CN104812696B - The composite material of improved glass fiber reinforcement - Google Patents

Abstract

The composite material for having the glass fiber reinforcement of improved physical property is provided.Core shell rubber nano particle is introduced in the sizing composition that the composite material of glass fiber reinforcement is directly coated in the resinoid bond of the composite material and/or on individual glass fibre.

Description

The composite material of improved glass fiber reinforcement

This application claims the U.S. Provisional Applications 61/679,196 and 2012 year that August in 2012 is submitted on the 3rd to mention November 16 The priority of the U.S. Provisional Application 61/727,453 of friendship introduces their full text herein by reference.

Background technique

It is online to glass fibre by applying bituminous coating, while still soft, sand is embedded in bituminous coating Or other roofing granules (roofing granules), once then asphalt hardening, then segment the mesh Cheng Dan being thusly-formed Only roof boarding (shingle), to manufacture conventional asphalt shingle (roofing shingles).Usually by by suitable The glass fibre manufacture glass fiber mesh that is bonded together of resinoid bond.In addition, the inorganic particulate filler of fine grinding usually wraps It includes in bituminous coating, to reduce cost, improves the thermal deformation resistant of roofing board, and reduce the UV degradation of pitch.

Commonly assigned United States Patent (USP) No.7,951,240 (its complete disclosure is herein by reference in introducing) table The tearing strength of the bright roof boarding manufactured in such a way can be by the shadow for the particulate filler type for including in bituminous coating It rings.Particularly, if this patent shows using hard filler, such as dolomite, silica, slategray (slate dust), High carbon acid magnesium and analog, then the tearing strength of this roof boarding may be sacrificed.

It has been found that forming matrix or composite body, such as in manufacture roofing in resinoid bond in conjunction with polymer Before fiberglass packing used in plate, by being received in the resinoid bond being applied on glass fibre including core shell rubber Rice grain can improve the physical property of the fibre-reinforced polymer composites of many glass types.

And also found, when can be manufactured by them, received in the sizing agent being applied on fiber including core shell rubber Rice grain, rather than in subsequent manufacturing process (glass fibre being wherein glued in advance be used to manufacture useful product) with The individual polymer adhesive form being applied on fiber afterwards includes them, be easily manufactured carry these core shell rubbers receive The glass fibre of rice grain.

Summary of the invention

In some embodiments enumerated of the invention, it was found that can be by the resinoid bond of composite material Introduce core shell rubber nano particle, the physical property of the composite material of Lai Gaijin glass fiber reinforcement.

In the various embodiments enumerated of the invention, the composite material of glass fiber reinforcement is included in manufacture pitch room Improved top pad (roofing mat) of putting up a house used in panel.It is improved put up a house top pad some aspects enumerated include by The fiberglass packing of multiple glass fibres and the resinoid bond that individual glass fibre keeps together composition, the wherein tree Rouge binder includes rubber core-shell nanoparticles.

Moreover, according to the present invention further enumerate aspect, it was found that when they are manufactured, by being applied to fibre Include core shell rubber nano particle in sizing agent in dimension, rather than in addition, is being applied in subsequent manufacturing process Include nano particle in independent polymer adhesive on fiber, the glass for carrying these core shell rubber nano particles can be manufactured Glass fiber.

Therefore, the aspect that enumerates of the invention provides the polymer composites of glass fiber reinforcement, it includes matrix polymerization Object and the glass fibre dispersed in the matrix polymer, wherein the surface of glass fibre carries core shell rubber nano particle Coating.

The aspect according to the present invention that other are enumerated, providing makes in the polymer composites of manufacture glass fiber reinforcement Continuous glass fibre and fiber.Continuous glass fibre and fiber include the continuous glass fibre or fiber for carrying aqueous sizing composition coating Substrate, the aqueous sizing composition include film forming polymer, organosilanes coupling agent and core shell rubber nano particle.

The aspect that further enumerates of the invention also provides the continuity method of manufacture glass fibre, and this method includes introducing melting Glass produces the smelt flow of glass, allows the smelt flow of the glass hard by multiple holes in casing (bushing) Change, forms individual long filament.Individual long filament is available to contain lubricant, the initial sizing of film-forming resin and organosilanes coupling agent The coating of agent composition, and combine together, form fiber.This method can further comprise applying the painting of core shell rubber nano particle On layer to fiber.

Some embodiments enumerated provide the polymer composites of glass fiber reinforcement, it includes multiple individual glass The glass fiber and resinoid bond of glass fiber, wherein introducing core shell rubber nanometer in the resinoid bond of the composite material Grain.Individual glass fibre can form the fiberglass packing to keep together by resinoid bond.The resinoid bond can wrap The rubber core-shell nanoparticles of 0.1-20wt% or the rubber core-shell nanoparticles of 0.5-10wt%wt% are included, it is viscous based on this Tie the total amount of resin in agent.The average particle size of rubber core-shell nanoparticles can be less than or equal to 250nm.The resinoid bond It can be by Lauxite, the formation of or mixtures thereof acrylic resin.

In some embodiments enumerated, the core of rubber core-shell nanoparticles is by being selected from phenylethylene/butadiene, poly- fourth Diene, silicon rubber (siloxanes), the synthetic polymer rubber manufacture in acrylic rubber and its mixture.

In the embodiment that other are enumerated, which is asphalt shingle.

In the various embodiments enumerated, the improved top pad of putting up a house used in manufacture asphalt shingle is provided.Change Into put up a house top pad may include being formed by multiple glass fibres and by the resinoid bond that individual glass fibre keeps together Fiberglass packing.The resinoid bond may include rubber core-shell nanoparticles.The resinoid bond may include 0.1-20wt% Rubber core-shell nanoparticles, based on the resin total amount in the binder.The average particle size of rubber core-shell nanoparticles can be small In or equal to 250nm.The resinoid bond can be by Lauxite, the formation of or mixtures thereof acrylic resin.Rubber core-shell structure copolymer is received The core of rice grain can be by being selected from phenylethylene/butadiene, polybutadiene, silicon rubber (siloxanes), acrylic rubber and its mixing Synthetic polymer rubber manufacture in object.

It is enumerated in embodiment in still other, improved asphalt shingle is provided, it includes by multiple glass fibres It puts up a house to push up with the glass fibre for the resinoid bond composition that individual glass fibre keeps together and pads and cover the glass fibers Dimension, which is puted up a house, pushes up the bituminous coating of pad.Bituminous coating may include inorganic particulate filler.Bituminous coating can further contain to be wrapped in it The lid roofing granule buried.In some embodiments enumerated, it includes rubber that glass fibre, which puts up a house and pushes up the resinoid bond in padding, Core-shell nanoparticles.The resinoid bond may include 0.1-20wt% rubber core-shell nanoparticles or 0.5-10wt% rubber Core-shell nanoparticles, based on the resin total amount in binder.The average particle size of rubber core-shell nanoparticles can be less than or Equal to 250nm.The resinoid bond can be by Lauxite, the formation of or mixtures thereof acrylic resin.Rubber core-shell structure copolymer nanometer Core in grain can be by being selected from phenylethylene/butadiene, polybutadiene, silicon rubber (siloxanes), acrylic rubber and its mixture In synthetic polymer rubber manufacture.Bituminous coating may include that 30- 80wt% is selected from dolomite, silica, slategray and height Inorganic particulate filler in magnesium carbonate, the total weight of the pitch based on filling.

In the various embodiments enumerated, a kind of polymer composites of glass fiber reinforcement are provided, it includes base Body polymer and the glass fibre dispersed in the matrix polymer.The surface of glass fibre can carry core shell rubber nanometer The coating of grain.It is enumerated in embodiment in others, the surface of glass fibre carries nano particle containing core shell rubber and film forming is poly- Close the coating of the mixture of object.It is enumerated in embodiment in others, the surface of glass fibre carries in fiber manufacture process Apply the first coating of the initial sizing composition on fiber, which includes core shell rubber nanometer Grain, film forming polymer and organosilanes coupling agent.Initial sizing composition can contain chloroflo.

