KR20150039822A - Improved fiberglass reinforced composites - Google Patents

Abstract

Fiberglass reinforced composites have improved physical properties. The fiberglass reinforced composites incorporate core-shell rubber nanoparticles within the resin binder of the composite and / or within a sizing composition that is coated directly onto the individual glass fibers.

Description

[0001] IMPROVED FIBERGLASS REINFORCED COMPOSITES [0002]

This application claims priority to U.S. Provisional Application No. 61 / 679,196, filed August 3, 2012, and No. 61 / 727,453, filed November 16, 2012, all of which are incorporated herein by reference .

Conventional asphalt roofing shingles are produced by applying an asphalt coating to a fiberglass web and sanding sand or other roofing granules into a still soft asphalt coating and then once the asphalt is cured Is formed by subdividing the formed web into individual planks. Fiberglass webs are usually made of glass fibers joined together by suitable resin binders. In addition, finely ground inorganic microfine fillers are usually included in the asphalt coating to reduce cost, improve the thermal deformation resistance of the board, and reduce asphalt UV degradation.

Commonly assigned U.S. Patent No. 7,951,240, the entire contents of which is incorporated herein by reference, show that the tear strength of roofing boards made in this way can be influenced by the type of particulate filler contained in the asphalt coating. In particular, this patent shows that if tough fillers such as dolomite, silica, slate powder, high magnesium carbonate, etc. are used, the tear strength of such roofing planks may be reduced.

The physical properties of many types of fiberglass reinforced polymer composites are that the glass fibers are applied to the glass fibers prior to being combined with the matrix or composites of composites such as fiberglass mats, - shell rubber nanoparticles. ≪ / RTI >

Moreover, glass fibers bearing such core-shell rubber nanoparticles may contain fibers rather than particles in a separate polymeric binder that is subsequently applied to the fibers in subsequent manufacturing processes in which pre-sized glass fibers are used to make useful products, Can be made easily by including the particles in a size that is applied to the fibers as they are made.

In some exemplary embodiments of the present invention, it has been found that the physical properties of the fiberglass reinforced composites may be improved by incorporating core-shell rubber nanoparticles within the resin binder of the composite.

In various exemplary embodiments of the present invention, the fiberglass reinforced composites include an improved roof construction mat for use in manufacturing asphalt roofing construction boards. Some exemplary embodiments of the improved roof construction mat include a fiber glass mat comprising a plurality of glass fibers and a resin binder that holds together the individual glass fibers, wherein the resin binder comprises rubber core-shell nanoparticles.

Further, according to further exemplary aspects of the present invention, the glass fibers carrying these core-shell rubber nanoparticles may be incorporated into a separate polymeric binder that is subsequently applied to the fibers in a subsequent manufacturing process, In addition, it has been discovered that core-shell rubber nanoparticles may be made by including core-shell rubber nanoparticles in the sizing agent applied to the fibers when the fibers are made.

Thus, exemplary embodiments of the present invention provide a fiberglass reinforced polymer composite comprising glass fibers dispersed in a matrix polymer and a matrix polymer, wherein the surfaces of the glass fibers carry a coating of core-shell rubber nanoparticles.

In accordance with other exemplary aspects of the present invention, there are provided glass filaments and fibers for use in making fiberglass reinforced polymer composites. Glass filaments and fibers include glass filaments or fibrous substrates carrying a coating of an aqueous size composition, and the aqueous size composition includes film forming polymers, organosilane coupling agents and core-shell rubber nanoparticles.

Additional exemplary embodiments of the present invention are directed to a method of making a glass comprising filling a molten glass through multiple orifices in a bushing to produce molten streams of glass and allowing the molten streams of the glass to solidify to form individual filaments It also provides a continuous process for making fibers. The individual filaments may be coated with an incipient size composition containing a lubricant, a film forming resin and an organosilane coupling agent, or may be combined together to form fibers. The process may further comprise applying a coating of core-shell rubber nanoparticles to the fibers.

