 ounce per square yard).Using the instance of another indefiniteness fabric patterns of D900E-spun glass is Style108, and its per 5 centimetres have 118 warp thread and 93 weft yarns (60 warp thread of per inch and 47 weft yarns); Use 55.51x2 (D9001/2) warp thread and weft yarn; Have nominal fabric thickness 0.061mm (0.0024 inch) and fabric weight 47.5g/m ²(1.40 ounce per square yard).Using the instance of the indefiniteness fabric patterns of E225 and D450E-spun glass simultaneously is Style2113, and its per 5 centimetres have 118 warp thread and 110 weft yarns (60 warp thread of per inch and 56 weft yarns); Use 7221x0 (E2251/0) warp thread and 5111x0 (D4501/0) weft yarn; Have nominal fabric thickness 0.079mm (0.0031 inch) and fabric weight 78.0g/m ²(2.30 ounce per square yard).Using the instance of the indefiniteness fabric patterns of G50 and G75E-glass fiber yarn simultaneously is Style7535, and its per 5 centimetres have 87 warp thread and 57 weft yarns (44 warp thread of per inch and 29 weft yarns); Use 9681x0 (G751/0) warp thread and 9991x0 (G501/0) weft yarn; Have about 0.201mm of nominal fabric thickness (about 0.0079 inch) and the about 232.3g/m of fabric weight ²(about 6.85 ounce per square yard).These with other fabric patterns that is suitable for explanation see IPC-EG-140 " be used for printed substrate by ' the woven finished product fabric explanation of E ' glass " switching and assembling circuit institute publication (1997.6), it is introduced here as a reference.Although what aforesaid fabric patterns was used is the yarn of twisting, comprises and use non-twist yarn or rove together with twist yarn or replace twist yarn these or other fabric patterns constructed in accordance.Also comprise in the fabric some or all warp thread have with first kind of resin compatible Hairstyling composition coated fibres; And some or all weft yarn have with the second kind of resin compatible coating coated fibres that is different from first kind of compsn, promptly second kind of compsn (1) contains different component on the component chemical of at least a and first kind of Hairstyling composition; Or (2) contain at least a with first kind the contained component of Hairstyling composition is identical but component that consumption is different.

Can known by one of skill in the art conventional loom form and be fit to the suitable reinforcement property fabric 14 of weaving of the present invention, for example shuttle-type or rapier loom, but preferably use the air spray loom to form.When using air spray technology Woven fabric, the air spray loom inserts weft yarn in the warp thread shed open and promotes yarn through the pressurized air stream from one or several air nozzle crosses width of fabric.Preferred air spray loom can be purchased acquisition from the Tsudakoma of Japan, and model is 103,103I and 1033; And Sulzer Ruti L-5000, L-5100, the L-5200 type that can be purchased acquisition from Zurich, Switzerland Sulzer Brothers company; The Sulzer Ruti L-5000 of Switzerland Sulzer Ruti company, L-5100 and L-5200 product communique, it is introduced here as a reference.

Referring now to Fig. 1,, can use fabric 14 to come form layers casting die 10, through with 12 coatings of heat of polymerization plasticity or thermoset matrix material and/or flood one or more layers fabric 14.Laminate 10 is suitable as charge carrier.

Can be used for substrate material of the present invention and comprise thermosetting material such as thermosetting polyester class, vinyl ester, epoxides (molecule contains at least one epoxy or Oxyranyle, like the polyglycidyl ether of polyvalent alcohol or mercaptan), phenoplast, aminoplastics, heat-curable urethane class, its verivate and mixture.The preferred substrate material that is used to form the laminate of use in printed circuit board is FR-4 epoxy resin, polyimide and liquid crystalline polymers, and its composition is known in those skilled in the art.If further need the information of relevant this compsn, referring to 1 The electronic material handVolume ^TM, ASM International (1989) 534-537 pages or leaves.

The non-limiting example of suitable thermoplastic polymer matrix's material comprises polyolefins, polyamide-based, thermoplastic polyurethanes and thermoplastic polyester class, vinyl polymer class and composition thereof.The instance of the thermoplastic material that other is useful comprises polyimide, polyethersulfone, polyphenylsulphine, polyetherketone, ppe, polyphenylene sulfide, polyacetal, SE and polycarbonate.

A kind of useful substrate material prescription is made up of EPON1120-A80 epoxy resin, Dyhard RU 100, glyoxal ethyline and DOWANOL PM.

Other component that matrix material and reinforcement property material can comprise in the composite members comprises tinting material or pigment, lubricant or processing aid, ultraviolet ray (UV) stablizer, inhibitor, other filler and extender.

Can fabric 14 be immersed in coating and impregnate fabric 14, for example R.Tummala (volume) in the bath of matrix material 12 Microelectronics assembling handbook(1989) 895-896 pages or leaves are described, and it is introduced here as a reference.Can according to the factors such as type of used matrix material matrix material 12 and fabric 14 be processed to form composite members or laminate 10 through the whole bag of tricks.For example, concerning thermoset matrix material, can be through compression moulding or injection moulding, pultrusion, hand coating, or through plate material forming after compression moulding or the injection moulding, form layers casting die.Can be through in substrate material, being mingled with linking agent and/or the thermosetting polymer substrate material being solidified through using for example to heat.The suitable linking agent that can be used for the crosslinked polymer matrix material as stated.The solidification value of thermosetting polymer substrate material and time are depended on the thickness factors such as (only giving some instances) of the type of used matrix material, other additive in the matrix system and composite members.

