MX2015001470A

MX2015001470A - Improved fiberglass reinforced composites.

Info

Publication number: MX2015001470A
Application number: MX2015001470A
Authority: MX
Inventors: Mohammed Tazi; Jianxia Chen; Helen Huang; William G Hager; Jerry H C Lee
Original assignee: Ocv Intellectual Capital Llc
Priority date: 2012-08-03
Filing date: 2013-08-05
Publication date: 2015-08-20
Also published as: JP6320380B2; CN104812696A; EP2879989A1; KR102111816B1; CN104812696B; BR112015002386A2; CA2880548A1; US20140038481A1; KR20150039822A; WO2014022845A1; JP2015531015A

Abstract

A fiberglass reinforced composite is provided with improved physical properties. The fiberglass reinforced composite incorporates core-shell rubber nanoparticles within the resinous binder of the composite and/or within a sizing composition coated directly onto the individual glass fibers.

Description

COMPOSITE PRODUCTS, IMPROVED, REINFORCED WITH FIBER GLASS Field and Background of the Invention Conventional asphalt roof shingles are manufactured by applying an asphalt coating to a fiberglass network, incorporating sand or other roof granules into the asphalt covering while it is still soft, and then subdividing the network of this formed way in the individual tiles once the asphalt has hardened. The glass fiber network is normally made of glass fibers bonded together by a suitable resinous binder, in addition, a finely ground inorganic particulate filler is normally included in the asphalt coating to reduce cost, improve the resistance to tile heat distortion and reduce the UV degradation of the asphalt.

U.S. Patent No. 7,951,240, the entire disclosure of which is incorporated herein by reference, indicates that the tear resistance of roof tiles manufactured in this manner can be affected by the type of particulate filler contained in the asphalt coating. In particular, this patent indicates that the tear resistance of these roof tiles is can compromise if hard fillers such as dolomite, silica, slate dust, high hardness magnesium carbonate and the like are used.

It has been found that the physical properties of many types of fiberglass reinforced polymer composite products can be improved by including core-shell rubber nanoparticles in the resinous binder that is applied to the glass fibers before they are combined with the polymer that forms the matrix or body of a composite product, such as a fiberglass mat for use in the manufacture of tiles.

On the other hand, it has also been discovered that the glass fibers bearing these core-shell rubber nanoparticles can be easily fabricated by including them in the size that is applied to the fibers as manufactured before they are included in a separate polymer binder. subsequently applied to the fibers in a final manufacturing process, in which pre-prepared glass fibers are used to make useful products.

Brief Description of the Invention In some exemplary embodiments of the present invention, it has been discovered that the physical properties of a glass fiber reinforced composite product can be improved by incorporating core-shell rubber nanoparticles within the resinous binder of the composite.

In various exemplary embodiments of the present invention, the fiberglass reinforced composite product comprises an improved roofing mat for use in the manufacture of asphalt roofing shingles. Some exemplary aspects of the improved roof mat comprises a glass fiber mat composed of multiple glass fibers and a resinous binder which holds together the individual glass fibers, wherein the resinous binder includes core-shell rubber nanoparticles.

On the other hand, in accordance with further exemplary aspects of this invention, it has been found that the glass fibers bearing these core-shell rubber nanoparticles are manufactured by including core-shell rubber nanoparticles in the sizing applied. to the fibers as manufactured prior to, or in addition, including the particles in a separate polymer binder subsequently applied to the fibers in a later manufacturing process.

In this manner, the exemplary aspects of this invention provide a composite product of glass fiber reinforced polymer comprising a matrix polymer and glass fibers dispersed in the matrix polymer, wherein the surfaces of the glass fibers carry a coating of rubber nanoparticles core-cover.

In accordance with other exemplary aspects of the present invention, filaments and glass fibers are provided for use in the manufacture of a composite product of glass fiber reinforced polymer. The filaments and glass fibers comprise a glass fiber or filament substrate coated with an aqueous sizing composition, the aqueous sizing composition comprising a film-forming polymer, an organosilane coupling agent and rubber nanoparticles. core-cover.

Additional exemplary aspects of the present invention also provide a continuous process for manufacturing glass fibers, which comprises comprising charging molten glass through multiple orifices in a bearing to produce glass melt streams, allowing the melted streams of glass to flow through. solidify to form individual filaments. The individual filaments can be coated with an incipient sizing composition containing a lubricant, a film-forming resin and an organosilane coupling agent, and combined together to form the fiber. The process may further comprise applying a coating of core-shell rubber nanoparticles to the fiber.

Some example modalities provide fiberglass reinforced polymer composite products comprising a plurality of individual glass fibers and a resinous binder, wherein the core-shell rubber nanoparticles are incorporated into the resinous binder of the composite product. The individual glass fibers can form a glass fiber mat held together by the resinous binder. The resinous binder may include from 0.1 to 20% by weight of core-shell rubber nanoparticles, or from 0.5 to 10% by weight of core-shell rubber nanoparticles, based on the total amount of the resin in the binder. The average particle size of the core-shell rubber nanoparticles can be 250 nm or less. The resinous binder can be formed from a urea formaldehyde resin, an acrylic resin or a mixture thereof.

In some exemplary embodiments, the nucleus of the core-shell rubber nanoparticles is made of a synthetic polymer rubber selected from the group consisting of styrene-butadiene, polybutadiene, silicone rubber (siloxanes), acrylic rubbers and mixtures of the same.

In other example embodiments, the composite product is an asphalt roof tile.

In several example modalities, it is provided an improved roof mat for use in the manufacture of asphalt roof tiles. The improved roof mat comprises a glass fiber mat composed of multiple glass fibers and a resinous binder which holds the individual glass fibers together. The resinous binder may include core-shell rubber nanoparticles. The resinous binder may include from 0.1 to 20% by weight of core-shell rubber nanoparticles, based on the total amount of the resin in the binder. The average particle size of the core-shell rubber nanoparticles can be 250 nm or less. The resinous binder can be formed from a urea formaldehyde resin, an acrylic resin or a mixture thereof. The core of the core-shell rubber nanoparticles can be made of a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxanes), acrylic rubbers and mixtures thereof.

In yet other exemplary embodiments, an improved asphalt roof tile comprising a fiberglass roof mat composed of multiple glass fibers and a resinous binder that holds together the individual glass fibers and an asphalt coating that covers the fiberglass ceiling mat. The asphalt coating can include a inorganic particulate filler. The asphalt coating may also contain roof granules incorporated therein. In some exemplary embodiments, the resinous binder of the fiberglass roof mat includes core-shell rubber nanoparticles. The resinous binder may include from 0.1 to 20% by weight of core-shell rubber nanoparticles, or from 0.5 to 10% by weight of core-shell rubber nanoparticles, based on the total amount of resin in the binder. The average particle size of the core-shell rubber nanoparticles can be 250 nm or less. The resinous binder can be formed from a urea-formaldehyde resin, an acrylic resin or a mixture thereof. The core of the core-shell rubber nanoparticles can be made of a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxanes), acrylic rubbers and mixtures thereof. The asphalt coating may include from 30 to 80% by weight, based on the full weight of the filled asphalt, of an inorganic particulate filler selected from the group consisting of dolomite, silica, slate powder and high hardness magnesium carbonate.