Some exemplary embodiments provide a fiberglass reinforced polymer composite comprising a plurality of discrete glass fibers, a fiberglass and a resin binder, wherein the core-shell rubber nanoparticles are incorporated into the resin binder of the composite. The individual glass fibers may form a fiberglass mat held together by a resin binder. The resin binder may comprise 0.1 to 20 weight percent of the rubber core-shell nanoparticles, or 0.5 to 10 weight percent of the rubber core-shell nanoparticles, based on the total weight of the resin in the binder. The average particle size of the rubber core-shell nanoparticles may be 250 nm or less. The resin binder may be formed from urea formaldehyde resin, acrylic resin or a mixture thereof.

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

In other exemplary embodiments, the composite is a plank for building an asphalt roof.

In various exemplary embodiments, there is provided an improved roof construction mat for use in manufacturing asphalt roofing construction boards. The improved roof construction mat may comprise a fiberglass mat consisting of multiple glass fibers and a resin binder that holds the individual glass fibers together. The resin binder may comprise rubber core-shell nanoparticles. The resin binder may contain 0.1 to 20 wt% of the rubber core-shell nanoparticles based on the total amount of the resin in the binder. The average particle size of the rubber core-shell nanoparticles may be 250 nm or less. The resin binder may be formed from urea formaldehyde resin, acrylic resin or a mixture thereof. The core of the rubber core-shell nanoparticles may be made of a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber, and mixtures thereof.

In still other exemplary embodiments, an improved asphalt roofing construction board comprising a fiberglass roofing mat and fiberglass roofing mat comprising a plurality of glass fibers and a resin binder to hold the individual glass fibers together Is provided. The asphalt coating may also comprise an inorganic particulate filler. The asphalt coating may also contain additional roofing granules embedded in the interior. In some exemplary embodiments, the resin binder of the fiberglass roofing mat comprises rubber core-shell nanoparticles. The resin binder may comprise 0.1 to 20 weight percent of the rubber core-shell nanoparticles, or 0.5 to 10 weight percent of the rubber core-shell nanoparticles, based on the total weight of the resin in the binder. The average particle size of the rubber core-shell nanoparticles may be 250 nm or less. The resin binder may be formed from urea formaldehyde resin, acrylic resin or a mixture thereof. The core of the rubber core-shell nanoparticles may be made of a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber, and mixtures thereof. The asphalt coating may comprise 30 to 80 wt% of an inorganic particulate filler selected from the group consisting of dolomite, silica, slate powder and high magnesium carbonate, based on the total weight of the filled asphalt.

In various exemplary embodiments, there is provided a fiberglass reinforced polymer composite comprising glass fibers dispersed in a matrix polymer and a matrix polymer. The surfaces of the glass fibers may also carry a coating of core-shell rubber nanoparticles. In other exemplary embodiments, the surfaces of the glass fibers carry 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 initial size composition applied to the fibers during fiber fabrication, and the initial size composition comprises core-shell rubber nanoparticles, a film forming polymer and an organosilane couple Lt; / RTI > Initial size compositions may also contain hydrocarbon waxes.

In some exemplary embodiments, the glass fibers are made by combining together multiple attenuated glass filaments to form individual fibers, and the initial size composition is applied to the individual glass filaments before the individual glass filaments are combined .

In some exemplary embodiments, after the individual glass filaments are combined, a second coating of the secondary initial size composition during fiber production is applied to the fibers, the secondary initial size composition comprising additional core-shell rubber nanoparticles and film forming Polymer.

The glass fibers may be made by combining multiple weakened glass filaments together to form individual fibers and the surfaces of the glass fibers may be coated with a first coating of initial size composition applied to individual glass filaments before individual glass filaments are combined Wherein the initial size composition comprises a film forming polymer and an organosilane coupling agent and wherein the surfaces of the glass fibers further comprise a second coating of secondary initial size composition applied to the fibers during fiber fabrication after the individual glass filaments are combined, And the secondary initial size composition comprises core-shell rubber nanoparticles and a film forming polymer.

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

In some exemplary embodiments, the core-shell rubber nanoparticles are applied to the reinforced glass fibers in the form of a mixture of core-shell rubber nanoparticles and film-forming resin, and the mixture further comprises a total amount of film- 0.1 to 20 weight percent of the rubber core-shell nanoparticles, and 0.5 to 10 weight percent of the rubber core-shell nanoparticles.