Concerning the thermoplastic matrix material, the proper method that forms composite members comprise direct mold pressing or extrude compound, then injection moulding.Be used for the visible I.Rubin of method and apparatus that aforesaid method forms composite members Plastic material and TM(1990) 955-1062,1179-1215 and 1225-1271 page or leaf, it is introduced here as a reference.

Be not restricted to the present invention, in an embodiment shown in Figure 5, composite members or laminate 210 comprise the fabric 214 with compatible matrix material 212 dippings.Can the fabric of this dipping be pressed between one group of metering roll or bar then, leaving the substrate material of measured quantity for, and the dry charge carrier that forms semicure base material form or prepreg form.Can conductance layer 250 be set in the position along prepreg one side 252 parts, its mode is discussed as follows, and prepreg is solidified, form layers casting die 210, and it works charge carrier 254 effects that have conductance layer.In another embodiment of the invention, and more typically in charge carrier industry, two or more prepregs and one or more conductance layer are merged, and laminated together and solidify the formation charge carrier with the mode that well known to a person skilled in the art.For example (but not limiting the present invention) can through under high temperature and high pressure with the predetermined long time (for example between the polishing steel plate) of stack compacting so that cure polymer substrate material and form the laminate of desired thickness comes lamination prepreg stack.Lamination with solidify before or after, apply conductance layer for the part of one or more prepregs have at least the laminate of one deck conductance layer (below be called " coating laminate ") so that the charge carrier of gained is a part of surface of exposed surface.

Then, use the technology of well known to a person skilled in the art to form circuit, to be configured to the charge carrier of circuit card form by the conductance layer of single or multiple lift shape charge carrier.

If desired; Can be through any mode that makes things convenient for known in the art; In charge carrier, form aperture or hole (being also referred to as " path "), allow the circuit on the relative two sides of charge carrier and/or element to be electrically connected each other, comprise (but being not limited thereto) machine drilling and laser drill.Say that more specifically referring to Fig. 6, aperture 360 extends through one deck at least 362 of the fabric 312 on the charge carrier 354 of the present invention.Fabric 312 comprises coated fibres yarn thigh, and said silvalin thigh contains at least a spun glass, and this spun glass has one deck and the compatible layer of said various polymer matrix material here.In the process that forms aperture 360, charge carrier 354 is positioned under the hole-forming device, like drill bit 364 or laser head.Through using brill 364 or laser drill, part 366 places on one deck at least 362 of fabric 312 form hole 360.After the hole forms, electro-conductive material is deposited upon on the wall in hole or use the electro-conductive material filling orifice, so that help required electrical connection and/or heat dissipation between charge carrier 354 lip-deep one or more conductive layers (demonstration among Fig. 6).

Conductance layer, layer 250 as shown in Figure 5 can known by one of skill in the art any method form.For example (but being not limited thereto) conductance layer can be through forming metallic substance paper tinsel or tab laminate at least a portion of semicure or curing prepreg or laminate one side.Perhaps, conductance layer can through use well known to a person skilled in the art technology comprise (but being not limited thereto) metallide, electrodeless plating or sputter metallic substance is deposited upon semicure solidify prepreg or at least a portion of laminate one side on form.The metallic substance that is suitable as the conductance layer use comprises (but being not limited thereto) copper (preferably), silver, aluminium, gold, tin, tin-lead alloy, palladium and combination thereof.

In another embodiment of the invention, charge carrier can be through the form with the multilayer shape circuit card of one or more circuit cards (as stated) and one or more coating laminate (as stated) and/or one or more prepreg (as stated) formation laminated together.If desired, can additional conductance layer be admixed in the charge carrier, for example on the part of multilayer shape circuit card exposed side.In addition, if desired, can form additional circuit by conductance layer by aforesaid mode.Should understand the relative position according to each layer of multilayer shape circuit card, plate can not only have internal circuit but also have external circuit.Can be formed as described above part and pass or pass completely through the addition of vias of plate, allow between the layer of select location, to be electrically connected.The structure that should understand gained can have some apertures that extend fully through structure, some extend aperture that part only passes structure and some all are positioned at the aperture of structure.

Preferably, the thickness that forms the laminate of charge carrier 254 is greater than about 0.051mm (0.002 inch), and more preferably about 0.13mm (0.005 inch) is to about 2.5mm (about 0.1 inch).For eight flaggy laminate of 7628 type fabrics, its thickness is generally about 1.32mm (0.052 inch).The number of plies of fabric 14 can be according to the required thickness of laminate and difference in the laminate 10.

Resin content in the laminate can be the about 80wt% of about 35-, more preferably from about the about 75wt% of 40-.The amount of fabric can be the about 65wt% of about 20-in the laminate, more preferably from about the about 60wt% of 25-.