In some embodiments enumerated, the continuous glass fibre by combining multiple drawing-downs together, is formed individually fine Dimension manufactures glass fibre, and applies on initial sizing composition to individual continuous glass fibre, is bonded to later one It rises.

In some embodiments enumerated, after combining individual continuous glass fibre, apply in fiber manufacture process In the second coating to fiber of the initial sizing composition of auxiliary, wherein the initial sizing composition assisted includes additional Core shell rubber nano particle and film forming polymer.

By together, in conjunction with the filament of glass fiber of multiple drawing-downs, individual fiber can be formed, glass fibre is manufactured, wherein The surface of glass fibre carries before the combination of individual continuous glass fibre, is applied to the of the initial sizing composition on them One coating, the initial sizing composition include film forming polymer and organosilanes coupling agent, and further wherein glass fibers The surface of dimension carries after combining individual continuous glass fibre, and the initial of the auxiliary on fiber is applied in fiber manufacture process The second coating of sizing composition, the initial sizing composition of the auxiliary include that core shell rubber nano particle and film forming are poly- Close object.

The average particle size of core shell rubber nano particle can be less than or equal to 250nm.In rubber core-shell nanoparticles Core can be by being selected from phenylethylene/butadiene, polybutadiene, silicon rubber (siloxanes), the conjunction in acrylic rubber and its mixture It is manufactured at polymer rubber.

In some embodiments enumerated, apply the form of mixtures of core shell rubber nano particle and film-forming resin On core shell rubber nano particle to the glass fibre of enhancing, and further wherein the mixture includes 0.1-20wt% rubber Core-shell nanoparticles, 0.5-10wt%wt% rubber core-shell nanoparticles, the total amount based on film-forming resin in the mixture.

In some embodiments enumerated, the polymer composites of glass fiber reinforcement are roof boarding

In some embodiments enumerated, provide manufacture glass fiber reinforcement polymer composites used in Continuous glass fibre.Continuous glass fibre may include the continuous glass fibre substrate for carrying the coating of initial sizing composition, and wherein this is initially applied Size composition includes film forming polymer, organosilanes coupling agent and core shell rubber nano particle.

Enumerated in embodiment in others, provide manufacture glass fiber reinforcement polymer composites used in Glass fibre.The glass fibre may include the glass fibre for carrying the coating containing film forming polymer and core shell rubber nano particle Substrate.

Glass fibre can be made of combined multiple continuous glass fibres, and the surface of continuous glass fibre is carried to be combined in long filament Before, it is applied to the first coating of the initial sizing composition on them, wherein the initial sizing composition includes film forming Polymer, organosilanes coupling agent and core shell rubber nano particle.

The surface of glass fibre carries initially applying for the auxiliary being applied on fiber after combining the long filament for forming fiber The second coating of size composition, wherein the initial sizing composition of the auxiliary includes additional core shell rubber nano particle And film forming polymer.

It is enumerated in embodiment in others, by combining multiple drawing-down continuous glass fibres together, forms fiber, manufacture glass Glass fiber, wherein the surface of glass fibre carries before the combination of independent continuous glass fibre, the initial sizing agent being applied on them The first coating of composition, wherein the initial sizing composition includes film forming polymer and organosilanes coupling agent.Glass In addition the surface of fiber can carry the initial sizing agent group for the auxiliary being applied on fiber after combining individual continuous glass fibre The second coating of object is closed, wherein the initial sizing composition of the auxiliary includes film forming polymer and core shell rubber nano particle.

The average particle size of core shell rubber nano particle can be less than or equal to 250nm.In addition, rubber core-shell structure copolymer nanometer The core of grain can be by being selected from phenylethylene/butadiene, polybutadiene, silicon rubber (siloxanes), in acrylic rubber and its mixture Synthetic polymer rubber manufacture.

The core shell rubber nano particle of the form of mixtures of core shell rubber nano particle and film-forming resin can be applied to glass On glass long filament or fiber, and further wherein the mixture includes 0.1-20wt% core shell rubber nano particle, is based on the mixing The total amount of film-forming resin in object.

In the embodiment further enumerated, the continuity method of manufacture glass fibre is provided, this method includes introducing Melten glass produces the smelt flow of glass, the smelt flow of glass is allowed to harden by multiple holes in casing, is formed single Only long filament, with lubricant is contained, the initial sizing composition coating of film-forming resin and organosilanes coupling agent is individually long Silk, and individual long filament is combined together, form fiber.This method can further comprise applying the painting of core shell rubber nano particle On layer to fiber.

Core shell rubber particle can be applied to glass fibers by including core shell rubber particle in initial sizing composition In dimension.

In some embodiments enumerated, by the auxiliary with nano particle containing core shell rubber and film forming polymer Initial sizing composition formed after core shell rubber particle, by coated glass fiber, apply core shell rubber particle to On glass fibre.The initial sizing agent can also contain core shell rubber nano particle.

The average particle size of core shell rubber nano particle can be less than or equal to 250nm, and rubber core-shell nanoparticles Core can be by being selected from phenylethylene/butadiene, polybutadiene, silicon rubber (siloxanes), in acrylic rubber and its mixture The manufacture of synthetic polymer rubber.

Detailed description of the invention

By reference to following attached drawings, it is better understood the present invention, in which:

Fig. 1 is the box traction substation (box plot) for illustrating the data of tensile strength of two kinds of certain fiberglass packings；

Fig. 2 is the box traction substation for illustrating the data of tearing strength of two kinds of certain fiberglass packings；

Fig. 3 is the box traction substation for illustrating the data of tensile strength of two kinds of certain asphalt shingles；

Fig. 4 is to show core shell rubber nano particle of the invention to the height of glass fiber winding made according to the present invention The bar chart for pressing the bursting strength of compound pipeline complex pipeline to influence；

Fig. 5 is to show these core shell rubber nano particles to the interlayer in the high-pressure composite pipe road of the glass fiber winding of Fig. 1 The chart that shear strength influences；With

Fig. 6 is to show these core shell rubber nano particles to the glass fiber winding in its manufacturing process, forming Fig. 4 High-pressure composite pipe road used in the chart that influences of the tension that generates on glass fibre.

Specific embodiment

Rubber core-shell particles

Rubber core-shell particles are known article of commerce described in several patents.For example, they are described in EP2 053 083 Al,EP5 830 086 B2,U.S.5,002,982,U.S.2005/0214534,JP11207848,U.S.4,666, In 777, U.S.7,919,549 and U.S.2010/0273382, wherein each disclosure is herein by reference in complete Text introduces.In general, they are made of nano particle, the nano particle have thermoplasticity or thermosetting polymer shell and by Synthetic polymer rubber, such as phenylethylene/butadiene, polybutadiene, silicon rubber (siloxanes) or acrylic rubber manufacture Core.Generally, their average particle size is to be more typically less than or be equal to about 200nm less than or equal to about 250nm, be less than or wait In about 150nm, or even less than or equal to about 100nm and the size distribution being rather narrow.They are available commercially from many different sources, Including Kenaka Corporation of Pasadena, Texas.