In some exemplary embodiments, the fiberglass reinforced polymer composite is a roofing construction board.

In some exemplary embodiments, a glass filament is provided for use in making a fiberglass reinforced polymer composite. The glass filament may comprise a glass filament substrate carrying a coating of the initial size composition, and the initial size composition comprises a film forming polymer, an organosilane coupling agent and core-shell rubber nanoparticles.

In other exemplary embodiments, glass fibers are provided for use in making fiberglass reinforced polymer composites. The glass fibers may comprise a glass-fiber substrate carrying a coating comprising a film-forming polymer and core-shell rubber nanoparticles.

The glass fibers may consist of multiple glass filaments combined together and the surfaces of the glass filaments carry a first coating of the initial size composition applied to the filaments before being combined and the initial size composition comprises a film forming polymer, Coupling agents and core-shell rubber nanoparticles.

The surfaces of the glass fibers carry a second coating of the secondary initial size composition applied to the fibers after the filaments forming the fibers have been combined and the secondary initial size composition contains the additional core-shell rubber nanoparticles and the film- .

In other exemplary embodiments, the glass fibers are made by combining multiple weakened glass filaments together to form the fibers, and the surfaces of the glass fibers have an initial size applied to the individual glass filaments before the individual glass filaments are combined Carrying a first coating of the composition, wherein the initial size composition comprises a film forming polymer and an organosilane coupling agent. The surfaces of the glass fibers may additionally carry a second coating of a secondary initial size composition applied to the fibers after the individual glass filaments are combined and the secondary initial size composition comprises film forming polymer and core- do.

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

The core-shell rubber nanoparticles may be applied to glass filaments or fibers in the form of a mixture of core-shell rubber nanoparticles and a film-forming resin, and further the mixture may contain 0.1 To 20% by weight of core-shell rubber nanoparticles.

In still other exemplary embodiments, a continuous process for producing glass fibers is provided and the process comprises the steps of filling the molten glass through multiple orifices in a bushing to produce molten streams of glass, Allowing the filaments to solidify to form filaments, coating the individual filaments with an initial size composition containing a lubricant, a film forming resin and an organosilane coupling agent, and combining the individual filaments together to form the fibers . The process may further comprise applying a coating of core-shell rubber nanoparticles to the fiber.

The core-shell rubber particles may be applied to glass fibers by including core-shell rubber particles in the initial size composition.

In some exemplary embodiments, the core-shell rubber particles are applied to the glass fiber by coating the glass fibers with a secondary initial size composition comprising the core-shell rubber nanoparticles and the film-forming polymer after the glass fibers are formed. The initial sizing agent also contains core-shell rubber nanoparticles.

The average particle size of the core-shell rubber nanoparticles may be 250 nm or less, and the core of the rubber core-shell nanoparticles may be selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber, It can also be made of rubber.

The invention can be better understood with reference to the following drawings.

Figure 1 is a box plot of data showing the tensile strength of two optional fiberglass mats.
Figure 2 is a box plot of data showing the tear strength of two optional fiberglass mats.
3 is a box plot of data showing the tensile strength of two arbitrary asphalt roofing planks.
Figure 4 is a bar graph showing the impact of the core-shell rubber nanoparticles of the present invention on the burst strength of the glass fiber wound high pressure composite pipes made according to the present invention.
Fig. 5 is a graph showing the effect of the core-shell rubber nano-particles on the interlayer shear strength of the glass fiber-wound high-pressure composite pipes of Fig.
Figure 6 is a graph showing the effect of these core-shell rubber nanoparticles on the tensile force applied to the glass fibers used to form the glass fiber-wound high pressure composite pipes of Figure 4 during the manufacture of the pipes.

Rubber Core - Shell Particles

Rubber core-shell particles are known commercial articles described in various patents. For example, it is described in EP 2 053 083 Al, EP 5 830 086 B2, US 5,002,982, US 2005/0214534, JP 11207848, US 4,666,777, US 7,919,549 and US 2010/0273382, each of which is incorporated herein by reference in its entirety . Generally speaking, the rubber core-shell particles are composed of nanoparticles having a core made of a thermoplastic or thermosetting polymer shell and a synthetic polymer rubber such as styrene / butadiene, polybutadiene, silicone rubber (siloxane) or acrylic rubber. Generally, the rubber core-shell particles have a significantly narrower particle size distribution with an average particle size of less than about 250 nm, more typically less than about 200 nm, less than about 150 nm, or even less than about 100 nm. Rubber core-shell particles are commercially available from numerous other sources, including Kenaka Corporation of Pasadena, Texas.