By weaving E-glass fabric and the laminate of using FR-4 epoxy matrix material base material to process, its minimum second-order transition temperature is about 110 ℃; The required minimum bend intensity of machine direction or width (perpendicular to the longitudinal axis of fabric) is greater than 3 * 10 according to IPC-4101 " the basic material explanation that rigidity and multilayer board are used " the 29th page (switching and assembling circuit institute publish (1997.12)) ⁷Kg/m ², be preferably greater than about 3.52 * 10 ⁷Kg/m ²(about 50kpsi) is more preferably greater than about 4.9 * 10 ⁷Kg/m ²(about 70kpsi).The content of IPC-4101 is all introduced here as a reference.(longitudinal axis that generally is parallel to fabric) along its length, required minimum bend intensity is greater than about 4 * 10 ⁷Kg/m ², be preferably greater than 4.23 * 10 ⁷Kg/m ²Flexural strength uses the metal of through etching fully removing coating to measure according to switching and the ASTM D-790 of assembling circuit institute and IPC-TM-650 test methods manual (1994.12) (introducing as a reference) here, and wherein said etching is the 3.8.2.4 part according to IPC-4101.The advantage of charge carrier of the present invention comprises high bending strength (stretching and compressive strength) and high-modulus, can reduce the distortion of the circuit card that comprises laminate thus.

The charge carrier of copper cap rock FR-4 epoxy resin laminate form of the present invention; It is along 50 ℃-288 ℃ thermal expansivity (" Z-CTE ") of laminate Z direction; Promptly pass the thickness of laminate; Preferably less than about 5.5%, the about 5.0wt% of more preferably about 0.01-is according to IPC TP 2.4.41 (being incorporated herein by reference).Each such laminate preferably contains eight layer of 7628 type fabric, also can change the fabric of 106,108,1080,2113,2116 or 7535 types of use.In addition, the combination that laminate can these fabric patterns of fusion.The as a rule difficult distortion of expanding and shrinking and can reduce plate of laminate with low thermal coefficient of expansion.

The present invention also comprises the manufacturing of multilayer shape laminate and circuit card; Wherein said multilayer shape laminate and circuit card comprise one deck at least according to the composite bed of telling about making here and one deck at least use with the composite members layer of telling about here the composite bed made of different modes, as use conventional spun glass compounding technology making.More specifically say and as well known to a person skilled in the art; Traditionally; Long filament in the glass continuous filament yarn thigh that uses in the Woven fabric is handled with starch/oily setting agent; Said setting agent contains starch or amylose starch, Wecobee M, positively charged ion wetting agent, emulsifying agent and the water of partially or completely gelatinization, comprises (but being not limited thereto) LowensteinDisclosed in the 237-244 page or leaf (the 3rd edition, 1993), it is introduced here as a reference.To before weaving, use solution-treated by the warp thread of these yarn thigh productions afterwards, and not receive the abrasion in the weaving process with protection yarn thigh, and for example use like US patent 4,530,67 row-Di 11 row disclosed gathering (vinyl alcohol) of 4 hurdles of 876 the 3rd hurdles, it is introduced here as a reference.This operation is commonly referred to as sizing.It is as a rule incompatible with the matrix material that composite members manufacturers uses to gather (vinyl alcohol) and starch/oily setting agent; And fabric must pass through cleaning, so that woven textile impregnation is being removed organic substances all on the fiberglass surfacing before basically.This can accomplish through variety of way, and for example through cleaning fabric, more common is to come heat-treated fabric through mode well known in the art.The result of clean operation makes between the fiberglass surfacing of matrix material that impregnate fabric uses and cleaning not have suitable interface, so that must use coupling agent to fiberglass surfacing.This performance field technique personnel are called textile finishing sometimes.The most frequently used coupling agent is a silane in the textile finishing operation, comprises (but being not limited thereto) E.P.Plueddemann Silane coupling agent(1982) 146-147 pages or leaves are disclosed, and it is introduced here as a reference.Also referring to Loewenstein249-256 page or leaf (the 3rd edition, 1993).Through after the silane treatment, with the matrix material dipping of fabric, between the metering roll group, press and drying with consistency, form the prepreg of aforesaid semicure.Employed matrix resin in character, clean operation and/or the composite members according to setting agent should be understanded, sizing and/or textile finishing step can be exempted.Then, can prepreg and one or more fusion prepreg of the present invention of the conventional spun glass compounding technology of one or more fusion is combined, form aforesaid charge carrier, be multilayer shape laminate or circuit card specifically.About making the more information of circuit card, referring to 1 The electronic material handbook ^TM ASMInternatioanl (1989) 113-115 pages or leaves; R.Tummala (volume) Microelectronics assembling handbook(1989) 858-861 and 895-909 page or leaf; M.W.Jawitz The printed substrate handbook(1997) 9.1-9.42 page or leaf and C.F.Coombs, Jr. (volume) The printed substrate handbook(the 3rd edition, 1988) 6.1-6.7 page or leaf, it is introduced here as a reference.

The composite members and the laminate that form charge carrier of the present invention can be used to form the assembly in the electronic industry, the one-level of more specifically saying so, secondary and/or three level assemblies, and disclosed like Tummala 25-43 page or leaf, it is introduced here as a reference.In addition, the present invention can also be used for other component-level.

The present invention will illustrate through following concrete indefiniteness embodiment now.

Embodiment 1

The electricity level laminate that test is processed by the prepreg of fusion fabric; Said fabric contains the yarn with different Hairstyling compositions; To estimate its boring performance, more specifically say (i) on laminate boring brill the bit wear rate and (ii) bored the tolerance range of position in the hole of laminate.Contrast A and sample B are the laminate of foregoing fusion 7628 type fabrics.Fabric among the contrast A is the fabric that thermal cleaning and silane were put in order, and it can be purchased acquisition from Clark Schwebel, and regards as 7628-718.Fabric among the sample B is by the yarn weaving that contains spun glass, and said spun glass is coated with like said and the resin compatible setting agent shown in the table 1 here.The ignition loss that is woven into the spun glass of sample B is 0.35%.