The manufacture of glass fibre

Typically via continuous manufacture, glass fibre is manufactured, wherein melten glass is forced through the hole of " casing ", by The logistics of this melten glass formed hardens into long filament, and combines long filament together, forms fiber or " rove " or " strand ".It is this kind of The manufacturing method of glass fibre is known and is described in many patents.Example includes U.S.3,951,631, U.S.4,015, 559, U.S.4,309,202, U.S.4,222,344, U.S.4,448,911, U.S.5,954,853, U.S.5,840,370 and U.S.5,955,518, wherein each disclosure is introduced herein by reference in full text.Typically via these methods The order of magnitude of rate when producing glass fibre is 4,000-15,000 feet/min (about 1,220-4,572 ms/min).Cause This, it is understood that time when this glass fibre manufacture technique occurs, that is to say, that when melten glass leaves the time of casing Period between the time when glass fibre or strand packaging, storage and/or the use for being glued and being formed completely is very It is short, it is one second a fraction of of order of magnitude.

It can be by any kind of glass manufacture glass fibre.Example includes A- type glass fibre, C- type glass fibre, E- type Glass fibre, S- type glass fibre, ECR- type glass fibre is (for example, be available commercially from Owens Corning's Glass fibre), Hiper-tex^TM, wool glass fibers and combinations thereof.In addition, synthetic resin fiber, such as by polyester, polyamides Amine, those of aromatic polyamides and its mixture manufacture also are included in fiberglass packing of the invention.Similarly, may be used Including by one or more naturally occurring materials, such as cotton, jute, bamboo, ramie, bagasse, hemp, coir, Flax (linen), mestha, sisal hemp, flax (flax), the fiber of He Nakun leaf fibre and combinations thereof manufacture equally can be carbon Fiber.

Usually after continuous glass fibre hardening, but before they are contacted with drawing-down with rotary spindle, by aquifer coating or " sizing agent " is applied on continuous glass fibre.This sizing agent contains lubricant typically to protect fiber to avoid damaging because of abrasion Bad, containing film-forming resin to assist on viscose fibre to polymer, which is formed in the composite material in it using fiber Main body or matrix, and containing organosilanes coupling agent to improve film-forming resin and matrix polymer to fiberglass surfacing Adhesion.Although this sizing agent can be applied by spraying, typically via make long filament on the liner or roller containing sizing agent On the surface thereof by applying them.

It uses in the manufacture of the polymer composites of a variety of different glass fiber reinforcements and manufactures in such a way The glass fibre being glued.In these most of manufacturing process, in conjunction with the glass fibre being glued and composite material is formed The matrix polymer of main body or matrix, later with final form arranged glass fiber in product to be manufactured.In another party In method, the glass fibre being glued is assembled into " preform " first, then with the matrix resin for forming composite body Dipping.This is method used in manufacture roof boarding, and wherein it is (preforming to be formed certainly-support mesh for glass fibre Body), and it is coated with the mesh so manufactured with pitch, it then hardens, forms final asphalt roofing panel products.

When being exposed under stress and the power occurred when operating preform and/or being impregnated with matrix resin, independent The glass fibre being glued be not separated from each other in the sense that for, in this process used in glass fibre preform Body be usually from-support or at least cohesion.For this purpose, the glass fibre being glued leads to usual additional Film-forming resin coating, make fibres bond together.For convenience's sake, the coating composition used in this purpose exists It is referred to as " binder sizing agent (binder sizes) " in this document.These binder sizing agents are understood to be different from making For a part of its manufacturing process, the sizing composition being applied on continuous glass fibre and fiber, the latter's quilt in this document Referred to as " initial sizing agent (incipient sizes) " or " initial sizing composition ".

According to above, it should be apparent that manufacture glass fibre method and using glass fibre method industrially by It is considered as independent of one another and different.Due to this, the processing step or operation allusion quotation that occur during glass fibre manufacture It is referred to as " online " step or operation to type.On the contrary, during the glass fibre that use front manufactures, such as in manufacture glass The processing step or operation occurred in fibre-reinforced polymer composites is typically referred to as " offline " step or operation.This One term for example for above-mentioned U.S.5,840,370 and U.S.8,163,664, U.S.7,279,059, U.S.7, 169,463, U.S.6,896,963 and particularly in U.S.6,846,855.The disclosure that these patents are each is herein It is introduced by reference.This term also uses in the present disclosure of the invention.

The polymer composites of glass fiber reinforcement

Each aspect of the present invention further relates to manufacture the polymer composites of any kind of glass fiber reinforcement.These are produced Product are industrial well known, and are commonly referred to as " plastics of glass fiber reinforcement ".They are formed multiple by glass reinforced fiber peacekeeping The fluoropolymer resin of the main body of condensation material or " matrix " composition.For convenience's sake, these polymer in this document sometimes Referred to as " matrix polymer ".In the context of this case, " fluoropolymer resin " and " polymer " is also widest with them Meaning uses, including artificial synthetic resin and naturally occurring resin material, such as both pitch and analog.

The polymer composites of glass fiber reinforcement of the invention can be by any kind of glass fibre manufacture.Example packet A- type glass fibre is included, C- type glass fibre, E- type glass fibre, S- type glass fibre, ECR- type glass fibre is (for example, quotient It is purchased from Owens Corning'sGlass fibre), Hiper-tex^TM, and combinations thereof.

The polymer composites of glass fiber reinforcement of the invention may also comprise by the material manufacture other than glass Fiber, the example includes synthetic resin fiber, such as by polyester, polyamide, aromatic polyamides and its mixture manufacture that A bit.Similarly, it may also comprise by one or more naturally occurring materials, such as cotton, jute, bamboo, ramie, bagasse, greatly Fiber crops, coir, flax (linen), mestha, sisal hemp, flax (flax), the fibre of He Nakun leaf fibre and combinations thereof manufacture Dimension, equally can be carbon fiber.Similarly, the polymer composites of glass fiber reinforcement of the invention may also comprise non-fiber Filler, the example include calcium carbonate, silica and wollastonite.Preferably, the polymer of glass fiber reinforcement of the invention is multiple Condensation material contains the combination total amount no more than about 5wt% non-glass fiber and filler, based on all fibres in the composite material The weight of peacekeeping filler.It is further preferred that all or substantially all fibers in glass fiber compound material of the invention are Glass fibre.

Similarly, the polymer composites of glass fiber reinforcement of the invention can be manufactured by any resinoid bond, it In advance used or in the future can manufacture glass fiber reinforcement plastic composite main body or matrix in be used as Matrix polymer.Example includes polyolefin, polyester, polyamide, polyacrylamide, polyimides, polyethers, polyvingl ether, is gathered Phenylethylene, poly oxide, polycarbonate, polysiloxanes, polysulfones, polyanhydride, polyimides, epoxides, acrylic compounds, poly- second Alkenyl esters, polyurethane, maleic acid resin, carbamide resin, melamine resin, phenol resin, furane resins, blend polymer, Alloys and mixts.Particularly preferred epoxy resin.

The resinoid bond dosage that should include in the polymer composites of glass fiber reinforcement of the invention can be wide Change generally, and any conventional amount used can be used.In some embodiments enumerated, in fiberglass packing, resin The dosage of binder is about 10-30wt%, more typically about 14-25wt% or even about 16-22wt%, is based on fiberglass packing Weight as a whole.

Glass fiber reinforcement can be manufactured including simple coating and laminating method by a variety of different manufacturing technologies Polymer composites, but most commonly by molding manufacture.Usually using the different molding methods of two classes, wet process method of molding With composite material method of molding.In wet process method of molding, after molding, glass reinforced fiber peacekeeping matrix is combined in mold immediately Polymer.For example, fiberglass packing produced by the invention can be manufactured by wet-laying material method of molding, wherein wet chopped Glass fibre from deposited in aqueous slurry diaphragm it is online after, be coated with the aqueous dispersion of resinoid bond, then It dries and solidifies.Be formed by nonwoven webs be bonded together in their gap location by resinoid bond it is random The assembly of the individual continuous glass fibre of dispersion.