In several example embodiments, a composite product of glass fiber reinforced polymer is provided comprising a matrix polymer and glass fibers dispersed in the matrix polymer. The surfaces of the glass fibers can be coated with core-shell rubber nanoparticles. In other exemplary embodiments, the surfaces of the glass fibers have a coating comprising a mixture of core-shell rubber nanoparticles and a film-forming polymer. In other exemplary embodiments, the surfaces of the glass fibers carry a first coating of an incipient sizing composition applied to the fibers during the manufacture of the fibers, the incipient sizing composition comprising core-shell rubber nanoparticles, a film-forming polymer and an organosilane coupling agent. The incipient sizing composition may contain a hydrocarbon wax.

In some exemplary embodiments, the glass fibers manufactured by combining multiple glass filaments attenuated together to form individual fibers and the incipient sizing composition are applied to the individual glass filaments before they are combined.

In some exemplary embodiments, a second coating of an incipient sizing composition secondary to the fibers is applied during the manufacture of the fibers after the glass filaments Individuals are combined, the secondary incipient sizing composition comprising additional core-shell rubber nanoparticles and a film-forming polymer.

Glass fibers can be manufactured by combining multiple glass filaments attenuated together to form individual fibers, wherein the surfaces of the glass fibers carry a first coating of an incipient sizing composition applied to the individual glass filaments before they are coated. combine, the incipient sizing composition comprising a film-forming polymer and an organosilane coupling agent, and wherein in addition the surfaces of the glass fibers carry a second coating of a secondary incipient sizing composition applied to the fibers during the After the individual glass filaments are combined, the secondary incipient sizing composition comprises core-shell rubber nanoparticles and a film-forming polymer.

The average particle size of the core-shell rubber nanoparticles can be 250 nm or less. The core of the core-shell rubber nanoparticles can be manufactured from a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxanes), acrylic rubbers and mixtures thereof.

In some exemplary embodiments, the core-shell rubber nanoparticles are applied to the reinforcing glass fibers in the form of a mixture of the core-shell rubber nanoparticles and a film-forming resin, and wherein the Mixture includes from 0.1 to 20% by weight of core-shell rubber nanoparticles, 0.5 to 10% of core-shell rubber nanoparticles based on the total amount of the film-forming resin in the mixture.

In some exemplary embodiments, the composite product of glass fiber reinforced polymer is a roof tile.

In some exemplary embodiments, a glass filament is provided for use in the manufacture of a composite product of glass fiber reinforced polymer. The glass filament may include a glass filament substrate that bears a coating of an incipient sizing composition, the incipient sizing composition comprising a film-forming polymer, an organosilane coupling agent and core-shell rubber nanoparticles. .

In other exemplary embodiments, a glass fiber is provided for use in the manufacture of a composite product of glass fiber reinforced polymer. The fiber The glass can comprise a glass fiber substrate carrying a coating comprising a film-forming polymer and core-shell rubber nanoparticles.

The glass fiber can be composed of multiple glass filaments combined together, the surfaces of the glass filaments carry a first coating of an incipient sizing composition applied to the filaments before being combined, the incipient sizing composition comprises a forming polymer of film, an organosilane coupling agent and core-shell rubber nanoparticles.

The surfaces of the glass fiber carry a second coating of a secondary incipient sizing composition applied to the fiber after the filaments forming the fiber are combined, the secondary incipient sizing composition comprises additional core-shell rubber nanoparticles and a film-forming polymer.

In other exemplary embodiments, a glass fiber is made by combining multiple glass filaments attenuated together to form the fiber, wherein the surfaces of the glass fiber carry a first coating of an incipient sizing composition applied to the glass filaments before they are combined, the incipient sizing composition comprises a film-forming polymer and an organosilane coupling agent. The surfaces of the glass fiber can additionally carry a second coating of a secondary incipient sizing composition which is applied to the fiber after the individual glass filaments are combined, the secondary secondary sizing composition comprises a film forming polymer and nanoparticles of core-shell rubber.

The average particle size of the core-shell rubber nanoparticles can be 250 n or less. Additionally the core of the core-shell rubber nanoparticles can be manufactured from a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxanes), acrylic rubbers and mixtures thereof.

The core-shell rubber nanoparticles can be applied to the filaments or glass fibers in the form of a mixture of the core-shell rubber nanoparticles and a film-forming resin, and wherein the mixture also includes 0.1 to 20% by weight of core-shell rubber nanoparticles, based on the total amount of the film-forming resin in the mixture.

In still further example modalities, provides a continuous process to manufacture the glass fiber which includes loading the molten glass through multiple holes in a bearing to produce glass melt streams, allowing the melted glass streams to solidify to form individual filaments, coating the individual filaments with an incipient sizing composition containing a lubricant, a film-forming resin and an organosilane coupling agent, and combining the individual filaments together to form the fiber. The process may further comprise applying a coating of core-shell rubber nanoparticles to the fiber.

The core-shell rubber particles can be applied to the glass fiber by including the core-shell rubber particles in the incipient sizing composition.

In some exemplary embodiments, the core-shell rubber particles are applied to the glass fiber by coating the glass fiber after a secondary incipient sizing composition comprising core-shell rubber nanoparticles and a polymer is formed. movie maker The incipient sizing can also contain core-shell rubber nanoparticles.

The average particle size of the core-shell rubber nanoparticles can be 250 nm or less and the core of the core-shell rubber nanoparticles can be manufactured from a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxanes), acrylic rubbers and mixtures of the same.

Brief Description of the Figures This invention can be better understood by reference to the following figures wherein: Figure 1 is a data box plot illustrating the tensile strengths of two certain glass fiber mats; Figure 2 is a data box plot illustrating the tensile strengths of two certain glass fiber mats; Figure 3 is a data box plot illustrating the tensile strengths of two certain asphalt roof shingles; Figure 4 is a bar graph showing the effect of the core-shell rubber nanoparticles of this invention having on the breaking strengths of the high pressure composite product tubes wound with glass fiber manufactured in accordance with this invention; Figure 5 is a graph showing the effect of these core-shell rubber nanoparticles having on the interlaminar shear strength of the fiberglass wound high pressure composite product tubes of Figure 1; Y Figure 6 is a graph showing the effect of these core-shell rubber nanoparticles having on the tension exerted on the glass fibers used to form the fiberglass-wound high pressure composite product tubes of Figure 4 during its manufacture.

Detailed description of the invention Core-Cover Rubber Particles The core-shell rubber nanoparticles are known articles of commerce described in several patents. For example, they are described in EP 2 053 083 Al, EP 5 830 086 B2, U.S. 5,002,982, U.S. 2005/0214534, JP 11207848, U.S. 4,666,777, U.S. 7,919,549 and U.S. 2010/0273382, the descriptions of each one that is incorporated herein by way of reference in their totalities. In general terms, they are composed of nanoparticles having a thermoplastic or thermosetting polymer shell and a core made of a synthetic polymer rubber such as styrene / butadiene, polybutadiene, silicone rubber (siloxanes) or acrylic rubbers. Generally, they have average particle sizes of about 250 nm or less, more commonly of about 200 nm or less, about 150 nm or less or even about 100 nm or less and a particle size distribution quite reduced. They are commercially available in number from different sources including Kenaka Corporation of Pasadena, Texas.

Manufacture of Fiberglass Glass fibers are typically manufactured by a continuous manufacturing process in which the molten glass is passed through the holes of a "bearing", the currents of the molten glass formed accordingly solidify into the filaments, and the filaments they combine to form a fiber or "wick" or "thread". Fiberglass manufacturing processes of this type are known and described in numerous patents, examples include 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, the descriptions of each one that is incorporated herein by way of reference in their totalities. The speed at which glass fibers are typically produced by these processes is in the order of about 1,220 to 4,572 meters per minute (4,000 to 15,000 feet per minute). It will therefore be appreciated that the time over which such a glassmaking process occurs, ie the period between the time when the molten glass leaves the bearing and the time when fully prepared and formed glass fibers or strands are packed , are stored and / or used is very short, in the order of a fraction of a second.