Fiberglass manufacturing

The glass fibers are typically made by a continuous manufacturing process in which molten glass is forcibly moved through the holes of the "bushing " so that the streams of molten glass formed thereby solidify into filaments, Or "roving" or "strand ". Glass fiber manufacturing processes of this type are known and are described in a number of patents. Examples include US 3,951,631, US 4,015,559, US 4,309,202, US 4,222,344, US 4,448,911, US 5,954,853, US 5,840,370, and US 5,955,518, each of which is incorporated herein by reference in its entirety. The speed at which glass fibers are typically produced by these processes is approximately 4,000 to 15,000 feet per minute (about 1,220 to 4,572 meters per minute). Thus, the time between the time at which this glass manufacturing process occurs, in other words the time at which the molten glass leaves the bushing, is sufficient to cause the formed glass fibers or strands to be packaged, stored and / or used to be very short, A fraction of a second.

The glass fibers can be made of any type of glass. Examples include A-type glass fibers, C-type glass fibers, E-type glass fibers, S-type glass fibers, ECR-type glass fibers (e.g., Advantex® glass fiber commercially available from Owens Corning ), Hiper-tex (TM), 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 fiberglass mats of the present invention. Similarly, one or more naturally occurring materials, such as cotton, jute, veneer, burgez, hemp, coir, linen, cotton, sisal, flax, henequen, and combinations thereof, such as carbon fibers, The fibers made may also be included.

Usually an aqueous coating or "sizing agent " is applied to the glass filaments before the glass filaments are solidified and then contacted with the rotating spindle for attenuation. These sizing agents typically include a lubricant that protects the fibers from damage by abrasion, a film-forming resin that assists in binding the fibers to the polymer that forms the body or matrix of the composite in which the fibers are to be used, An organic silane coupling agent which improves the adhesion of the resin and the matrix polymer. While these sizing agents can be applied by spraying, sizing agents are typically applied by passing the filaments over a pad or roller containing sizing agents to the surfaces.

Sized glass fibers made in this way are used in the manufacture of a variety of different fiberglass reinforced polymer composites. In most of these manufacturing processes, the sized glass fibers are combined with the matrix polymer forming the body or matrix of the composite before being arranged in final form in the product from which the glass fibers are to be made. In another approach, the sized glass fibers are first assembled into a "preform " which is then impregnated with the matrix resin forming the body of the composite. This is the approach used for the production of roofing boards, where the glass fibers are formed into a self-supporting web (preform) and the web thus made is coated with asphalt, which is then solidified to form the final asphalt board product.

The fiberglass preforms used in this approach are usually self-supporting or at least coherent in the sense that the individual sized glass fibers are not separated from each other when exposed to stresses and forces generated when the preform is manipulated and / or impregnated with a matrix resin. Coherent. For this purpose, the sized glass fibers are usually 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 agents ". These binder sizing agents will be understood to be different from the size compositions applied to glass filaments and fibers as part of the manufacturing process, referred to herein as " initial sizing agents "or"

From the above it is clear that processes for making glass fibers and processes for using glass fibers are regarded as distinct from each other in the industry. For this reason, the process steps or operations that occur during the manufacture of glass fibers are typically referred to as "in-line" steps or operations. On the other hand, the process steps or operations that occur during the use of already made glass fibers, such as in the production of fiberglass reinforced polymer composites, are typically referred to as "off-line" steps or operations. This term is used, for example, in the aforementioned US 5,840,370 as well as in US 8,163,664, US 7,279,059, US 7,169,463, US 6,896,963 and especially US 6,846,855. The contents of each of these patents are incorporated herein by reference in their entirety. This term is also used in this disclosure.