As described above, fiberglass packing of the invention includes the resinoid bond held the fibers in together.For this For purpose, can be used in advance used or can future manufacture asphalt shingle used in fiberglass packing manufacture Used in any resinoid bond as resinoid bond of the invention.Example includes Lauxite, and acrylic resin gathers Urethane resin, epoxy resin, polyester resin etc..It is preferred that Lauxite and acrylic resin, while even more preferably ureaformaldehyde The mixture of resin and acrylic resin.In these mixtures, the dosage of acrylic resin is as needed about 2- 30wt%, more desirably about 5-25wt%, or even in about 10-20wt% binder Lauxite and acrylic resin knot Resultant, based on drying solid.

The dosage for the resinoid bond that should include in fiberglass packing of the invention can vary widely, and can make With any convention amount.In general, the dosage of resinoid bond is about 10-30wt%, more typically about 14-25wt%, or even about 16-22wt%, the weight based on fiberglass packing as a whole.

The physical structure of fiberglass packing is not crucial in the present invention, and in advance it is used or can future manufacture pitch Any physical structure used in roof boarding fiberglass packing can be used for manufacturing fiberglass packing of the invention.For example, glass The nonwoven web of fiber and weaving and non-woven fiberglass fabric or scrim (scrim) can be used for manufacturing this hair Bright fiberglass packing.

However, most commonly, by wet-laying networking method, fiberglass packing of the invention is manufactured, wherein wet chopped glass Glass fiber deposited to by aqueous slurry diaphragm it is online after, be coated with the aqueous dispersion of resinoid bond, then dried And solidify.It is formed by the list that nonwoven web is the random dispersion being bonded together in their gap location by resinoid bond The assembly of only continuous glass fibre.

Roof boarding

In some embodiments enumerated, using conventional production method, i.e., by applying molten asphalt Coating material composition Object is online to glass fibre of the invention, embeds sand or other tops of putting up a house in this bituminous coating while still soft Particle, once then coating asphalt harden, then the mesh being thusly-formed is segmented into individual roof boarding, thus by the above institute The fiberglass packing of the invention stated manufactures asphalt shingle of the invention.Can be used it is used or in the future use in life Produce the potentially suitable any production method of fiberglass packing and roof boarding of the invention.In advance it is used or can future using use It is suitably adapted for making in manufacturing fiberglass packing and roof boarding of the invention in any fiberglass packing of manufacture asphalt shingle With.

It is used in advance or any drip for manufacturing asphalt shingle can be used in future for this purpose Green coating composition can suitably be used as bituminous coating in the present invention.U.S.7 as described above, described in 951,240, This asphalt coating composition includes the inorganic particulate filler of significant quantity.In addition, they can be by various types and grade Pitch manufactures and may also comprise a variety of different optional members, such as polymer modifiers, wax and analog.Described herein What different grades of pitch and any different inorganic particulate filler and optional compositions described herein are suitably adapted for manufacturing Roof boarding of the invention.

Other than these ingredients, the asphalt coating composition being used in the present invention further includes inorganic particulate filler.It is right For this purpose, known any inorganic particulate filler used in manufacture asphalt shingle can be used.For example, can be used Calcite (lime stone of crushing), dolomite, silica, slategray, high carbon acid magnesium, the rock other than the lime stone of crushing Powder and analog.Total weight based on bituminous coating, it is the concentration of 30-80wt% that the order of magnitude, which can be used, although about 40- 70wt%, or the concentration of even about 50-70wt% is more typical.

As mentioned above, it is known that some pitches that can be negatively affected using the manufacture of these materials in these inorganic particulate fillers The tearing strength of roof boarding.Specifically, it is known that with by softer inorganic filler, for example, calcite (lime stone of crushing) and The identical roof boarding of other situations of analog manufacture is compared, and shows inorganic the filling out of high rigidity (i.e. hardness is greater than about 3Moh) Material, such as dolomite, silica, slategray, the productions such as high carbon acid magnesium have the asphalt shingle of lower tearing strength.Cause This, common practice is to use calcite or other soft inorganic granular objects as asphalt filler in this industry, at least When it is expected the asphalt shingle of excellent tearing strength.Tearing strength is important performance, because it reflects the roof boarding of installation Collapse resistance or the ability for being torn roof substrate by strong wind in other cases.It is said that this is unlikely to be the feelings for tensile strength Shape, because tearing strength is not relative to each other usually with tensile strength, at least asphalt shingle and the glass being produced from it at them It is in this way in glass fiber mat.Really, in some in these products, tearing strength and tensile strength can even be inversely proportional.

Core-shell structure copolymer fiberglass packing

Various aspects according to the present invention, it was found that can be by introducing core shell rubber particle to asphalt shingle of the invention In resinoid bond used in the manufacture for the fiberglass packing being produced from it, overcomes or in other cases, avoid routine Asphalt shingle difference tearing strength the problem of.Therefore, various aspects according to the present invention, can be even by their pitch Include hard inorganic filler, such as dolomite, silica, slategray, high carbon acid magnesium and analog in coating composition, comes Production shows the asphalt shingle of excellent tearing strength.

Once asphalt coating composition of the invention is applied on fiberglass packing of the invention, then still soft at it While, such as under conventional mode, the particle, such as sand or the like on conventional top of putting up a house are applied to this pitch On coating and it is embedded in it.Then bituminous coating is allowed to harden, and then the mesh for the hardening being thusly-formed is subdivided into list Only roof boarding.

It has been proposed using the latex of these rubber core-shell nanoparticles as fiberglass packing binder.Referring to Such as above-described 2 053 083 Al of EP, EP 5 830 086 B2 and U.S.2005/0214534.However, in these use On the way, glass fiber binder is made of these rubber core-shell nanoparticles completely.On the contrary, some being enumerated of the invention , can be a small amount of in aspect, but the polymerization that these rubber core-shell nanoparticles form resinoid bond main body as improvement is introduced in right amount The additive of resin performance.According to certain aspects of the invention, include in the resinoid bond of fiberglass packing these The dosage of rubber core-shell nanoparticles is about 0.1-20wt%, more typically about 0.5-10wt%, or even about 1-4wt%, base It in the total amount of other polymers resin in the binder, i.e., does not include the weight of rubber core-shell nanoparticles itself.

It is also known that can be mentioned by including these rubber core-shell nanoparticles in solid polymer material as filler The tensile strength of the high solid polymer material (this is reflected by its fracture toughness, peel strength and lap shear strength). However, as described above, tearing strength and tensile strength are uncorrelated each other in asphalt shingle place.This is illustrated in Fig. 1 and 2 In, they are the box traction substations for showing tensile strength and tearing strength using the fiberglass packing of various conventional binder manufacture. Fig. 3 is seen also, it is the similar case for showing the tearing strength of the asphalt shingle using these different fiberglass packing manufactures Line chart.As shown in Figure 1, being better than the stretching of the cushion using binder B manufacture using the tensile strength of the cushion of binder A manufacture Intensity.On the contrary, the tearing of tearing strength (Fig. 2) and the asphalt shingle manufactured with adhesive A of the cushion manufactured with adhesive A Intensity (Fig. 3) is worse than with the tearing strength of the adhesive B cushion manufactured and roofing board.This shows in asphalt shingle and they Relevant fiberglass packing between tearing strength and tensile strength be not present direct relationship.This itself demonstrates the present invention The improvement tearing strength of cushion and roof boarding is the phenomenon different from improved tensile strength shown by the prior art.

The shell of rubber core-shell nanoparticles as used in the present invention can be by substantially any thermoplasticity or thermosetting property Polymer is formed, as long as it and polymer phase used in the resinoid bond for forming fiberglass packing used in the present invention Appearance.And " compatible " refers to or physically or chemically stability or generation are disagreeable or undesired by negatively affecting it By-product, formed the polymer of shell not with resinoid bond negatively reaction.