Table 1

The component of used setting agent is in the weight percent of total solids among the sample B

Component	Sample B
		The thermoplastic polyester film-forming polymer 94	27.0
The thermoplastic polyester film-forming polymer 95	36.2
		PVP K120 96	9.0
Epoxy functionalized organo silane coupling agent 97	2.1
		The functional organo silane coupling agent of vinylformic acid 98	4.4
The polyoxyalkylene group block copolymer 99	9.0
		Polymeric amide 100。	4.4
Emulsifying agent 101	5.4
		The boron nitride powder particle 102	0.9
25wt% SP 1 aqueous dispersions 103	1.5
		Acetate	<0.1

The 94RD-847A vibrin can be purchased acquisition from the Borden Chemicals of Ge Lunbiya (Ohio)

The polyethylene glycol adipate glycol of 95DESMOPHEN2000 can be purchased acquisition from the Bayer of Pittsburgh (Pennsylvania)

96PVP K-30 PVP K120 can be purchased acquisition from the ISP chemical company of Wayne (New Jersey)

97A-187 γ glycidoxypropyltrime,hoxysilane can be purchased acquisition from the OSi Specialties company of Tarrytown (New York)

98A-174 γ methacryloxypropyl trimethoxy silane can be purchased acquisition from the 0Si Specialties company of Tarrytown (New York)

99PLURONICTMF-108 polyoxypropylene-polyoxyethylene copolymer can be purchased acquisition from BASF AG of Parsippany (New Jersey)

The 100VERSAMID140 polymeric amide can be purchased from General Mills chemical company and obtain 101MACOL NP-6 nonylphenol tensio-active agent, can be purchased acquisition from the BASF of Parsippany (New Jersey)

102

PT160 boron nitride powder particle, can be purchased acquisition from the Advanced Ceramics company of Lakewood (Ohio)

103 ORPAC BORON NITRIDE RELEASECOAT-CONC can be purchased acquisition from the ZYP Coatings company of Oak Ri dge

Through hand coating prepared prepreg, comprise and use painting brush to apply standard FR-4 epoxy resin (the EPON1120-A80 resin can be purchased acquisition from shell chemical company) to fabric.Immediately that resin is saturated fabric " drying ", and in the baking oven of heat release air, descended the about 3-in second rank (B-stages) about 3.25 minutes in 163 ℃ (325 ℉), until reaching 171 ℃ of required gelation times that (340 ℉) is following 124 seconds.Prepreg is trimmed to the section of 46cm * 46cm (18 inches * 18 inches), and weighs to confirm resin content.In lamination process subsequently, only using resin content is 44% ± 2% prepreg.

Pile up the prepreg of 8 floor heights and at Wabash Press in 177 ℃ (350 ℉) and 345 newton/cm ²(500psi) molded is 70 minutes.All laminate are carried out moulding and are not had copper foil layer.Remaining air in various degree in the laminate.It is believed that and lack in lamination process that vacuum helps and temperature fluctuation will help this situation.

Tool wear is analyzed

Carry out first campaign, estimate the wearing and tearing of drill bit.The wearing and tearing of drill bit are expressed by term " drill bit percentage wear rate ", use following formula to calculate it:

Drill bit percentage wear rate=100 * (P _i-P _f)/P _i

P wherein _iThe original width of=original cut edge

P _f=bored the width of original cut edge after the hole of regulation

Referring to Fig. 7, bore the width 470 of 474 original cut edge 472 in drill bit circumferential edge edge calculations.

Use the single head punch to hole.On the laminate (as stated) of 3 heap floor heights, hole, wherein laminate has the thick thick phenolic coated base plate of the paper heart of aluminium inlet (entry) and 1.88mm (0.074 inch) of 0.203mm (0.008 inch).Once bore the normally standard operation in the industry of 3 laminate.Measure the drill bit percentage wear rate of two kinds of drill diameters: 0.35mm (0.0138 inch) and 0.46mm (0.018 inch).Two kinds of brills all are the 508 serial carbide burs that obtain from Gardenia (California) Tulon company.In the boring procedure each instrument is kept 0.001 constant cutting load.Here said " cutting load " refers to bore the ratio that inserts speed (pressing the PM inch measures) and spindle speed (measuring by rotations per minute (rpm)).Concerning the brill of 0.35mm, spindle speed is 100,000rpm and insert speed be 100 inches (254cm)/minute.Concerning the brill of 0.46mm, spindle speed is determined as 80,000rpm and insert speed be 80 inches (203cm)/minute.To these two kinds of tool diameters, keep constant retraction rate 2.54m (1000 inches)/minute and the drill bit upper limit of 1.65mm (0.065 inch).Here said " the drill bit upper limit " refers to that drill bit returns the distance of removing more than the laminate upper surface.

By shown in Figure 8; Boring pattern based on 500 holes calculates drill bit percentage wear rate; Be included in and bore 391 holes (section 580) in 0.635cm * 10.16cm (0.25 inch * 4 inches) piece; Then the pattern by 10 * 10 holes bores 100 holes (section 582), and then the pattern by 3 * 3 holes bores 9 holes (section 584).Hole density with 62 hole/square centimeters (400 hole/square inches) is bored the hole in each section.Repeat this pattern other three times, reach 2000 holes altogether.Use Uniline2000 single head punch to carry out drill test 1 and 2, and use CNC-7 single head punch to carry out drill test 3.Two kinds of punchs are all from the Esterline Technologies of Bellevue (Washington).