Fiberglass reinforced polymer composites

Various aspects of the present invention also relate to the manufacture of any type of fiberglass reinforced polymer composites. These products are well known in the industry and are often referred to as "fiberglass reinforced plastics ". It consists of glass reinforcing fibers and a polymeric resin that forms the body or "matrix" of the composite. For convenience, these polymers are sometimes referred to in the literature as "matrix polymers ". Further, in the context of the present disclosure, the terms "polymer resin" and "polymer" are used in the broadest sense to include both natural resin materials such as asphalt and the like, as well as synthetic resins.

The fiberglass reinforced polymer composites of the present invention can be made of any type of glass fiber. Examples include A-type glass fibers, C-type glass fibers, E-type glass fibers, S-type glass fibers, ECR-type glass fibers (e.g., Advantex® glass fiber commercially available from Owens Corning ), Hiper-tex (TM), and combinations thereof.

The fiberglass reinforced polymer composites of the present invention 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, one or more naturally occurring materials, such as cotton, jute, veneer, burgez, hemp, coir, linen, cotton, sisal, flax, henequen, and combinations thereof, such as carbon fibers, The fibers made may also be included. Similarly, the fiberglass reinforced polymer composites of the present invention may also include non-fibrous fillers, examples of which include calcium carbonate, silica sand and wollastonite. Preferably, the fiberglass reinforced polymer composites of the present invention contain up to about 5% by weight of non-glass fibers and fillers, all based on the weight of all fibers and fillers in the composite. More preferably, all of the fibers of the fiberglass composites of the present invention or essentially all of them are glass fibers.

Similarly, the fiberglass reinforced polymer composites of the present invention may be made of any resin binder previously used or may be used in the future as a matrix polymer for making the body or matrix of fiberglass reinforced plastic composites. Examples are polyolefins, polyesters, polyamides, polyacrylamides, polyimides, polyethers, polyvinyl ethers, polystyrenes, polyoxides, polycarbonates, polysiloxanes, polysulfones, polyanhydrides, polyimines, Vinyl esters, polyurethanes, maleic resins, urea resins, melamine resins, phenolic resins, furan resins, polymeric admixtures, alloys and mixtures thereof. Epoxy resins are particularly preferred.

The amount of resin binder to be included in the fiberglass reinforced polymer composites of the present invention can vary widely and any conventional amount can be used. In some exemplary embodiments, in the case of fiberglass mats, the amount of resin binder is from about 10 to 30 weight percent, more typically from about 14 to 25 weight percent, or even about 16 to 22% by weight.

Fiberglass reinforced polymer composites are most typically made by molding, although they can be made by a variety of different fabrication techniques, including simple coating and laminating processes. Two different types of forming processes, wet forming processes and composite forming processes are commonly used. In the wet forming processes, the glass reinforcing fibers and the matrix polymer are combined in a mold just prior to molding. For example, fiberglass mats prepared according to the present invention can be prepared by wet laid forming processes in which the chopped glass fibers are coated with an aqueous dispersant of a resin binder and then dried and cured, . The formed nonwoven web is an assembly of individual randomly dispersed glass filaments that are bonded together in the gaps by a resin binder.

As described above, the fiberglass mats of the present invention comprise a resin binder for holding fibers together. For this purpose, any resin binder previously used or may be used in the future for producing fiberglass mats used in the production of asphalt roofing boards can be used as the resin binder of the present invention. Examples include urea formaldehyde resins, acrylic resins, polyurethane resins, epoxy resins, polyester resins and the like. Urea formaldehyde resins and acrylic resins are preferred, and mixtures of urea formaldehyde resins and acrylic resins are even more preferred. In such mixtures, the amount of acrylic resin is preferably from about 2 to about 30 weight percent, more preferably from about 5 to about 25 weight percent, or even from about 5 to about 25 weight percent, based on the dry solids, of the combined amount of urea formaldehyde resin and acrylic resin in the binder About 10 to 20% by weight.

The amount of resin binder to be included in the fiberglass mats of the present invention can vary widely and any conventional amount can be used. Usually, the amount of resin binder will be from about 10 to 30 weight percent, more typically about 14 to 25 weight percent, or even 16 to 22 weight percent, based on the weight of the fiberglass mat as a whole.