The composite material of additional glass fiber reinforcement

The embodiment enumerated according to other, is formed by modular molding, forms the composite material of glass fiber reinforcement, In before being introduced into mold, reinforcing glass fiber and matrix polymer are combined into " pre-preg material ".This pre-preg material There can be certainly-support body form of wherein glass fibre random orientation, such as form glass fibers used in asphalt shingle Tie up sheet material or " surface layer (veil) ".In addition, they are also possible to certainly-support that wherein glass fibre is orientated in a predetermined direction Body form, such as the load of formation complicated shape undertake the three-dimensional " skeleton " that product uses, such as are made for automotive suspension Rocker arm.This prepreg can also be the grain being made of the matrix polymer of the short glass fiber containing random distribution Material, pastille or aggregate form.

Manufacture the specific example packet of moulding technology workable for the polymer composites of glass fiber reinforcement of the invention Injection molding is included, scraper plate molding, pressing mold, vacuum-bag technique (vacuum bag molding), intentionally interlayer is around (mandrel Wrapping), wet-laying, chopper gun apply (chopper gun application), filament winding (filament Winding), the Resin Transfer Moulding of extrusion molding, pultrusion, Resin Transfer Moulding and vacuum aided.

According to some embodiments enumerated, the polymer composites of glass fiber reinforcement include by filament winding or Intentionally interlayer is around the pressure resistant vessel formed, such as pipeline (pipe) and tank, and particularly wherein matrix polymer is epoxy resin This kind of product.This product is well known and is for example described in above-mentioned U.S.5,840,370 and U.S.7,169,463 In.Just as described in these patents, it is usually wound one needed for container upwardly through around rotation steel shaft specifically taking A little or polymer impregnated all substrates continuous glass fibres, manufactures this pressure resistant vessel.Then any additional matrix is added Then polymer solidifies the matrix polymer and extracts mandrel out, to produce product container.Alternatively, can be by around static steel shaft Winding forms the pre-formed sheet material or surface layer of the glass fibre of some or all of matrix polymer pre-preg needed for container, connects Optionally, add additional matrix polymer, solidify the matrix polymer and draw mandrel, to manufacture this product.Into One step is as described in these patents, in fiber manufacture process, generallys use containing lubricant, film-forming resin and coupling agent The binder sizing agent of (it is usually organosilanes), sizing form glass fibre used in this product.

Core shell rubber nano particle can be introduced into initial sizing agent, institute by the aspect more according to the present invention enumerated It states initial sizing agent to be applied on glass fibre, when manufacturing them.It has been found that from the point of view of manufacture, according to this Mode introduce it is not only very convenient on these nano particles to fiber, but also when a variety of different glass fiber reinforcements polymerization In use, effectively generating the glass fibre with improved enhancing performance in the application of object composite material.

In general, it is expected the average particle size of core shell rubber particle as used in the present invention than it according to the present invention Be applied to reinforcing glass fiber thereon average diameter it is small 100 times (that is, less than 1%), average particle size is than reinforcing glass fibre It is equally interesting for tieing up small 150 times (i.e. less than 0.67%) or even small 200 times (that is, less than 0.5%).

As mentioned above, it is known that can be solid to improve by including these core shell rubber nano particles in material as filler The tensile strength of body polymer masses (this is reflected by fracture toughness, peel strength and lap shear strength).Referring to " Structure-Property Relationship In Core-Shell Rubber Toughened Epoxy Nanocomposites ", Ki Tak Gam submit to the Office of Graduate Studies of Texas A&M The paper of University, part meet the requirement of in December, 2003 PH.D degree.However, as described in detail above, drip The tearing strength and its tensile strength of green roof boarding are uncorrelated each other.This proves changing for asphalt shingle made according to the present invention Into tearing strength be the phenomenon different from the improved tensile strength shown in the prior art.

About this point, it should be understood that the tensile strength of solid polymer material be understood to be its cohesive strength letter Number, i.e., when under tension load, ability that material keeps together itself.On the contrary, the tearing strength of asphalt shingle is wanted It is not understood as the function of entirely different phenomenon, i.e. the glass fibre surface layer of binder sizing composition coating roof boarding, to promote The ability bonded between the bituminous coating (matrix polymer) into surface layer and then applied.In addition, when using core shell rubber particle When improving the tensile strength of solid polymer material, entire polymer masses are filled using these sufficient nano particles.Phase Instead, the core shell rubber nano particle of dosage much less is used in the present invention, because these nano particles are merely present in glass On the surface of fiber itself, the polymer composites main body of glass fiber reinforcement of the invention is formed without being distributed in In matrix polymer material.

According to the present invention, the matrix for forming the polymer composites main body of glass fiber reinforcement of the invention can applied Before polymer, apply on core shell rubber nano particle to reinforcing glass fiber of the invention at any time.Thus, for example After they are by manufacture and storage, in the manufacture work as the polymer composites for producing glass fiber reinforcement of the invention In the independent application step of a part of skill, core shell rubber nano particle can be applied to the enhancing in binder sizing agent On glass fibre.

Alternatively, a part as glass fibre manufacture technique itself, during glass fibre manufacture, they can " In Line " is applied on glass fibre.Usually these long filaments are combined to be formed before fiber together, this is by being applied to form glass Include in initial sizing composition on individual continuous glass fibre used in fiber these core shell rubber nano particles come into Row.Alternatively, after they are formed in individual aqueous sizing composition, can apply these core shell rubber nano particles to On glass fibre.For convenience's sake, these independent sizing compositions in this document referred to as " apply by the initial of auxiliary Jelly ".In third method, both processes can be used, before forming glass fibre, some core shell rubber particles are applied Be added on the individual long filament in initial sizing agent and remaining after the fibers are formed, in the initial sizing agent of auxiliary Apply.

It is unrelated with these methods are used, it is online to apply so that these core shell rubber particles are during glass fibre manufacture Easily applied, this itself eliminates the manufacturing process in the polymer composites of glass fiber reinforcement then of the invention In, the demand to individual " offline " processing step.In addition, final application can be reduced by applying core shell rubber nano particle online The dosage of film forming polymer on to glass fibre, at least when the initial sizing composition used in fiber manufacture process It is interior include nano particle when.This is because in order to promote core shell rubber nano particle to be adhered on glass fibre, nano particle It should apply together with film forming polymer.Therefore, be omitted from conjunction with these nano particles and initial glass sizing agent to second, with The demand of film-forming resin coating afterwards.

As described above, core shell rubber nano particle of the invention can be applied to glass fibers together with suitable film-forming resin In dimension or long filament substrate.It, can be suitably using used or can be in future in glass fibre in advance for this purpose And/or any film-forming resin used in long filament sizing agent as film-forming resin.

As is understood in the art, conventional practice is to be selected in initial sizing agent or binder sizing agent at this time The film-forming resin used, to select the tree compatible with matrix resin used in the glass fiber compound material for manufacturing final production Rouge.For example, compatible epoxy resin is usually selected when manufacturing special glass fiber compound material according to epoxy resin-base It selects as glass fiber size film-forming resin.This identical customary practice is in accordance with the present invention, i.e., selection is containing as needed There are used film-forming resin and glass fiber reinforcement to be produced in the sizing agent of core shell rubber nano particle of the invention Matrix resin in polymer composites is compatible.