Table 2 shown 0.35 with the brill of 0.46mm diameter for contrast A and sample B with 2000 drill bit percentage wear rates afterwards of aforesaid pattern boring.During each on-test with new drill bit.

Table 2

As shown in table 2; Sample B in the test 1 and 2; It contains glass fiber, and said glass fiber has been coated with the setting agent compatible with the laminate matrix resin of the present invention, bored 2000 drill bit percentage wear rates after the hole be starkly lower than the contrast A; Contain glass fiber among the contrast A, this glass fiber had carried out thermal cleaning before the arrangement setting agent of coating silane.Test 3 has only shown the MIN improvement of drill bit percentage wear rate, but it is believed that this be since in this test used CNC-7 punch more outmoded and the contrast than low degree is provided in drill test than testing 1 and 2 used Unil ine2000 punchs.

Position precision

The tolerance commonly used of estimating laminate boring performance is the tolerance range of hole site.The deviation in range of the position imaginary, definite position in this test determination hole with it.Measurement is carried out on the lower surface of the lowest layer casting die of 3 laminate heap layer, wherein bore and leave laminate heap layer since the position that reckons with this hole with expect or " correct " hole site maximum deviation is arranged.This difference is estimated by " offset distance ", the hole of promptly boring on the laminate surface distance between the imaginary real center position in heart position and hole of hitting really.Boring 500 holes as described above continuously and repeating after 4 times, promptly each instrument bores altogether after 2000 holes, the measurement deviation distance.Measure the offset distance of last 100 boring patterns (being last boring section 582).Use 508 series brill borings of the 0.46mm of Tulon company type (0.018 inch) diameter as stated.As what use in the tool wear test, the spindle speed of brill is 80, and 000rpm and insertion speed are 80 inch per minute clocks, and cutting load is 0.001.To contrast A and sample B revision test 8 times, use green bit during on-test at every turn.

Table 3 has shown that contrast A and sample B are in the result of position precision test after 2000 that holes.

Table 3

This shows that sample B comparison is showed lower offset distance according to A, this situation is especially obvious when laminate being used as the charge carrier of big metering-orifice of fusion and circuit.Drill bit percentage wear rate data shown in this and the last table 2 are consistent.More specifically say, can reckon with that the lower laminate of drill bit percentage wear rate also shows lower offset distance, because drill bit can sharply long boring number.

Embodiment 2

In embodiment 2, also carry out the test of drilling tool percentage wear rate.Test the electricity level laminate contrast C of aforesaid fusion 7628 type fabrics and the drilling tool percentage wear rate of sample D, E and F.Fabric among the contrast C is the 7628-718 fabric of Clark-Schwebel company.Fabric among sample D, E and the F is woven by weft yarn that contains spun glass and warp thread; Wherein the spun glass in the weft yarn is coated with as described here and at the resin compatible setting agent shown in the table 4; Spun glass in the warp thread is coated with various polymerization thing substrate material consistency coating composition (warp thread is the commercially available fiber glass ends product of PPG Industries Inc., is designed to the G-75 glass fiber yarn with PPG Industries Inc.'s 1383 adhesive coated).

Table 4

The component of sample D, E and the used setting agent of F is in the weight percent of total solids

105PVP K-30 PVP K120 can be purchased acquisition from the ISP chemical company of Wayne (New Jersey)

106 STEPANTEX 653 can be purchased acquisition from the Stepan company of Maywood (NJ)

107A-187 γ glycidoxypropyltrime,hoxysilane can be purchased acquisition from the OSiSpecialties company of Tarrytown (NY)

108A-174 γ methacryloxypropyl trimethoxy silane can be purchased acquisition from the OSiSpecialties company of Tarrytown (NY)

109

the amidated polymine of 6717 parts, can be purchased acquisition from Henkel Corp. of Kankakee (Illinois State)

110MACOL OP-10 ethoxylated alkyl phenols can be purchased acquisition from the BASF of Parsippany (NJ)

The epoxyethane derivative of 111TMAZ-81 sorbitol ester can be purchased acquisition from the BASF of Parsippany (NJ)

112MAZU DF-136 skimmer can be purchased acquisition from the BASF of Parsippany (NJ)

The 113SAG10 skimmer, it can be purchased acquisition from the OSi Specialties company of Danbury (Connecticut)

114

HP-1055; 1.0 the micron particle dispersion liquid, can be from Philadelphia the Rohm andHaas company of (PA) be purchased acquisition

115

OP-96; 0.55 the micron particle dispersion liquid, can be from Philadelphia the Rohm andHaas company of (PA) be purchased acquisition

116ORPAC BORON NITRIDE RELEASECOAT-CONC SP 1 dispersion liquid can be purchased acquisition from the ZYP Coatings company of Oak Ridge (TN)

117 the PT160 boron nitride powder, can be purchased acquisition from the AdvancedCeramics company of Lakewood (OH)

The 118RD-847A vibrin can be purchased acquisition from the Borden Chemicals of Ge Lunbiya (Ohio)