Glass fibers can be manufactured from any type of glass. Examples include Type A glass fibers, Type C glass fibers, Type E glass fibers, Type S glass fibers, Type ECR glass fibers (for example, Advantex ™ glass fibers commercially available from Owens Corning), Hiper-tex ™, wool glass fibers, and combinations thereof. In addition, synthetic resin fibers such as those made of polyester, polyamide, aramid, and mixtures thereof may also be included in the glass fiber mats of this invention. Similarly, fibers made from one or more materials of natural origin such as cotton, jute, bamboo, ramie, bagasse, hemp, coconut fiber, Indian hemp, salt, flax, henequen and combinations thereof may also be included. , as can be carbon fibers.

Normally, an aqueous coating or "sizing" is applied to the glass filaments after they have solidified but before they come into contact with the rotating spindle for attenuation. These sizes typically contain a lubricant to protect the fibers from damage by abrasion, a film-forming resin to aid in the bonding of the fibers to the polymer forming the body or matrix of the composite product in which the fibers will be used, and a organosilane coupling agent for improve the adhesion of the film-forming resin and the matrix polymer to the surfaces of the glass fibers. Although these sizes can be applied by spraying, they are typically applied by passing the filaments on a mat or roll containing the sizing on their surfaces.

Finished glass fibers manufactured in this way are used in the manufacture of a variety of different polymer composite products reinforced with glass fiber. In most of these manufacturing processes, the prepared glass fibers are combined with the matrix polymer that forms the composite body or matrix before the glass fibers are finally fixed in the product to be manufactured. In another process, the prepared glass fibers are first assembled into a "preform, which is then impregnated with the matrix resin that forms the body of the compound". This is the procedure used in the manufacture of roofing tiles, in which the glass fibers are formed in a self-supporting network (preform) and the network manufactured in this way is coated with asphalt, which is then solidified to form the product of final asphalt tile.

The fiberglass preforms used in this process are normally self-supporting or at least coherent in the sense that glass fibers Individual primers will not separate from each other when exposed to stresses and forces that arise when the preform is manipulated and / or impregnated with the matrix resin. For this purpose, the sized glass fibers are normally coated with an additional film-forming resin to bond the fibers together. For convenience, the coating compositions used for this purpose are referred to herein as "binder sizing." These binder sizes will be understood to be different from the sizing compositions applied to the filaments and glass fibers as part of their manufacturing process, which are referred to herein as "incipient sizing" or "incipient sizing compositions".

From the above, it must be expensive that the processes to manufacture glass fibers and processes to use glass fibers are considered in the industry as separate and different from each other. For this reason, the steps or process operations that occur during the manufacture of glass fibers are typically referred to as "in-line" steps or operations. In contrast, the process steps or operations that occur during the use of previously manufactured glass fibers, such as in the manufacture of polymer composite products reinforced with glass fiber, are typically referred to as steps or "offline" operations. This terminology is used, for example, in U.S. 5,840,370 mentioned above, as well as U.S. 8,163,664, U.S. 7,279,059, U.S. 7,169,463 U.S. 6,896,963 and especially U.S. 6,846,855. The descriptions of each of these patents are incorporated herein by way of reference in their entireties. This terminology is also used in this description.

Products composed of polymers reinforced with fiberglass.

Various aspects of this invention also relate to the manufacture of any type of composite product of glass fiber reinforced polymer. These products are well known in the industry, and are often referred to as "fiberglass reinforced plastics". They are composed of glass reinforcing fibers and a polymer resin that forms the body or "matrix" of the composite product. For convenience, these polymers are sometimes referred to herein as "matrix polymers". Also, in the context of this case, "polymer resin" and "polymer" are used in their broadest sense to include both synthetic resins made by hand as well as resinous materials of natural origin such as asphalt and the like.

The composite products of glass fiber reinforced polymers of this invention can be manufactured from any type of fiberglass Examples include Type A glass fibers, Type C glass fibers, Type E glass fibers, Type S glass fibers, Type ECR glass fibers (for example, Advantex ™ glass fibers commercially available from Owens Corning), Hiper-tex ™, and combinations thereof.

The inventive glass fiber reinforced polymer composite products may also include fibers made of materials other than glass, examples of which include synthetic resin fibers such as those made of polyester, polyamide, aramid, and mixtures thereof. Similarly, fibers made of one or more materials of natural origin such as cotton, jute, bamboo, ramie, bagasse, hemp, coconut fiber, linen, Indian hemp, sisal, henequen, and combinations thereof can also be include, how can be carbon fibers. Similarly, inventive fiberglass reinforced polymer composite products may also include non-fibrous fillers, examples of which include calcium carbonate, silica sand and wollastonite. In a preferred embodiment, the glass fiber reinforced polymer composite products of this invention contain a combined total of no more than about 5% by weight of non-glass fibers and fillers, based on the weight of all fibers and fillers in the glass fiber. compound. By way of Most preferably, all or essentially all of the fibers in the glass fiber composites of this invention are glass fibers.

Similarly, the glass fiber reinforced polymer composite products of this invention can be made from any resinous binder that has previously been used or can be used in the future as the matrix polymer to make the body or matrix of composite products. plastic reinforced with fiberglass. Examples include polyolefins, polyesters, polyamides, polyacrylamides, polyimides, polyethers, polyvinyl ethers, polystyrenes, polyoxides, polycarbonates, polysiloxanes, polysulfones, polyanhydrides, polyimines, epoxies, acrylics, polyvinyl esters, polyurethanes, maleic resins, ureic resins, melamine resins, resins of phenol, furan resins, polymer blends, alloys and mixtures thereof. Epoxy resins are especially preferred.

The amount of resinous binder that must be included in the glass fiber reinforced polymer composite products of this invention can vary widely and any conventional amount can be used. In some exemplary embodiments, in the case of glass fiber mats, the amount of the resin binder will be from about 10 to 30% by weight. weight, more typically from about 14 to 25% by weight, or even from about 16 to 22% by weight, based on the weight of the glass fiber mat in general.

Glass fiber reinforced polymer composite products can be manufactured by a variety of different manufacturing techniques including simple coating and lamination processes, but are more commonly manufactured by molding. Two different types of molding process are commonly used, wet molding processes and compound molding processes. In wet molding processes, the glass reinforcing fibers and the matrix polymer are combined in the mold immediately before molding. For example, the glass fiber mats produced in accordance with this invention can be manufactured by a wet lay molding process in which wet crushed glass fibers, after being deposited on a mobile screen of an aqueous suspension, are coated with an aqueous dispersion of a resin binder which is then dried and cured. The formed nonwoven web is an assembly of individual, randomly dispersed glass filaments joined together in their interstices by the resinous binder.

As stated above, the glass fiber mats of this invention include a resinous binder to hold the fibers together. For this one purpose, any resinous binder that has previously been used or can be used in the future to manufacture fiberglass mats used in the manufacture of asphalt roofing shingles can be used as the resinous binder of this invention. Examples include formaldehyde urea resins, acrylic resins, polyurethane resins, epoxy resins, polyester resins and so on. Urea formaldehyde resins and acrylic resins are preferred, while mixtures of urea formaldehyde resins and acrylic resins are even more preferred. In these blends, the amount of acrylic resin is desirably from about 2 to 30% by weight, more desirably about 5 to 25% by weight or even about 10 to 20% by weight of the combined amounts of urea resin formaldehyde and acrylic resin in the binder, on a dry solids basis.