As further described above, present invention discover that it is especially compound in the polymer by epoxy resin manufacture glass fiber reinforcement Use in material, this is because these polymer have excellent physical property (for example, tensile strength) and chemical resistance.It is right For this purpose, in some embodiments enumerated, it is expected that selection contains core shell rubber particle, intermediate molecular weight The sizing agent of linear bisphenol A type epoxy resin resin is as film-forming resin.In the context of the present invention, " intermediate molecular weight " refers to weight Average molecular weight is about 10,000-250,000.Preferable weight-average molecular weight is 15,000-100,000 or even 20,000-50,000. Linearly bisphenol A type epoxy resin resin is required, because the polymer composites of many glass fiber reinforcements, and particularly require Those of high-intensitive and good chemical resistance is by linear bisphenol-A type epoxy matrix resin manufacture.These molecular weight be it is required, Because epoxy resin will not be effectively formed film, and He Ruoqi molecular weight is too low, then in coating apparatus if its molecular weight is too high Undergo undesired crystallization.

Other than linear bisphenol A type epoxy resin resin, it is possible to use modified epoxy.Such as, it is possible to use epoxy can Resite (epoxy novolacs).

The commercially available epoxy resin as film-forming resin can be used together with core shell rubber nano particle of the invention Specific example is to be obtained from obtained from the AD-502 epoxy aqueous emulsion of AOC obtained from the Neoxil 962/D aqueous emulsion of DSM The EpiRez 5003 of Momentive, 3511 epoxy emulsion of EpiRez obtained from Momentive.Blend is also effective, spy Other ground ratio is the AD-502+EpiRez 5003 of 95:5.

It can existing film-forming resin dosage can be in the aqueous sizing agent containing core shell rubber nano particle of the invention It varies widely, and can be used and the substantially any dosage of effective coating composition is provided.Typically, film-forming resin dosage For the about 60-90wt% of aqueous sizing agent, based on drying solid (not including water).Preferred amount grade is about 65- The concentration of 85wt% or even 73-77wt%, based on dry weight.

Sizing agent with combination particle

As described above, the aqueous sizing agent containing core shell rubber nano particle of the invention can also contain film-forming resin.To the greatest extent Each managed in these ingredients can be applied independently and be included in this aqueous sizing composition, but in spy of the invention In a not interesting embodiment, these ingredients are in the emulsified particles for including in this aqueous sizing composition It combines together.

Core shell rubber nano particle in the form of a variety of different commercially available from.Form as a kind of is that (do not have molten pure Agent) organic emulsion of rubber nano particle that disperses in liquid epoxies.The example of these products includes being obtained from Kaneka The Kane Ace of the CSR Liquid Epoxy Emulsions of Belgium NV^TMMX series.These liquid epoxy/rubber are received Rice grain lotion is included in various different types of liquid epoxies (including bisphenol-a type liquid epoxies, bis-phenol- F type liquid epoxies, epoxidized phenol bakelite type liquid epoxies, triglycidyl group p-aminophenyl phenolic Liquid epoxies, four glycidyl group methylene dianiline (MDA) type liquid epoxies and alicyclic type liquid epoxies) body The stable dispersions of about 25-40wt%CSR (core shell rubbers nano particle) in being.They are to be previously used for flexibilizing epoxy and other Matrix resin, including the commercial known of matrix resin used in the polymer composites for forming glass fiber reinforcement Product, such as the pipeline and analog of filament winding.

About this point, it should be remembered that the present invention and the prior art manufacture the glass fibers containing core shell rubbers nano particle The significant difference for tieing up the composite material of enhancing is, in the present invention, in the matrix tree of these fibers and formation composite body Before rouge combines, core shell rubbers nano particle is coated on the reinforcing glass fiber of the composite material.This is totally different from early stage Technology, wherein core shell rubbers nano particle is dispersed in entire matrix resin material.Therefore, the present invention with this is used in combination The difference of the related prior art of commercially available liquid epoxy core shell rubbers nano particle lotion a bit is, in the present invention, at this Before a little fibers are in conjunction with matrix resin, these lotions are used to form the initial sizing agent being coated on the glass fibers.On the contrary, In earlier technique, these lotions are used to form matrix resin itself.

These commercially available liquid epoxy/rubber nano grain emulsions represent core shell rubber nano particle of the invention Convenient source, because they have contained two kinds of main ingredients in initial sizing agent of the invention, i.e. core shell rubbers Grain and epoxy resin film-forming agent.

According to some embodiments enumerated, these commercially available liquid epoxy/rubber nano grain emulsions can be used Before manufacturing initial sizing agent of the invention, they are converted to aqueous emulsion.This can be easily by using conventional height Emulsification pretreatment technology carries out.For example, conventional high shear mixing technology and the conventional suitable surface-active of epoxy-can be used Agent, such as ethylene oxide/propylene oxide block copolymer contain 25wt% rubber nano particle and 75wt% liquid by emulsification The rubber nano particle that the weight ratio of the organic emulsion of epoxy resin, manufacture rubber nano particle and epoxy resin is 25/75 Aqueous sizing composition.

The core shell rubber amount of particles being applied on glass fibre or long filament substrate of the invention typically accounts for them and includes The about 0.01-25wt% of aqueous sizing composition solid content in it.More generally, the dosage of core shell rubber particle For the about 0.1-5wt% of these solids, about 0.3to 2wt%, about 0.5-1.5wt%, or even about 0.7-1.3wt%.Therefore, Typically via at least two different aqueous resins dispersion liquids are combined, to manufacture rubber nano particle of the invention containing water sizing Agent composition, one of emulsifying resins particle contain the combination of film-forming resin and core shell rubber nano particle, another cream Change resin particle and only contains film-forming resin.

Additional ingredient

Other than film-forming resin, the aqueous sizing composition containing core shell rubber nano particle of the invention can also Contain various additional optional members.

For example, these aqueous sizing compositions can contain about 5-30wt%, more generally about 8-20wt%, or even about The organosilanes coupling agent of 10-15wt% is based on solid content.For this purpose, thing can be used in the present invention Elder generation is used or can be in future for improving film-forming binder resin to any organic group silicon of glass fabric substrates adhesion strength Alkane coupling agent.In addition, as the case where binder resin, should select organosilanes coupling agent and it is to be used it is specific at Film adhesive resin is compatible.

The specific example of useful organosilanes coupling agent is Silquest A-1524 ureido silane, Silquest A- 1100 amino silanes, the poly- azimid of silylation of the Silquest A-1387 in methanol, obtained from Momentive's The poly- azimid of silylation of the Y-19139 in ethyl alcohol, Silquest A-174 methacryloxypropyl silane, Silquest A-187 epoxy radicals silicone hydride, Silquest A-1170 trimethoxy pair-silane, tri- second of Silquest A-11699 Oxygroup pair-silane, these wholes are obtained from Momentive and Silquest Al120.Silquest A-1524 and The blend of Silquest A-1387 and Silquest A-1100 are preferably used together with epoxy resin film-forming resin.

Another ingredient for including in the aqueous sizing composition for the particle containing rubber nano that can be used in the present invention is Lubricant.The example for being suitable for the commercially available lubricant of this purpose includes Katex 6760 (also referred to as Emery 6760) sun Ion lubricant, PEG400 monoleate (PEG400MO, Emerest 2646), PEG-200 monolaurate (Emerest 2620), PEG400 monostearate (Emerest 2640), PEG600 monostearate (Emerest2662).Typically use Dosage is 0.001-2wt%, the more typically 0.2-1wt% of sizing agent solids weight, or the cation profit of even about 0.5wt% Lubrication prescription, such as Katex 6760.At the same time, typically use dosage for 0.1-22wt%, more typically about 1-10wt%, or The even PEG lubricant of about 7wt% solid content.

Include in the aqueous sizing composition for the particle containing rubber nano that can be used in the present invention is another conventional Lubricant is wax.Any wax that is used or can be used as lubricant wax can be in the aqueous sizing composition of glass fibre It is used as wax in the aqueous sizing composition of rubber nano particle of the invention.280 wax of Michelman Michemlube is good Example.The order of magnitude is that the concentration of about 0.1-10wt% sizing agent solids weight is useful, while preferably from about 2-6wt% or very To the concentration of 4-5wt%.