The polyethylene glycol adipate glycol of 119DESMOPHEN2000 can be purchased acquisition from the Bayer of Pittsburgh (Pennsylvania)

120PLURONICTMF-108 polyoxypropylene-polyoxyethylene copolymer can be purchased acquisition from BASF AG of Parsippany (New Jersey)

121ALKAMULS EL-719 polyoxy ethylization vegetables oil can be purchased acquisition from Rhone-Poulenc

122ICONOL NP-6 alkoxylate nonylphenol can be purchased acquisition from the BASF of Parsippany (New Jersey)

Use Tg fabric to be formed prepreg subsequently for about 140 ℃ FR-4 epoxy resin (the 4000-2 resin of Anaheim (CA) Nelco international corporation design).Before presoak, from fabric, do not remove Hairstyling composition.Through piling up 8 layers of prepreg and 4 layers 1 ounce copper (being described below) and under about 355 ℉ (about 179 ℃), about 300 pounds/square inch (about 2.1 million pascals) pressure, their about 150 minutes laminated together (total cycle times) being processed laminate.The thickness range of copper bearing laminate is about 0.052 inch (about 0.132cm) to about 0.065 inch (0.165cm).In the formation of laminate, pile up 8 layers of prepreg and copper layer by following arrangement:

One deck l oz/ft ²Glossy copper layer

Three layers of presoak lamella

One deck loz/ft ²RTF (reverse side processing paper tinsel) copper layer

Two-layer presoak lamella

One deck loz/ft ²RTF copper layer

Three layers of presoak lamella

One deck loz/ft ²Glossy copper layer

The finished product laminate is trimmed to 40.6cm * 50.8cm (16 inches * 20 inches).

Use Uniline2000 single head punch to hole.On the laminate (as stated) of 3 heap floor heights, hole, wherein laminate has 0.010 inch (0.254mm) thick aluminium inlet and 0.1 inch (2.54mm) thick coated particle board base plate of aluminium.Measure the drilling tool percentage wear rate of 0.34mm (0.0135 inch) tool diameter, this brill is 80 serial carbide burs from the Tulon company acquisition of Gardenia (CA).Cutting load remains on 0.001 constantly in the boring procedure, and spindle speed is 95,000rpm and insert speed be 95 inches (241cm)/minute.The retraction rate of boring be 90 inches (2.29m)/minute with drill bit on be limited to 0.059 inch (1.5mm) drill bit upper limit.

Measure drill bit percentage wear rate according to 1500 and 2500 hole drill sectional hole patterns.Hole density with 28 hole/square centimeters (about 178 hole/square inches) is holed in each section

Table 2 has shown that contrast C and sample D, E and F are at the drill bit percentage wear rate of holing after 1500 and 2500.When beginning, every group of hole, and each laminate heap layer is divided into the grouping in 10 1500 holes and the grouping in 10 2500 holes with new drill bit.Every kind of fabric type is bored three heap laminate heap layer, so that measure the drill bit percentage wear rate of 30 brills of every kind of sample

Table 5

As shown in table 5; Sample D, E and F; It contains glass fiber, and said glass fiber has been coated with the setting agent compatible with the laminate matrix resin of the present invention, bored 1500 percentage wear rates after the hole be starkly lower than the contrast A; Contain glass fiber among the contrast A, this glass fiber had carried out thermal cleaning before the arrangement setting agent of coating silane.After boring 2500 holes, the amount of the drilling tool percentage wear rate of sample D, E and F still is lower than contrast C, but wear rate is lower.This expectation obtains, because most of tool wear occurs in during the boring early, rather than in dividing into groups last boring the time.

Based on above-mentioned; Be not limited to the present invention, the drill bit percentage of the prepreg made from glasscloth (said glasscloth has been coated with the compatible setting agent of polymeric matrix of the present invention) wastes loss rate, on 3 laminate heap layers, bore 2000 holes after mensuration; Preferably be not more than about 32%; More preferably no more than about 30%, it is about 25% that first-selection is not more than, and wherein each laminate comprises 8 prepregs; With the cutting load of 400 holes/square inch hole density and 0.001, with the carbide bur of 0.46mm (0.018 inch) diameter.

In addition, based on above-mentioned, be not limited to the present invention; The offset distance of the prepreg made from glasscloth (said glasscloth has been coated with the compatible setting agent of polymeric matrix of the present invention); Measure after on 3 laminate heap layers, boring 2000 holes, preferably be not more than about 36 microns, more preferably no more than about 33 microns; First-selection is not more than about 31 microns; Wherein each laminate comprises 8 prepregs, with the cutting load of 400 holes/square inch hole density and 0.001, with the carbide bur of 0.46mm (0.018 inch) diameter.

Do not look to the support of any concrete theory, it is believed that in the glass fiber coating compositions disclosed herein to have solid lubricant, and in a concrete embodiment, have SP 1, bring improved boring performance can for laminate of the present invention.Say that more specifically solid lubricant can reduce the wearing and tearing of brill and improve the tolerance range of bore position.

Boring improvement in performance with in the laminate of spun glass (said spun glass has been coated with resin compatible setting agent of the present invention) manufacturing provides lot of advantages.At first, make that to bore time limit of service longer, explain each be drilled in passivation or lose before can bore more hole.Secondly, because therefore the tolerance range of bore position can expect that greater than the laminate of routine the laminate of piling up more than three layers holes at one time on the laminate of the present invention, can reach tolerance range identical when piling up three layers of conventional laminate.These two advantages can make drilling operation more effective economically, in addition, can improve the tolerance range of bore position on laminate, so that improve the quality of the charge carrier of fusion laminate.