The amount of resinous binder that should be included in the glass fiber mats of this invention can vary widely and any conventional amount can be used. Typically, the amount of resinous binder will be from about 10 to 30% by weight, more typically from about 14 to 25% by weight or even from about 16 to 22% by weight, based on the weight of the fiber mat glass in general.

The physical structure of the fiber structure of Glass of this invention is not critical and any physical structure that has been previously used, or can be used in the future to manufacture fiberglass mats for asphalt roof tiles, can be used for the fiberglass mat of this invention. For example, glass fiber non-woven webs as well as woven and nonwoven fiberglass fabrics or scrim can be used to manufacture the glass fiber mats of this invention.

More commonly, however, the glass fiber mat of this invention will be manufactured by a wet laying process in which the wet crushed glass fibers, after being deposited on a movable screen of an aqueous suspension, are coated with an aqueous dispersion of a resin binder which is then dried and cured. The formed nonwoven web is an assemblage of individual, randomly dispersed fiber filaments joined together in their interstices by the resinous binder.

Ceiling tile In some exemplary embodiments, an inventive asphalt roof tile is fabricated from the inventive fiberglass network, as described above, using conventional production methods, i.e., by applying a molten asphalt coating composition to network of inventive fiberglass, by incorporating sand or other roofing granules into this asphalt coating while still soft, and then subdividing the net in this manner formed into individual roof tiles once the coating asphalt has hardened. Any production method that can be used that has been used, or used in the future, can be suitable in the production of inventive fiberglass mats and tiles. Any fiberglass mat that has been previously used, or may be used in the future, to manufacture asphalt roof shingles may be suitable for use in the manufacture of inventive fiberglass mats and shingles.

For this purpose, any asphalt coating composition that has previously been used or may be used in the future to manufacture asphalt roof shingles may be suitable for use as the asphalt shroud in this invention. As described in the U.S. 7,951,240 indicated in the foregoing, these asphalt coating compositions include a substantial amount of inorganic particulate filler. In addition, they can be manufactured from a variety of different types and grades of asphalt and can also include several different optional ingredients such as polymeric modifiers, waxes and the like. Any of the different grades of asphalts described herein, as well as any of different inorganic resin particulate fillers and optional ingredients described herein, may be suitable for manufacturing the roof tiles of this invention.

In addition to these ingredients, the asphalt coating composition used in this invention also includes an inorganic particulate filler. For this purpose, any inorganic particulate filler that is or has been known for use in the manufacture of asphalt roof tiles can be used. For example, calcite (crushed limestone), dolomite, silica, slate dust, high hardness magnesium carbonate, rock dust different from crushed limestone, and the like can be used. Concentrations in the order of 30 to 80% by weight, based on the full weight of the asphalt coating, can be used although concentrations of about 40 to 70% by weight or even about 50 to 70% by weight are more typical.

As indicated above, some of these inorganic particulate fillers are known to adversely affect the tear strength of asphalt roof tiles made with these materials. In particular, inorganic fillers that exhibit a high degree of hardness (ie, hardness greater than about 3) Moh) such as dolomite, silica, slate dust, high hardness magnesium carbonate, etc., are known to produce asphalt shingles that have lower tear strengths than the otherwise identical shingles made of softer inorganic filler such as calcite (crushed limestone) and the like. Therefore, it is common practice in this industry to use calcite or other soft inorganic particulate material as the asphalt filler, at least when the asphalt shingles of higher tear strengths are desired. Tear resistance is an important property because it reflects the ability of an installed tile to resist being destroyed or otherwise detached from a roof substrate by a strong wind. The same can not be said for the tensile strength, since the tear strength and the tensile strength do not correlate with each other normally, at least in the asphalt roof tiles and fiberglass mats of the which are manufactured. In fact, tear resistance and tensile strength can still be inversely proportional in some of these products. Core-Fiberglass Glass Mats In accordance with various aspects of this invention, it has been discovered that the problem of poor tear resistance of asphalt roof tiles can be overcome or otherwise overlooked by incorporating core-shell rubber particles in the resin binder used to make the fiberglass mat from which the inventive asphalt roof tile is manufactured. Therefore, according to various aspects of this invention, asphalt roof tiles showing superior tear strengths can be produced although hard inorganic fillers such as dolomite, silica, slate dust, high hardness magnesium carbonate, and the like are included in their asphalt coating compositions.

Once the asphalt coating composition of this invention is applied to the inventive fiberglass mat, a conventional roofing granule such as sand or the like is applied to and incorporated in this asphalt coating while still soft, such as in a conventional way. The asphalt coating is then allowed to harden, and the thus-hardened net formed in this way is subdivided into individual roof tiles.

It has already been proposed to use latexes of these core-shell rubber nanoparticles as binders for glass fiber mats. See, for example, EP 2 053 083 Al, EP 5830 086 B2 and U.S.2005 / 0214534 indicated in the foregoing. In such use, however, the fiber binder Glass is completely composed of these core-shell rubber nanoparticles. In contrast, in some exemplary aspects of this invention, the core-shell rubber nanoparticles can be incorporated in small amounts but suitable as additives to improve the properties of a polymer resin that forms the body of the resin binder. According to some aspects of the present invention, the amount of these core-shell rubber nanoparticles included in the resin binder of the glass fiber mat is from about 0.1 to 20% by weight, more particularly from about 0.5 to 10% by weight or even about 1 to 4% by weight, based on the total amount of the other binder polymer resins, i.e., excluding the weight of the core-shell nanoparticles of the rubber.

It is also already known that the tensile strength of a solid polymer mass (as reflected by its fracture toughness, peel strength, and overlap shear strength) can be improved by including these core rubber nanoparticles. covered in the mass as fillers. However, as indicated in the above, the tear strength and tensile strength do not correlate with each other in the field of asphalt roof tiles. This is shown in Figs. 1 and 2, which are cash graphs showing the tensile strengths and tear strengths of fiberglass mats manufactured with different conventional binders. See, also, Figure 3, which is a similar box graph showing the tear resistance of asphalt roof tiles made with these different fiberglass mats. As shown in Figure 1, the tensile strength of the mat made with the binder A was better than the tensile strength of the mat made with the binder B. In contrast, both the tear resistance of the manufactured mat with the binder A (Figure 2) as the tear strength of the asphalt roof tile made with the binder A (Figure 3), they were worse than the tear strength of the mat and the tiles made with the binder. shows that there is no direct correlation between tear strength and tensile strength in asphalt roof tiles and their associated fiberglass mats. This, in turn, shows that the improved tear strengths of the inventive mats and tiles is a different phenomenon from the improved tensile strengths shown in the prior art.

The cover of the core-shell rubber nanoparticles used in this invention can be formed essentially from a thermoplastic or a polycarbonate or thermoplastic material. thermosetting as long as it is compatible with the polymer used to form the resinous binder of the glass fiber mat used in this invention. And by "compatible" it is proposed that the polymer forming the shell did not react adversely with the resinous binder, either by adversely affecting its physical or chemical stability or by generating an unpleasant or unwanted byproduct.