The physical structure of the fiberglass mat of the present invention is not critical and any physical structure previously used or may be used in the future for making fiberglass mats for asphalt roofing planks may be used to produce the fiberglass mat of the present invention Can be used. For example, woven and nonwoven fiberglass fabrics or scrims as well as nonwoven webs of glass fibers can be used to make the fiberglass mats of the present invention.

Most commonly, however, the fiberglass mat of the present invention will be prepared by a wet laid process in which wet-cut glass fibers are coated with an aqueous dispersant of a resin binder after being immersed in an aqueous slurry onto a moving screen, followed by drying and curing. The formed nonwoven web is an assembly of randomly dispersed individual glass filaments that are bonded together in the gaps by a resin binder.

Roofing panels

In some exemplary embodiments, the asphalt roofing plank of the present invention, as described above, is fabricated using conventional manufacturing methods, i.e., applying a molten asphalt coating composition to a fiberglass web of the present invention, Once sanded or other roofing granules are sandwiched in this asphalt coating, once the coated asphalt is cured, it is produced from the fiberglass web of the present invention by subdividing the web thus formed into individual roofing planks. Any manufacturing method used or used in the future may be used, or it may be suitable for producing the fiberglass mat and planks of the present invention. Any fiberglass mats that have been or may be used in the past for making asphalt roofing platters may be suitable for use in making fiberglass mats and planks of the present invention.

For this purpose, any asphalt coating composition previously used or may be used in the future for making asphalt roofing planks may be suitable for use as an asphalt coating in the present invention. As described in the above-mentioned US 7,951, 240, these asphalt coating compositions comprise a significant amount of an inorganic particulate filler. In addition, the asphalt coating compositions can be made in a variety of different types and grades of asphalt and can also contain a variety of different optional components such as polymer modifiers, waxes, and the like. Any of the different grades of asphalt described herein, as well as any of the different inorganic particulate fillers and optional ingredients described herein, may be suitable for making the roofing slabs of the present invention.

In addition to these components, the asphalt coating composition used in the present invention also includes an inorganic particulate filler. For this purpose, any inorganic particulate filler known or known for use in the production of asphalt roofing planks may be used. For example, calcite (crushed limestone), dolomite, silica, slate powder, high magnesium carbonate, rock dust other than crushed limestone can be used. Although concentrations of about 40-70 wt.% Or even about 50-70 wt.% Are more typical, concentrations of about 30-80 wt.%, Based on the total weight of the asphalt coating, can be used.

As indicated above, some of these inorganic particulate fillers are known to adversely affect the tear strength of asphalt roofing boards made of these materials. In particular, inorganic fillers having high hardness (i.e., hardness greater than about 3 Moh), such as dolomite, silica, slate powder, high magnesium carbonate, and the like, are made of a softer inorganic filler such as calcite (crushed limestone) It is known to produce asphalt boards with lower tear strength than boards. Thus, it is common practice in the industry to use calcite or other soft inorganic microparticles as the asphalt filler when at least asphalt sheets of excellent tear strength are desired. Tear strength is an important property because it reflects the installed plank's ability to withstand the breaking or otherwise breaking of the roof substrate due to strong winds. At least for asphalt roofing boards and fiberglass mats that make it, tear strength and tensile strength are usually not correlated, so the same can not be said for tensile strength. Indeed, tear strength and tensile strength can even be inversely proportional to some of these products.

Core-shell fiberglass mats

According to various aspects of the present invention, the problem of poor tear strength of conventional asphalt roofing boards can be overcome by incorporating the core-shell rubber particles with the resin binder used to make the fiberglass mat making the asphalt roofing plank of the present invention If not, can be removed. Thus, according to various aspects of the present invention, asphalt roofing boards exhibiting excellent tear strength can be produced, although hard inorganic fillers such as dolomite, silica, slate powder, high magnesium carbonate, etc., are included in the asphalt coating compositions .

Once the asphalt coating composition of the present invention is applied to the fiberglass mat of the present invention, conventional roofing granules, such as sand, are applied and embedded in this asphalt coating, which is still soft, as in the conventional manner. The asphalt coating is then allowed to cure, and the cured web thus formed is then subdivided into individual roofing boards.