Can include in the aqueous sizing composition of the particle of the invention containing rubber nano it is other other it is conventional at Dividing includes acetic acid, citric acid or other organic acids, and dosage is enough effectively to hydrolyze existing silane, in Silquest A- In the case of 1100, pH about 4-6 is typically required that.The pH of final sizing agent is typically within the scope of 5-6.5.

Other additives, such as 200 multi-functional epoxy's oligomer of Coatosil MP, aqueous polyurethane polymer, such as Obtained from Michelman U6-01 or the Baybond PU-403 of Bayer, or obtained from the Witco W-296 or W- of Chemtura 298 and analog because function known to them can also include applying in the aqueous of the particle of the invention containing rubber nano with conventional amount used In size composition.

Water content and load

In a conventional manner using conventional coating apparatus, by the aqueous sizing agent group of the particle of the invention containing rubber nano Object is closed to be applied on their glass fibre and/or long filament substrate.Therefore, they are prepared using enough water, so as to them Rheologic behavio(u)r it is substantially the same with conventional aqueous sizing agent or at least quite.Therefore, these aqueous sizing compositions Typically contain the total solids content of about 2-10wt%, more generally 4-8wt%, or even 5-7wt% is based on aqueous sizing agent The total weight of composition.

In addition, these aqueous sizing compositions containing nano particle are applied to their glass fibers also with conventional dosage In dimension and/or long filament substrate.For example, being commonly applied these sizing compositions, dosage makes the glass obtained being glued The LOI (loss (loss on ignition) when igniting) of glass fiber and long filament is about 0.2-1.5%, more typically 0.4- 1.0%, or even 0.5-0.8%.The concentration of core-shell structure copolymer rubber nano particle is typically about 0.3- in these sizing agents 2wt%, about 0.5-1.5wt%, or the order of magnitude of even about 0.7-1.3wt%, it is based on drying solid, it means that with regard to LOI Speech, the dosage for these core shell rubber nano particles being applied on their glass fibre and/or long filament substrate are typically about 0.001-0.015%, more typically about 0.002-0.010%, or even about 0.0025-0.0080%.

Operation example

In order to which more thoroughly description is of the invention, operations described below example is provided.

Embodiment 1 and comparative example A

By conventional wet-laying coating process, manufacture two pieces of fiberglass packings, wherein the glass fibre of wet chopped from Aqueous slurry deposit to diaphragm it is online after, be coated with the aqueous dispersion of resinoid bond, it is then dry and solidify.Respectively Use commercially available acrylic latex (the Rhoplex GL 720 obtained from Dow Chemical) and commercially available Lauxite Latex (the FG 654A obtained from Momentive) prepares the resinoid bond being applied in the two meshes.Selection is applied Amount of resin be with drying solid so that in both binders, acrylic resin is identical to the weight ratio of Lauxite Basic (15/85), and further so that the total amount for the binder being applied in each mesh is substantially the same.Embodiment 1 Resinoid bond further include the commercially available rubber core-shell nanoparticles of 1.7wt%, especially be obtained from Kenaka Corporation The Kane Ace MX-113 rubber core-shell nanoparticles of of Pasadena, Texas, based on Lauxite and third in binder The combination weight of olefin(e) acid resinoid.

Then the tensile strength and tearing strength of the fiberglass packing that so obtains on vertical or horizontal are tested.Due to glass Glass fiber mat and the asphalt shingle being associated with usually horizontally are weaker than their longitudinal direction, therefore, drawing horizontally It stretches intensity and tearing strength obtains product overall strength and preferably indicates.

Other than these tests, also by the performance test of rock powder pad, these fiberglass packings are measured horizontally Tearing strength.In this test, each cushion use first same amount of dusting rock dirt (dust), then measure in transverse direction On tearing strength.Using this test, because it provides the inorganic particulate filler because including in the bituminous coating that then applies Can caused by good simulation to the negative effect of fiberglass packing performance.For every a sample, the property of this rock powder pad It can test and carry out three times, and report the average value obtained for each test below.

Acquired results are listed in table 1 below:

Table 1

The stretching and tearing strength of the fiberglass packing of embodiment 1 and comparative example A

In upper table, " BW " refers to base weight, it be cured cushion weight (glass fibre adds cured binder) pound/ 100 feet².At the same time, loss when " LOI " refers to igniting, it is the standard method of measurement in this industry, is shown Binder is dry and solidify the remaining aqueous binders part % being initially applied in mesh on the web later.It can lead to It crosses with BW multiplied by LOI, measurement after drying and curing, based on drying solid, is applied to the binder in mesh Total amount.

It can be seen that according to table 1, the presence of rubber core-shell nanoparticles, which there is no, in the binder of embodiment 1 draws The influence (difference in table 1 is within experimental error) of the fiberglass packing tensile strength manufactured by this binder is played, but Relative to the control fiberglass packing of comparative example A, horizontally the tearing strength of this pad increases.Although in addition, table 1 also shows Rock powder causes the two cushion tearing strengths to significantly reduce, but this reduction is more prominent in the case where comparative example A.Specifically Ground, the presence that table 1 shows these rubber core-shell nanoparticles make its starting tearing of the cushion reservation 77% of embodiment 1 Intensity, and the cushion of comparative example A retains only 66% its initial tear strength, when the two cushions are by rock dirt.

This is statistics indicate that add the tearing that these rubber core-shell nanoparticles can improve in fiberglass packing transverse direction strong Degree, not only under conditions of " manufacture (as-made) as former state " (uncoated), but also under the use condition of simulation.

Embodiment 2 and comparative example B

8 additional cushions are prepared, of the invention and four are without using rubber core-shell structure copolymer to receive wherein four represent The control of rice grain.Using with same processes used in embodiment 1 and ingredient, manufacture these cushions, except that The rubber core-shell nanoparticles amount that includes in binder of the invention is represented as 1.85wt%.

Then by being coated with the pad each glass fibre obtained with the asphalt coating composition manufactured by asphalt cutback Pad, is formed as asphalt shingle for cushion, wherein the asphalt coating composition also calcite inorganic granular containing 65wt% is filled out Material, as a whole based on asphalt coating composition.

The tensile strength for measuring each roof boarding in the longitudinal direction, such as roof boarding each in vertical and horizontal both direction Tearing strength it is the same.In addition, the total tearing for measuring each roof boarding is strong by adding vertical and horizontal tearing strength together Degree.Finally, normalizing the tearing strength and tensile strength of these measurements by the weight of roof boarding.

Acquired results are listed in the following table 2.

Table 2

The stretching and tearing strength of the roof boarding of embodiment 2 and comparative example B

	Longitudinal MD is stretched	Laterally tearing	Total tearing
				Comparative example B	192	1870	3317
Embodiment 2	185	2037	3615
				% variation	-3.65	8.93	8.98

Table 2 shows to add the bonding of fiberglass packing used in rubber core-shell nanoparticles to manufacture asphalt shingle Assign roof boarding the effect substantially the same with its imparting cushion in agent.Particularly, table 2 shows the glass fibre with embodiment 1 Pad is the same, is horizontally shown using the asphalt shingle that these nano particles manufacture than no these nano particles manufacture Compare the significantly biggish tearing strength of roof boarding.In addition, table 2 further demonstrates that, in this case, in the longitudinal direction rather than with Above embodiments 1 report that horizontally these nano particles also cause the tensile strength of these roof boardings slightly to decline.

Embodiment 3

In the following embodiments, by wrapped around a mandrel in advance with commercially available waterborne epoxy matrix resin dispersion liquid Impregnated glass fibre manufactures the high-pressure composite pipe road of filament winding.Then the winding being thusly-formed, cured epoxy base are heated Body resin, then draws mandrel, produces final product pipeline.