Composite Products Reinforced with Additional Fiberglass According to other exemplary embodiments, glass fiber reinforced composite products are formed by composite molding, wherein the glass reinforcing fibers and the matrix polymer are combined into a "pre-impregnated material" before being loaded into mold. These pre-impregnated materials can take the form of self-supporting objects in which the glass fibers are randomly oriented, such as the sheets of glass fiber or "veils" used to form the asphalt shingles. In addition, they can also take the form of self-supporting objects in which the glass fibers are oriented in predetermined directions, such as the three-dimensional "skeletons" used to form the load-bearing products of complex shape such as oscillating arms for automotive suspensions. These materials pre impregnated also take the form of pellets, pellets or agglomerates composed of the matrix polymer containing shredded randomly distributed glass fiber.

Specific examples of the molding process that can be used to make the glass fiber reinforced polymer composite products of this invention include injection molding, bubble molding, compression molding, vacuum bag molding, mandrel wrapping, lamination wet, chopper gun application, filament winding, extrusion molding, reverse extrusion, resin transfer molding and vacuum assisted resin transfer molding.

According to some exemplary embodiments, the composite product of glass fiber reinforced polymer includes pressure-bearing containers such as tubes and tanks formed by filament winding or mandrel wrapping, especially products of this type in which the matrix polymer It is an epoxy resin. These products are well known and are described, for example, in U.S. 5,840,370 and U.S. 7,169,463, mentioned in the above. As described in these patents, these pressure-bearing containers are normally manufactured by winding a continuous glass fiber that has been impregnated with some or all of the matrix polymer necessary to form the container around a rotating steel mandrel in orientations. specific. Any additional matrix polymer is then added, and the matrix polymer is then cured and the mandrel is removed, thereby producing the product container. Alternatively, these products can be manufactured by wrapping a preformed sheet or web of glass fibers, pre-impregnated with some or all of the matrix polymer necessary to form the container, around a stationary steel mandrel followed by adding additional matrix polymer. If necessary, cure the matrix polymer and remove the mandrel. As further described in these patents, the glass fibers used to form these products are normally prepared during manufacture of the fiber with a binder sizing containing a lubricant, a film-forming resin and a coupling agent which is normally an organosilane. .

According to some exemplary examples of this invention, core-shell rubber nanoparticles can be incorporated into the sizing stock that is applied to the glass fibers as manufactured. It has been found that incorporating these nanoparticles onto the fibers in this way is not only very convenient from a manufacturing point of view but also effective in the production of glass fibers with improved reinforcing properties when used in a variety of different applications. of composite products of polymers reinforced with fiber of glass.

In general terms, it is desirable according to this invention for the average particle size of the core-shell rubber particles used in this invention to be 100 times smaller (i.e., less than 1%) of the average diameter of the particles. glass reinforcing fibers to which it is applied. Average particle sizes 150 times smaller ie less than 0. 67%) or even 200 times smaller (that is, less than 0. 5%) of the glass reinforcing fibers are interesting as well.

As explained above, it is known that the tensile strength of a solid polymer mass (as reflected by its fracture toughness, peel strength and overlap shear strength) can be improved by including these nanoparticles of core-shell rubber in the mass as fillers. See, "Structure-Property Relationship In Core-Shell Rubber Toughened Epoxy Nanocomposites," A Dissertation by Ki Tak Gam Submitted to the Office of Graduate Studies of Texas A &M University in partial fiilment of the requirements for the degree of Doctor of Philosophy December 2003. However, as detailed in the above, the tear resistance of an asphalt roof tile and its tensile strength do not correlate with each other. This shows that the improved tear strengths of asphalt roof tiles manufactured in accordance with this invention is a different phenomenon from the improved tensile strengths shown in the prior art.

In this regard, it should be appreciated that the tensile strength of a solid polymer mass is understood to be a function of its cohesive strength, i.e. the ability of the mass to be held together when under a tensile load. In contrast, the tear strength of an asphalt roof tile is understood to be a function of a completely different phenomenon, i.e., the ability of the binder sizing composition that covers the glass fiber web of the tile to promote the adhesion between the web and the asphalt coating subsequently applied (matrix polymer). Additionally, when the core-shell rubber particles are used to improve the tensile strength of a solid polymer mass, enough of these nanoparticles are used to fill the mass of the complete polymer. In contrast, a much smaller amount of core-shell rubber nanoparticles is used in this invention, since these nanoparticles are present on the glass fiber surfaces and are not distributed in the mass of the matrix polymer that forms the body of reinforced polymer composite products with inventive fiberglass.

In accordance with this invention, the core-shell rubber nanoparticles of this invention can be applied to the glass reinforcing fibers at any time prior to the application of the matrix polymer forming the body of the composite polymer products reinforced with inventive fiberglass. Thus, for example, the core-shell rubber nanoparticles can be applied to the glass reinforcing fibers in a binder sizing after they are manufactured and stored, in a separate application step as part of the manufacturing process for producing the glass reinforced polymer composite products of this invention.

Alternatively, they can be applied to the glass fibers "in line" during the manufacture of the glass fiber as part of the fiberglass manufacturing process. Typically, this will be done by including these core-shell rubber nanoparticles in the incipient sizing composition applied to the individual glass filaments used to form the glass fiber, before these filaments are combined together to form the fiber. Alternatively, these core-shell rubber nanoparticles can be applied to the glass fibers after they are formed into a separate aqueous sizing composition. For convenience, these compositions of Separate sizing are referred to in this document as "secondary incipient readings". In a third procedure, both of these procedures can be used, some of the core-shell rubber particles are applied to the individual filaments in the incipient sizing before the glass fibers are formed and the rest is applied in a sizing incipient secondary after the fibers are formed.

Regardless of which of these procedures is used, in-line application allows these core-shell rubber particles to be applied conveniently during fiberglass fabrication, which in turn eliminates the need for a process step "outside" of line "separated during the subsequent manufacture of the inventive glass fiber reinforced polymer composite products. In addition, the on-line application of the core-shell rubber nanoparticles can reduce the amount of film-forming polymer that is finally applied to the glass fibers, at least when the nanoparticle is included in the incipient sizing composition used during the manufacture of fiber. This is because it promotes the adhesion of the core-shell rubber nanoparticles to the glass fibers, that the nanoparticles must be applied together with a film-forming polymer. Therefore, the combination of these Nanoparticles with incipient glass sizing eliminates the need for a second coating of subsequent film-forming resin.

As indicated above, the core-shell rubber nanoparticles of this invention can be applied to the glass fiber or filament substrates together with a suitable film-forming resin. For this purpose, any film-forming resin that has previously been used or may be used in the future as a film-forming resin in a fiberglass sizing and / or filaments may be suitable for use.

As seen in the art, it is conventional practice when selecting the film-forming resin that is used in an incipient sizing or binder sizing to select a resin that is compatible with the matrix resin to be used to make the composite product. fiberglass that is finally produced. For example, if a particular fiberglass composite product is to be manufactured with an epoxy resin matrix, then a compatible epoxy resin will normally be selected as the film-forming resin for fiberglass sizing. This same customary practice is followed according to this invention, that is, the film-forming resin used in the sizing containing the core-shell rubber nanoparticles of this The invention is desirably selected to be compatible with the matrix resin of the composite product of the glass fiber reinforced polymer that is produced.