The use of latexes of these rubber core-shell nanoparticles as binders for fiberglass mats has already been proposed. See, for example, EP 2 053 083 Al, EP 5 830 086 B2 and US 2005/0214534 cited above. However, in this application, the fiberglass binders are all made up of these rubber core-shell nanoparticles. On the other hand, in some exemplary embodiments of the present invention, these rubber core-shell nanoparticles may be incorporated in small but suitable amounts as additives for improving the properties of the polymer resin forming the body of the resin binder. According to some aspects of the present invention, the amount of these rubber core-shell nanoparticles contained in the resin binder of the fiberglass mat is determined by the weight of the rubber core-shell nanoparticles itself, i.e. the total amount of other polymeric resins in the binder , More typically about 0.5 to 10 wt%, or even about 1 to 4 wt%, based on the total weight of the composition.

It is also known that the tensile strength of the solid polymer mass (as reflected by the fracture toughness, peel strength and lap shear strength) can be improved by including these rubber core-shell nanoparticles in the mass as fillers. However, as shown above, tear strength and tensile strength are not correlated in the field of asphalt roofing boards. This is illustrated in Figures 1 and 2 which are box plots showing the tensile strength and tear strength of the fiberglass mats made of different conventional binders. 3, which is a similar box plot showing the tear strength of asphalt roofing boards made of these different fiberglass mats. As shown in Fig. 1, the tensile strength of the mat made of the binder (A) was higher than that of the mat made of the binder (B). On the other hand, both of the tear strength of the mat made of the binder (A) (FIG. 2) and the tear strength of the asphalt roofing construction board made of the binder (A) It was worse than the tear strength. This shows that there is no direct correlation between tear strength and tensile strength in asphalt roofing boards and their associated fiber glass mats. This, in turn, proves that the improved tear strength of the mats and planks of the present invention is a different phenomenon from the improved tensile strength shown in the prior art.

The shell of the rubber core-shell nanoparticles used in the present invention may be formed into essentially any thermoplastic or thermosetting polymer as long as it is compatible with the polymer used to form the resin binder of the fiberglass mat used in the present invention . And, "compatible" means that the polymer forming the shell does not adversely react with the resin binder by not adversely affecting physical or chemical stability, or by not causing unpleasant or undesirable effects by the product.

Additional fiberglass reinforced composites

According to other exemplary embodiments, the fiberglass reinforcing composites are formed by composite molding, and the glass reinforcing fibers and matrix polymer are combined into a "prepreg" before being filled into the mold. Such pre-prisms can take the form of freestanding objects in which glass fibers are randomly oriented, such as fiberglass sheets or "veils" used to form asphalt sheets. In addition, pre-pref [iota] nders can be used as stand-alone objects in which glass fibers are oriented in predetermined directions, such as three-dimensional "skeletons" used to form complex shaped load bearing products such as rocker arms for automotive suspension You can also take the form. Such prepregs may also take the form of pellets, pastilles or agglomerates of matrix polymers containing randomly distributed cut glass fibers.

Specific embodiments of molding processes that can be used to produce the fiberglass reinforced polymeric composites of the present invention include injection molding, bladder molding, compression molding, vacuum bag molding, mandrel wrapping, wet lay up, hopper gun application, filament winding, extrusion Molding, drawing, resin transfer molding and vacuum auxiliary resin transfer molding.

According to some exemplary embodiments, the fiberglass reinforced polymeric composites can be used in a variety of applications, such as pipes (tubes) and tanks formed by filament winding or mandrel lapping, especially pressure supports such as those of this type in which the matrix polymer is an epoxy resin Containers. These products are well known and are described, for example, in the aforementioned US 5,840,370 and US 7,169,463. As described in these patents, these pressure support vessels are typically made by winding continuous glass fibers impregnated with some or all of the matrix polymer necessary to form the vessel around the rotating steel mandrel in specific orientations. Any additional matrix polymer is then added, the matrix polymer is then cured and the mandrel withdrawn to produce a product container. Alternatively, these articles can be wrapped around a fixed steel mandrel by pre-forming sheets or bails of pre-formed glass fibers pre-impregnated with some or all of the matrix polymer required to form the container, , Curing the matrix polymer, and withdrawing the mandrel. As further described in these patents, the glass fibers used to form these products are sized during manufacture of the fibers, usually as a binder sizing agent containing a lubricant, a film-forming resin, and usually an organosilane coupling agent.