One skilled in the art will appreciate that under the prerequisite that does not deviate from generalized concept of the present invention and can change above-mentioned embodiment.Therefore be appreciated that to the invention is not restricted to disclosed specific embodiments, and desire the variation in covering essence of the present invention and scope, scope of the present invention defines claims of liking enclosed.

Claims (45)

1. prepreg that is used for charge carrier, this prepreg comprises

(a) matrix material; With

(b) fabric; This fabric contains the line thigh that comprises spun glass; At least a portion of fabric has the coating compatible with matrix material; Wherein this coating composition contains (i) a plurality of particles discrete, dimensional stabilizing, this particle form by the material that is selected from organic materials, polymeric materials and matrix material and composition thereof and at least one fiber and at least one adjacent fiber between have clearance space, the particulate average particle size particle size is the 0.1-5 micron; (ii) a plurality ofly be different from a plurality of discrete, dimensional stabilizing particulate solid lubricant particles; Wherein solid lubricant particle comprises (1) at least a inorganic solid lubricant particle that can not hydration, is selected from graphite, SP 1, metal dithionite and belongs to element thing (dichalcogenides), cadmium iodate, silver sulfide, indium, thallium, tin, copper, zinc, gold and silver, lime carbonate, Calcium Fluoride (Fluorspan), zinc oxide and composition thereof; (2) count the 1-60% of coating composition weight based on total solids; (iii) at least a film forming material, wherein at least a film forming material comprises at least a polymeric materials, and this polymeric materials is counted the 1-90% of coating composition weight based on total solids; The drill bit percentage wear rate of this prepreg is not more than 32%; Drill bit percentage wear rate is on the heap layer of 3 laminate, to bore mensuration after 2000 holes with the carbide bur of 0.46mm diameter with the cutting load of the hole density of 62 hole/square centimeters and 0.001, wherein comprises 8 prepregs in each laminate.

2. the prepreg of claim 1, wherein the drill bit percentage wear rate of prepreg is not more than 30%.

3. the prepreg of claim 2, wherein the drill bit percentage wear rate of prepreg is not more than 25%.

4. the prepreg of claim 1, wherein matrix material comprises at least a thermoset matrix material that is selected from thermosetting polyester class, vinyl ester, epoxides, phenoplast, aminoplastics, heat-curable urethane class and composition thereof.

5. the prepreg of claim 4, wherein matrix material comprises at least a thermoplastic matrix material who is selected from polyolefins, polyamide-based, thermoplastic polyurethanes, thermoplastic polyester class, vinyl polymer class, polyimide, polyethersulfone, polyphenylsulphine, polyetherketone, ppe, polyphenylene sulfide, polyacetal, polycarbonate and composition thereof.

6. the prepreg of claim 1, wherein at least a spun glass is selected from E-spun glass, D-spun glass, S-spun glass and combination thereof.

7. the prepreg of claim 1, inorganic solid lubricant particle that wherein can not hydration comprises the boron nitride particle of hexagonal crystal structure.

8. the prepreg of claim 1, wherein the hardness of solid lubricant particle is less than or equal to the hardness value of E-spun glass.

9. the prepreg of claim 1 wherein contains (1) polyester in the coating; (2) at least a polymkeric substance and the boron nitride particle that is selected from vinyl pyrrolidone polymer, vinyl alcohol polymkeric substance and starch.

10. the prepreg of claim 1, wherein at least a particle contains polymeric materials, and said polymeric materials is selected from inorganic polymeric materials, synthetic organic polymer material, semi-synthetic organic polymer material and natural organic polymer material.

11. the prepreg of claim 10, wherein at least a particle contains the thermoplastic organic polymer material, is selected from XPA, vinyl polymer, thermoplastic polyester class, polyolefins, polyamide-based, thermoplastic polyurethanes and composition thereof.

12. the prepreg of claim 11, wherein at least a particle is formed by PEMULEN TR2, and said PEMULEN TR2 is vinylbenzene and acrylic acid multipolymer.

13. the prepreg of claim 12; Wherein particle is first particle; And also contain a plurality of other particles discrete, dimensional stabilizing in the resin compatible based coating composition, this particle is different from first particle and is selected from metal, graphite, oxide compound, carbide, nitride, boride, sulfide, silicate and carbonate.

14. the prepreg of claim 1; Wherein contain lubricant in the coating, said lubricant is selected from palmitinic acid cetyl ester, LAURIC ACID 99 MIN cetyl ester, LAURIC ACID 99 MIN stearyl, tetradecanoic acid stearyl, palmitinic acid stearyl, Triple Pressed Stearic Acid stearyl and paraffin.

15. the prepreg of claim 1, wherein particle comprises boron nitride particle and the hollow bead that is formed by vinylbenzene and PEMULEN TR2.

16. the prepreg of claim 1, wherein at least a spun glass is with coating part coating at least.

17. the prepreg of claim 1, wherein fabric is selected from woven fabric, non-woven fabric, the fabric and the pad of braiding.

18. the prepreg of claim 1; Wherein the offset distance of prepreg is not more than 36 microns; Offset distance is on the heap layer of 3 laminate, to bore mensuration after 2000 holes with the carbide bur of 0.46mm diameter with the cutting load of the hole density of 62 hole/square centimeters and 0.001, wherein comprises 8 prepregs in each laminate.