As further indicated in the foregoing, this invention finds particular use in the manufacture of glass fiber reinforced polymer composite products of epoxy resins, due to superior physical properties (e.g., tensile strength) and chemical resistance of these polymers. For this purpose, in some exemplary embodiments, it is desirable to select as the film-forming resin in the sizing containing the core-shell rubber particles, a type A epoxy resin of linear bisphenol of moderate molecular weight. In this context, "moderate molecular weight" means a weight average molecular weight of about 10,000 to 250,000. Weight average molecular weights of 15,000 to 100,000 or even 20,000 to 50,000 are preferred. Linear bisphenol type A epoxies are desirable because many fiberglass reinforced polymer composite products, and especially those requiring high strength and good chemical resistance, are manufactured from linear bisphenol type A epoxy matrix resins. These molecular weights are desirable, because the epoxy resin will not effectively form a film if its molecular weight is very high and it will undergo crystallization undesired in the coating equipment if its molecular weight is very low.

In addition to linear bisphenol type A epoxies, modified epoxy resins can also be used. For example, epoxy novolacs can also be used.

Specific examples of commercially available epoxy resins which are useful as the film-forming resin which are used in conjunction with the core-shell rubber nanoparticles of this invention are the aqueous epoxide emulsion AD-502 of AOC, aqueous emulsion Neoxil 962 / Da of DSM, EpiRez 5003 by Momentive, epoxy emulsion EpiRez 3511 by Momentive. The mixtures are also effective, especially AD-502 + EpiRez 5003 in a ratio of 95: 5.

The amount of film-forming resin that can be present in the aqueous sizing containing the core-shell rubber nanoparticles of this invention can vary widely, and essentially any amount can be used that will provide an effective coating composition. Typically, the amount of film-forming resin will be from about 60 to 90% by weight of the aqueous size on a dry solids basis (i.e., excluding water). The concentrations in the order of about 65 to 85% by weight, or even 73 to 77% by weight, on a dry weight basis are preferred.

Sizes with Combination Particles As indicated above, the aqueous sizing containing the core-shell rubber nanoparticles of this invention may also contain a film-forming resin. While each of these ingredients can be separately supplied to and contained in this aqueous sizing composition, in one particularly interesting embodiment of this invention these ingredients are combined together in the emulsified particles contained in this aqueous sizing composition.

The core-shell rubber nanoparticles are commercially available in a variety of different forms. One such form is an organic emulsion of the rubber nanoparticles dispersed in the pure liquid epoxy resin (ie, without solvent). Examples of these products include the Kane AceMR MX line from CSR Liquid Epoxy Emulsions available from Kaneka Belgium NV. These liquid epoxy / rubber nanoparticle emulsions comprise stable dispersions of about 25 to 40% by weight of CSR (core-shell rubber nanoparticles) in several different kinds of liquid epoxy resin systems including bisphenol type A liquid epoxy resins, liquid epoxy resins type F of bisphenol, liquid epoxy resins type epoxy phenol novolac, liquid epoxy resins type triglycidyl-p-aminophenol, tetraglycidyl-methylene-dianiline liquid epoxy resins, and cycloaliphatic liquid epoxy resins. There are well-known articles from the trade that have previously been used to harden epoxy and other matrix resins, including matrix resins used to form polymer composite products reinforced with glass fiber such as filament wound tubes and the like.

In this regard, it should be remembered that a significant difference between this invention and the previous technology for manufacturing glass fiber reinforced composite products containing core-shell rubber nanoparticles is that, in this invention, the core rubber nanoparticles Coats are coated on the glass reinforcing fibers of the composite product before these rows are combined with the matrix resin that forms the body of the composite product. This is completely different from the prior technology in which the core-shell rubber nanoparticles are dispersed throughout the entire mass of the matrix resin. Thus, a difference between this invention and prior technology in connection with the use of these commercially available liquid epoxy core-shell rubber nanoparticle emulsions is that, in this invention, these emulsions are used to form the incipient sizing. which is coated on the fibers of glass before these fibers are combined with the matrix resin. In contrast, in the previous technology, these emulsions are used to form the matrix resin alone.

These commercially available liquid epoxy / rubber nanoparticle emulsions represent a convenient source of the core-shell rubber nanoparticles of this invention, because they already contain two main ingredients of the incipient sizes of this invention, i.e. core rubber / cover and epoxy resin film former.

According to some exemplary embodiments, before these commercially available liquid core-shell rubber nanoparticle emulsions can be used to make the incipient sizes of this invention, they are converted into aqueous emulsions. This can be easily done by using conventional high shear emulsification techniques. For example, an aqueous sizing composition of rubber nanoparticles in which the weight ratio of the rubber nanoparticles to epoxy resin is 25/75 can be manufactured by emulsifying an organic emulsion containing 25% by weight of rubber nanoparticles and 75% by weight of liquid epoxy resin using conventional high shear mixing techniques and conventional epoxy suitable surfactants such as ethylene oxide / sodium oxide block copolymers propylene.

The amount of core / shell rubber particles that will be applied to a glass fiber or filament substrate according to this invention will typically be represented from about 0.01 to 25% by weight of the solids content of the aqueous sizing compositions in the which are contained. Most commonly, the amount of core / shell rubber particles will be from about 0.1 to 5% by weight, about 0.3 to 2% by weight, from about 0.5 to 1.5% by weight, or even from about 0.7 to 1.3% by weight of these solids. Accordingly, the aqueous nanoparticle sizing compositions of this invention will typically be manufactured by combining at least two different aqueous resin dispersions, one of which emulsified resin particles contain a combination of film-forming resin and core-rubber nanoparticles. cover, the others whose emulsified resin particles contain only the film-forming resin.

Additional Ingredients In addition to the film-forming resin, the aqueous sizing composition containing the core-shell rubber nanoparticles of this invention may also contain several additional optional ingredients.

For example, these water-sized compositions they may contain from about 5 to 30% by weight, more commonly from about 8 to 20% by weight or even from about 10 to 15% by weight of an organosilane coupling agent based on the solids content. For this purpose, any organosilane coupling agent that has previously been used or may be used in the future to improve the bond strength of a film-forming binder resin to a glass fiber substrate can be used in this invention. Also, as in the case of the binder resin, the organosilane coupling agent must be selected to be compatible with the particular film-forming binder resin that is used.

Specific examples of useful organosilane coupling agents are silquest ureidosilane A-1524, Silquest A-1100 aminosilane, Silquest A-1387 silicylated polyazimide, Momentive ethalylated polyazimide in ethanol Y-19139, Silquest A-174 methacryloxysilane, epoxy-silane Silquest A-187, trimetoxy-bis-silane Silquest A-1170, triethoxy-bis-silane Silquest A-11699, all from Momentive and Silquest A1120. Silquest A-1524 as well as Silquest A-1387 and Silquest A-1100 blends are preferred for use with epoxy resin film forming resins.

Another ingredient that can be included in aqueous sizing compositions containing nanoparticles of rubber used in this invention is a lubricant.

Examples of commercially available lubricants that are suitable for this purpose include cationic lubricant Katex 6760 (also known as Emery 6760), monooleate PEG400 (PEG400 MO, Emerest 2646), monolaurate PEG-200 (Emerest 2620), monostearate PEG400 (Emerest 2640), PEG600 monostearate (Emerest 2662). Cationic lubricants such as Katex 6760 are typically used in amounts of 0.001 to 2% by weight, more typically 0.2 to 1% by weight, or even about 0.5% by weight of size solids. Meanwhile, PEG lubricants are typically used in amounts of 0.1 to 22% by weight, more typically of about 1 to 10% by weight, or even of about 7% by weight of solids content.