By above-described conventional glass fibre manufacture technique, glass used in the manufacture of each composite material is manufactured Glass fiber, wherein the continuous glass fibre drawn and attenuated before being combined into fiber, is coated with initial sizing agent.Carry out three different realities It tests.In the first experiment for representing the prior art, initial sizing agent is free of core shell rubber nano particle.It is tested in other two In, initial sizing agent contains 0.5wt% core shell rubber nano particle and 1wt% core shell rubber nano particle respectively.

The initial sizing agent dosage being applied on each glass fibre is listed in the following table 3, while being listed in the following table 4 The concrete composition of each initial sizing agent.

Table 3

Sizing agent load

Embodiment	Rubber grain % in sizing agent	LOI%	Yardage, code/pound	Tex,g/kg
					Control	0	0.55	243.98	2033.20
4	0.5	0.57	251.74	1970.51
					5	1.0	0.63	251.69	1970.94

Table 4

The chemical composition of initial sizing agent

*Kaneka's Kane Ace^TMThe aqueous emulsion of MX-125 epoxy base emulsion, containing 75wt% epoxy resin and 25wt% core shell rubbers nano particle.

Two different analysis tests are carried out to the compound pipeline complex pipeline of the filament winding so obtained.In the first test, survey Determine the bursting strength of products obtained therefrom pipeline.In the second test, according to NOL Ring test method, No.AD0449719 is assessed, Naval Ordinance Laboratory, White Oak, Maryland, measurement when be exposed to boiling water it is 500 hours lower when product The interlaminar shear strength (ILSS) of pipeline.Other than these analysis tests, measures and records during the manufacture of each pipeline, During winding operation, the tension that generates on glass fibre used in the manufacture pipeline.Gained knot is listed in Fig. 3-6 Fruit.

As shown in figure 3, the bursting strength of product pipeline of the invention is larger about 8-11% than the bursting strength in control tube road. This show core shell rubber nano particle of the invention provide glass fiber reinforcement made according to the present invention polymer it is compound The mechanical property of materials significantly improves.

At the same time, Fig. 4 is shown in the case where being exposed to boiling water after 500 hours, core shell rubber nano particle of the invention It there is no the interlaminar strength negative effect for assigning product pipeline of the invention.This shows core shell rubber nanometer of the invention Particle does not negatively affect the chemically-resistant of the polymer composites of glass fiber reinforcement of the invention in any significant way Property.

Finally, Fig. 5 shows during the winding operation used in the compound pipeline complex pipeline for forming filament winding of the invention in glass The tension generated on glass fiber there is no to be influenced by core shell rubber nano particle of the invention.This shows of the invention Core shell rubber nano particle produces the polymer of glass fiber reinforcement of the invention without negative effect in any significant way Manufacturing process used in composite material.

Although foregoing merely illustrates several embodiments of the invention, it is to be understood that can be of the invention in no disengaging Many modifications are made in the case where spirit and scope.For example, it may be possible to and even it is expected in some cases, in conjunction with of the invention The other technologies of the polymer composites of core shell rubber nano particle technology and manufacture glass fiber reinforcement.

For example, above-mentioned commonly assigned U.S.5,840,370 describe manufacture glass/polymer prepreg Method, wherein forming " online " of some or all of matrix polymers of the polymer composites of final glass fiber reinforcement Apply a part as technology for making glass.Can by applying core shell rubber nano particle of the invention first, then second The glass fibre that the coating being thusly-formed is impregnated with the matrix polymer of polymer composites, thus in conjunction with the technology and this hair Bright technology.

All these modifications are intended to cover in the scope of the present invention and relevant only by following the claims limitation In universal of the invention.

Claims (11)

1. a kind of polymer composites of glass fiber reinforcement, it includes fiberglass packing, is contained:

Multiple individual glass fibres, wherein the top sizing of the glass fibre has nano particle containing core shell rubber and film forming The coating of the mixture of polymer；With

The resinoid bond that individual glass fibre is kept together, the resinoid bond account for fiberglass packing total weight 10-30wt%, the resinoid bond contain:

The polymeric blends of Lauxite and acrylic resin；And

Based on the total amount for removing the polymeric blends other than core shell rubber nano particle, the core-shell structure copolymer rubber of 0.5-4wt% Glue nano particle, average particle size are less than or equal to 100nm.

2. the polymer composites of the glass fiber reinforcement of claim 1, wherein the individual glass fibre formation passes through The fiberglass packing that resinoid bond keeps together.

3. the composite material of the glass fiber reinforcement of claim 1, wherein the core of rubber core-shell nanoparticles is by being selected from benzene second Synthetic polymer rubber manufacture in alkene/butadiene, polybutadiene, silicon rubber, acrylic rubber and its mixture.

4. the composite material of the glass fiber reinforcement of claim 1, wherein the composite material is asphalt shingle.

5. a kind of improved asphalt shingle, it includes:

Glass fibre, which is puted up a house, pushes up pad, contains:

Multiple glass fibres, the top sizing of the glass fibre have the mixed of nano particle containing core shell rubber and film forming polymer The coating of object is closed, and

The resinoid bond that individual glass fibre is kept together, the resinoid bond account for glass fibre and put up a house top pad always The 10-30wt% of weight, the resinoid bond contain:

The polymeric blends of Lauxite and acrylic resin；And

Based on the total amount for removing the polymeric blends other than core shell rubber nano particle, the core-shell structure copolymer rubber of 0.5-4wt% Glue nano particle, average particle size are less than or equal to 100nm；

Cover glass fiber is puted up a house the bituminous coating of top pad, which includes that the inorganic granular in 30-80wt% in it is filled out Material, wherein the inorganic particulate filler has the hardness greater than 3Moh, wherein the acrylic acid tree being present in polymeric blends The amount of rouge is 10-20wt%, based on the total amount of the polymeric blends, based on drying solid.

6. the asphalt shingle of claim 5, wherein the core of rubber core-shell nanoparticles is by being selected from phenylethylene/butadiene, poly- fourth Synthetic polymer rubber manufacture in diene, silicon rubber, acrylic rubber and its mixture.

7. the asphalt shingle of claim 5, wherein bituminous coating includes that 30-80wt% is selected from dolomite, silica, slabstone Inorganic special filler in ash and high carbon acid magnesium, the total weight of the pitch based on filling.

8. a kind of polymer composites of glass fiber reinforcement, it includes:

Matrix polymer；With

The multiple glass fibres dispersed in the matrix polymer, wherein the top sizing of glass fibre has receives containing core shell rubber The coating of the mixture of rice grain and film forming polymer；With

The resinoid bond that single glass fibre is kept together, the resin binder account for glass fibre put up a house top pad gross weight The 10-30wt% of amount, the resinoid bond contain:

The polymeric blends of Lauxite and acrylic resin；And

Based on the total amount for removing the polymeric blends other than core shell rubber nano particle, the core-shell structure copolymer rubber of 0.5-4wt% Glue nano particle, average particle size are less than or equal to 100nm.

9. the polymer composites of the glass fiber reinforcement of claim 8, wherein the surface of glass fibre carries rubber containing core-shell structure copolymer The coating of the mixture of glue nano particle and film forming polymer.

10. the polymer composites of the glass fiber reinforcement of claim 8, wherein by by the continuous glass fibre knot of multiple drawing-downs Be combined to form individual fiber and manufacture glass fibre, and further wherein individual continuous glass fibre combination before, apply Add on initial sizing composition to individual continuous glass fibre.

11. the polymer composites of the glass fiber reinforcement of claim 8, wherein the surface of glass fibre is carried in fiber system During making, after combining individual continuous glass fibre, it is applied to the second coating of the initial sizing composition of auxiliary on fiber, The initial sizing composition of the auxiliary includes additional core shell rubber nano particle and film forming polymer.