19. the prepreg of claim 1, wherein at least a portion of fabric contains the spun glass of twisting.

20. the prepreg of claim 1, wherein at least a portion of fabric contains the spun glass of not twisting.

21. the prepreg of claim 1, wherein at least one spun glass is to use direct melt spun glass formation technology to make.

22. the prepreg of claim 1, wherein at least one spun glass is to use crucible melt spun glass formation technology to make.

23. the prepreg of claim 1, the wherein woven fabric of fabric right and wrong.

24. the prepreg of claim 1, wherein fabric is woven fabric.

25. the prepreg of claim 24, wherein fabric is woven on the air spray loom.

26. the prepreg of claim 25, wherein at least one spun glass is to use direct melt spun glass to form the glass fiber yarn that manufacturing and at least a portion fabric of technology contains twisting.

27. the prepreg of claim 24, wherein fabric is woven on the rapier loom.

28. the prepreg of claim 27, wherein at least one spun glass is to use direct melt spun glass to form the glass fiber yarn that manufacturing and at least a portion fabric of technology contains twisting.

29. being to use crucible melt spun glass to form manufacturing and at least a portion fabric of technology, the prepreg of claim 27, wherein at least a spun glass contain the spun glass of not twisting.

30. a prepreg that is used for charge carrier, this prepreg comprises

(a) matrix material; With

(b) woven reinforced textile; This fabric contains spun glass; At least a portion of fabric has the coating compatible with matrix material; Wherein this coating composition contains (i) a plurality of particles discrete, dimensional stabilizing, this particle form by the material that is selected from organic materials, inorganic materials, polymeric materials and matrix material and composition thereof and at least one fiber and at least one adjacent fiber between have clearance space, the particulate average particle size particle size is the 0.1-5 micron; (ii) a plurality ofly be different from a plurality of discrete, dimensional stabilizing particulate solid lubricant particles; Wherein solid lubricant particle comprises (1) at least a inorganic solid lubricant particle that can not hydration, is selected from graphite, SP 1, metal dithionite and belongs to element thing (dichalcogenides), cadmium iodate, silver sulfide, indium, thallium, tin, copper, zinc, gold and silver, lime carbonate, Calcium Fluoride (Fluorspan), zinc oxide and composition thereof; (2) count the 1-60% of coating composition weight based on total solids; (iii) at least a film forming material, wherein at least a film forming material comprises at least a polymeric materials, and this polymeric materials is counted the 1-90% of coating composition weight based on total solids; The offset distance of this prepreg is not more than 36 microns, and offset distance is on the heap layer of 3 laminate, to bore mensuration after 2000 holes with the carbide bur of 0.46mm diameter with the cutting load of the hole density of 62 hole/square centimeters and 0.001.

31. the prepreg of claim 30, wherein the offset distance of prepreg is not more than 33 microns.

32. the prepreg of claim 31, wherein the offset distance of prepreg is not more than 31 microns.

33. the prepreg of claim 30, wherein at least a spun glass is selected from E-spun glass, D-spun glass, S-spun glass and combination thereof.

34. the prepreg of claim 30, inorganic solid lubricant particle that wherein can not hydration comprises the boron nitride particle of hexagonal crystal structure.

35. the prepreg of claim 30, wherein the hardness of solid lubricant particle is less than or equal to the hardness value of E-spun glass.

36. the prepreg of claim 30 wherein contains (1) polyester in the coating; (2) at least a polymkeric substance and the boron nitride particle that is selected from vinyl pyrrolidone polymer, vinyl alcohol polymkeric substance and starch.

37. the prepreg of claim 30, wherein at least a particle contains polymeric materials, and said polymeric materials is selected from inorganic polymeric materials, synthetic organic polymer material, semi-synthetic organic polymer material and natural organic polymer material.

38. the prepreg of claim 37, wherein at least a particle contains the thermoplastic organic polymer material, is selected from XPA, vinyl polymer, thermoplastic polyester class, polyolefins, polyamide-based, thermoplastic polyurethanes and composition thereof.

39. the prepreg of claim 38, wherein at least a particle is formed by PEMULEN TR2, and said PEMULEN TR2 is vinylbenzene and acrylic acid multipolymer.

40. the prepreg of claim 39; Wherein particle is first particle; And also contain multiple other particle discrete, dimensional stabilizing in the resin compatible based coating composition, this particle is different from first particle and is selected from metal, graphite, oxide compound, carbide, nitride, boride, sulfide, silicate and carbonate.

41. the prepreg of claim 30; Wherein contain lubricant in the coating, said lubricant is selected from palmitinic acid cetyl ester, LAURIC ACID 99 MIN cetyl ester, LAURIC ACID 99 MIN stearyl, tetradecanoic acid stearyl, palmitinic acid stearyl, Triple Pressed Stearic Acid stearyl and paraffin.

42. the prepreg of claim 30, wherein particle comprises boron nitride particle and the hollow bead that is formed by vinylbenzene and PEMULEN TR2.

43. the prepreg of claim 30, wherein at least a spun glass is with coating part coating at least.

44. the prepreg of claim 30, wherein fabric is selected from woven fabric, non-woven fabric, the fabric and the pad of braiding.

45. be mixed with the laminate of the prepreg of claim 1 or 30.

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