Still another conventional lubricant that can be included in the aqueous sizing compositions containing rubber nanoparticles used in this invention is a wax. Any wax that seals or can be used as a lubricating wax in an aqueous fiberglass sizing composition can be used as the wax in the aqueous nanoparticle rubber sizing compositions of this invention. Michelman Michemlube 280 wax is a good example. Concentrations in the order of about 0.1 to 10% by weight of sizing solids are usable, while concentrations of about 2 to 6% by weight or even 4 to 5% are preferred.

Still other conventional ingredients that can be included in the aqueous sizing compositions containing rubber nanoparticles of this invention include acetic, citric or other organic acids in an amount sufficient to efficiently hydrolyze the silanes that are present, which typically require a pH of about 4-6 in the case of Silquest A-1100. The final sizing pH will typically be in the range of 5-6.5.

Other additives such as multifunctional epoxy oligomer Coatosil MP 200, aqueous urethane polymers such as Michelman U6-01 or Baybond PU-403 of Bayer, Witco W-296 or W-298 of Chemtura or the like can also be included in the sizing compositions Aqueous containing rubber nanoparticles of this invention for their known functions in conventional amounts.

Water Content and Loads The aqueous sizing compositions containing rubber nanoparticles of this invention are applied to their fiber and / or glass filament substrates in a conventional manner using conventional coating equipment. Therefore, they are formulated with sufficient amounts of water so that their rheological properties are essentially the same or at least comparable with those of conventional aqueous sizing. Therefore, these aqueous sizing compositions will typically contain a total solids content of about 2 to 10% by weight, more commonly 4 to 8% by weight or even 5 to 7% by weight, based on the total weight of the sizing composition. watery In addition, these aqueous sizing compositions containing nanoparticles are also applied to their fiber substrates and / or glass filaments in conventional amounts. For example, these sizing compositions will normally be applied in amounts such that the LOI (loss in ignition) of the prepared glass fibers and filaments obtained is from about 0.2 to 1.5%, more typically from 0.4 to 1.0% or even 0.5. to 0.8%. Since the concentration of the core-shell rubber nanoparticles in these sizes will typically be in the order of about 0.3 to 2% by weight, about 0.5 to 1.5% by weight, or even about 0.7 to 1.3% by weight, on a dry solids basis, this means that the amount of these core-shell rubber nanoparticles that will be applied to their fiber and / or glass filament substrates in terms of LOI will normally be from about 0.001 to 0.015%, so more typical from about 0.002 to 0.010% or even from about 0.0025 to 0.0080%.

Work examples In order to more fully describe this invention, the following working examples are provided.

Example 1 and Comparative Example A Two glass fiber mats were manufactured by a conventional wet laid coating process in which wet crushed glass fibers, after being deposited on a movable screen of an aqueous suspension, were coated with an aqueous dispersion of a resin binder. and then they dried and cured. Resin binders applied to both networks were each prepared using a commercially available acrylic latex (Rhoplex GL 720 available from Dow Chemical) and a commercially available urea formaldehyde resin latex (FG 654A available from Momentive). The amounts of resin applied were selected so that the weight ratio of the acrylic resin to urea formaldehyde resin in both binders was the same on a dry solids basis (15/85) and in addition so that the total amount of the binder applied to each res was essentially the same. The resin binder of Example 1 also included 1.7% by weight, based on the combined weights of urea formaldehyde and acrylic resins in the binder, of commercially available core-shell rubber nanoparticles, in particular Kane Ace MX-113 core-shell rubber nanoparticles available from Kenaka Corporation of Pasadena, Texas.

The fiberglass mats obtained in this manner were then tested for tensile strength and tear resistance in the cross or transverse direction. Because fiberglass mats and their associated asphalt roof tiles are generally weaker in their transverse direction than in their machine direction, the tensile and tear strengths in the transverse direction give a better indication of the general resistance of the product.

In addition to these tests, the tear strengths of these glass fiber mats in the transverse direction were also determined by a performance test of the rock dust mat. In this test, each mat was first powdered with the same amount of a powder rock and then measured for the tear strength in the transverse direction. This test was used, because it provides a good simulation of the adverse effect on the properties of the glass fiber mat that can be caused by the inorganic particulate fillers contained in a subsequently applied asphalt coating. This Performance test of the rock dust mat was carried out three times for each sample, with the average values obtained for each test reported below.

The results obtained are shown in the following Table 1: Table 1 Resistances to the Pull and Tear of the Fiberglass mats of Example 1 and Example Comparative A In the above table "BW" refers to the basis weight, which is the weight of the cured mat (fiberglass plus cured binder) pounds per 100 square feet. Meanwhile, "LOI" refers to the loss of ignition, which is a standard measurement in this industry indicating the portion of the aqueous binder originally applied to the network, in percent, that remains on the network after the binder has been dried and cured The total amount of Binder applied to the net after drying and curing, ie on a dry solids basis, can be determined by multiplying BW by LOI.

As can be seen from Table 1, the presence of core-shell rubber nanoparticles in the binder of Example 1 caused essentially no effect on the tensile strength of the glass fiber mat made of this binder ( the difference in Table 1 is within the experiment error), but the tear resistance of this mat is increased, in the transverse direction relative to the control fiberglass mat of Comparative Example A. In addition, Table 1 also shows that, while the rock dust caused a significant decrease in tear resistance of both mats, this decrease was more pronounced in the case of Comparative Example A. Specifically, Table 1 shows that the presence of these rubber nanoparticles of Core-shell allowed the mat of Example 2 to retain 77% of its original tear strength, while The mat of Comparative Example A retained only 66% of its original tear strength when both mats were covered with rock dust.

These data show that the addition of these Core-shell rubber nanoparticles improves the tear resistance of glass fiber mats in the transverse direction, not only in an "as-done" condition (uncoated) but also in a simulated use condition.

Example 2 and Comparative Example B Eight additional mats were prepared, four representing this invention and four being the controls in which core-shell rubber nanoparticles were not used. These mats were manufactured using the same procedures and ingredients as used in Example 1, except that the amount of core-shell rubber nanoparticles included in the binders representing this invention was 1.85% by weight.

Each fiberglass mat obtained afterwards was formed on an asphalt roof tile by coating the mat with an asphalt coating composition made of the coating asphalt, the asphalt coating composition also containing 65% by weight based on the Asphalt coating composition in general of an inorganic particulate calcite filling.

The tensile strength of each roof tile in the machine direction was measured, as was the tensile strength of each roof tile in both machine and cross directions. In addition, the resistance to total tearing of each roof tile was determined by adding the resistance to the tearing of the machine and cross. Finally, these resistance to tearing and traction measures were normalized by the weight of the tile.

The results obtained are shown in the following Table 2 Table 2 Resistances in the Pulling and Tearing of Ceiling Tiles of Example 2 and Comparative Example B Table 2 shows that the addition of the core-shell rubber nanoparticles to the binder of a fiberglass mat used to make an asphalt roof tile imparts essentially the same effect on the tile as it imparts to the mat. In particular, Table 2 shows that, similar to mats of fiberglass of Example 1, the asphalt shingles fabricated with these nanoparticles show resistance to tearing significantly higher in the transverse direction than the control shingles fabricated without these nanoparticles. Furthermore, Table 2 further shows that these nanoparticles also cause a slight decrease in the tensile strength of these tiles, in this case in the machine direction rather than in the transverse direction as reported in Example 1 in the above .

Example 3 In the following examples, high-pressure composite filament wound tubes with filaments were manufactured by winding around a mandrel glass fibers that have been previously impregnated with a commercially available aqueous epoxy resin resin dispersion. The coil formed in this manner was then heated to cure the epoxy matrix resin and the mandrel was then removed to produce the final product tube.

The glass fibers used to manufacture each composite product were manufactured by a conventional fiberglass manufacturing process as described above in which the attenuated glass filaments, before being combined into the fiber, were coated with a sizing incipient. Three different experiments were made. In the first experiment that represents the previous technique, the incipient sizing did not contain core-shell rubber nanoparticles. In the remaining two experiments, the incipient sizing contained 0.5% by weight of nanoparticles of core-shell rubber and 1% by weight of core-shell rubber nanoparticles, respectively.

The amount of incipient sizing applied to each glass fiber is set forth in the following Table 3, while the specific composition of each incipient sizing is set forth in the following Table 4.

Table 3 Spreads Table 4 Chemical composition of incipient preparations * Aqueous emulsion emulsion Kane AceMR MX-125 Kaneka epoxy containing 75% by weight of epoxy resin and 25% by weight of core-covered rubber nanoparticles The composite product tubes wound with filaments obtained in this way were subjected to two different analytical tests. In the first, the breaking strength of the product tubes obtained was determined. In the second, the interlaminar shear strength (ILSS) of the product tubes when exposed to boiling water for 500 hours was determined in accordance with Ring Test Method NOL, Accession No. AD0449719, Naval Ordinance Laboratory, White Oak, Maryland. In addition to these analytical tests, during the manufacture of each tube, the tension generated in the glass fibers used to manufacture the tubes during the winding operation was determined and recorded. The results obtained are shown in Figures 3-6.

As shown in Figure 3, the breaking strengths of the inventive product tubes were approximately 811% greater than the breaking strength of the control tube. This shows that the core-shell rubber nanoparticles of this invention provide a substantial improvement in the mechanical properties of glass fiber reinforced polymer composite products made in accordance with this invention.

Meanwhile, Figure 4 shows that the core-shell rubber nanoparticles of this invention imparted essentially no adverse effects on the interlaminar resistance of the inventive product tubes after 500 hours of exposure to boiling water. This suggests that the core-shell rubber nanoparticles of this invention do not adversely affect the strength chemistry of polymer composite products reinforced with inventive fiberglass in any significant way.

Finally, Figure 5 shows that the tension generated in the glass fibers during the winding operation used to form the composite product tubes wound with inventive filaments were not essentially affected by the core-shell rubber nanoparticles of this invention. This shows that the core-shell rubber nanoparticles of this invention do not adversely affect the manufacturing process used to produce the inventive glass fiber reinforced polymer composite products in any significant way.

Although only some embodiments of this invention have been described in the foregoing, it should be appreciated that many modifications can be made without departing from the spirit and scope of this invention. For example, it is possible and still desirable in some cases, to combine the core-shell rubber nanoparticle technology of this invention with other technologies for making polymer composite products reinforced with glass fiber.

For example, the U.S. 5,840,370 of shared ownership mentioned above describes a process for manufacturing a pre-impregnated glass / polymer material in the which the application of some or all of the matrix polymer that forms the final fiberglass reinforced polymer composite product is applied "on-line" as part of the glassmaking process. This technology can be combined with the technology of this invention by applying the core-shell rubber nanoparticles of this invention first, followed by impregnating the coated glass fibers formed in this manner with the matrix polymer of the second polymer composite product.

All these modifications are proposed to be included within the scope of this invention and the related general inventive concepts, which will be limited only by the following claims.

Claims

1. A composite product of glass fiber reinforced polymer, characterized in that it comprises a plurality of individual glass fibers and a resinous binder, wherein the core-shell rubber nanoparticles are incorporated within the resinous binder of the composite product.

2. The fiberglass reinforced polymer composite product according to claim 1, characterized in that the individual glass fiber forms a glass fiber mat held together by the resinous binder.

3. The composite product of glass fiber reinforced polymer according to claim 1, characterized in that the resinous binder includes from 0.1 to 20% by weight of core-shell rubber nanoparticles, based on the total amount of resin in the binder.

4. The composite product of glass fiber reinforced polymer according to claim 1, characterized in that the average particle size of the core-shell rubber nanoparticles is 250 nm or less.

5. The composite product of glass fiber reinforced polymer according to claim 1, characterized in that the resinous binder is formed of a urea formaldehyde resin, an acrylic resin or a mixture thereof.

6 The composite product of glass fiber reinforced polymer according to claim 1, characterized in that the core of the core-shell nanoparticles is made of a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, rubber silicone (siloxanes), acrylic rubbers and mixtures thereof.

7. The composite product of glass fiber reinforced polymer according to claim 1, characterized in that the composite product is an asphalt roof tile.

8. An improved roof mat for use in the manufacture of asphalt roof tiles, the improved roof mat characterized in that it comprises a glass fiber mat composed of multiple glass fibers and a resinous binder that holds the individual glass fibers together , wherein the resinous binder includes core-shell rubber nanoparticles.

9. The roof mat according to claim 8, characterized in that the resinous binder includes from 0.1 to 20% by weight of core-shell rubber nanoparticles, based on the total amount of resin in the binder.

10. The ceiling mat according to claim 8, characterized in that the resinous binder is formed of a urea formaldehyde resin, a acrylic resin or a mixture thereof.

11. The roof mat according to claim 8, characterized in that the core of the core-shell rubber nanoparticles is made of a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxanes) , acrylic rubbers and mixtures thereof.

12. An improved asphalt roof tile, characterized in that it comprises a fiberglass roof mat composed of multiple glass fibers and a resinous binder that holds together the individual glass fibers, an asphalt covering the fiber roof mat of glass, the asphalt coating that includes an inorganic particulate filler therein, the asphalt coating also containing roof granules incorporated therein, wherein the resinous binder of the fiberglass roof mat includes rubber nanoparticles of core-cover.

13. The asphalt roof tile according to claim 12, characterized in that the resinous binder includes from 0.1 to 20% by weight of core-shell rubber nanoparticles, based on the total amount of the resin in the binder.

14. Asphalt roof tile in accordance with claim 12, characterized in that the resinous binder is formed of a urea formaldehyde resin, an acrylic resin or a mixture thereof.

15. The asphalt roof tile according to claim 12, characterized in that the core of the core-shell rubber nanoparticles is made of a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber ( siloxanes), acrylic rubbers and mixtures thereof.

16. The asphalt roof tile according to claim 12, characterized in that the asphalt coating includes from 30 to 80% by weight, based on the total weight of the asphalt filled with an inorganic particulate filler selected from the group consisting of dolomite, silica , slate dust and magnesium carbonate of high hardness.

17. A composite product of glass fiber reinforced polymer, characterized in that it comprises a matrix polymer and glass fibers dispersed in the matrix polymer, wherein the fiber surfaces are coated with core-shell rubber nanoparticles.

18. The composite product of glass fiber reinforced polymer according to claim 17, characterized in that the surfaces of the glass fibers have a coating comprising a mixture of core-shell rubber nanoparticles and a film-forming polymer.

19. The fiberglass reinforced polymer composite product according to claim 17, characterized in that the glass fibers are manufactured by combining multiple glass filaments attenuated together to form individual fibers, and wherein the incipient sizing composition is also applied to the individual fiber filaments before they combine.

20. The fiberglass reinforced polymer composite product according to claim 17, characterized in that the surfaces of the glass fibers carry a second discovery of a secondary incipient sizing composition applied to the fibers during the manufacture of the fibers after the fibers. individual glass filaments are combined, the secondary incipient sizing composition comprising additional core-shell rubber nanoparticles and a film-forming polymer.