According to some exemplary aspects of the present invention, the core-shell rubber nanoparticles may be incorporated into an initial sizing agent applied to glass fibers when the glass fibers are made. It has been found that incorporating these nanoparticles into the fibers in this way is not only very convenient from a manufacturing standpoint but is also effective in producing glass fibers with improved reinforcing properties when used in a variety of different fiberglass reinforced polymer composites applications.

Generally speaking, according to the present invention, it is preferred that the average particle size of the core-shell rubber particles used in the present invention is 100 times smaller (i. E. Less than 1%) of the average diameter of the glass reinforcing fibers to which it is applied. The average particle sizes 150 times smaller (i.e., less than 0.67%) or even 200 times smaller (i.e., less than 0.5%) of the glass-reinforced fibers are also interesting.

As described above, it is known that the tensile strength of the solid polymer mass can be improved by incorporating these core-shell rubber nanoparticles into the mass as fillers (as reflected by the fracture toughness, peel strength and lap shear strength). In December 2003, Ki Tak Gam's article "Structure-Property Relationship In Core-Shell Rubber Toughened Epoxy Nanocomposites" was submitted to a graduate laboratory at Texas A & M University as part of the requirements for a doctoral degree. However, as explained in detail above, the tear strength of the asphalt roofing board and its tensile strength are not correlated with each other. This proves that the improved tear strength of asphalt roofing boards made according to the present 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 the solid polymer mass is understood as a function of its cohesive strength, i.e. the ability of the mass to hold itself together when under tensile load. On the other hand, the tear strength of the asphalt roofing plank is a function of a completely different phenomenon, i.e. the ability of the binder size composition to coat the glass fiber veil of the plank that can promote adhesion between the veil and the asphalt coating (matrix polymer) I understand. Also, when core-shell rubber particles are used to improve the tensile strength of the solid polymer mass, a sufficient amount of these nanoparticles is used to fill the entire polymer mass. On the other hand, since these nanoparticles are only present in the surfaces of the glass fibers themselves and are not distributed in the mass of the matrix polymer forming the body of the fiberglass reinforced polymer composites of the present invention, a much smaller amount of core- Particles are used in the present invention.

According to the present invention, the core-shell rubber nanoparticles of the present invention can be applied to glass reinforced fibers at any time prior to application of the matrix polymer forming the body of the fiberglass reinforced polymer composites of the present invention. Thus, for example, in a separate application step as part of the manufacturing process for producing the fiberglass reinforced polymer composites of the present invention, the core-shell rubber nanoparticles are made in glass binder Lt; / RTI > fibers.

Alternatively, the core-shell rubber nanoparticles may be "in-line" applied to glass fibers during fiberglass production as part of the glass fiber manufacturing process itself. Usually, this will be done by including these core-shell rubber nanoparticles in an initial size composition applied to the individual glass filaments used to form the glass fibers before the filaments are combined together to form the fibers. Alternatively, these core-shell rubber nanoparticles can be applied to glass fibers after the glass fibers are formed in separate aqueous size compositions. For convenience, these separate size compositions are referred to herein as "secondary initial sizing agents ". In a third approach, both of these procedures can be used, and some core-shell rubber particles are applied to the individual filaments in the initial sizing agent before the fibers are formed and the remaining particles are applied to the secondary initial sizing agent do.

Regardless of which of these approaches is used, in-line application allows these core-shell rubber particles to be conveniently applied during glass fiber fabrication, which ultimately leads to the use of separate "fibers " in subsequent manufacture of the fiberglass- Eliminating the need for "off-line" process steps. In addition, when at least nanoparticles are included in the initial size composition used during fiber production, in-line application of core-shell rubber nanoparticles can reduce the amount of film forming polymer ultimately applied to the glass fibers. This is because the nanoparticles must be applied with the film-forming polymer in order to promote adhesion of the core-shell rubber nanoparticles to the glass fibers. Thus, combining these nanoparticles with an initial glass sizing agent eliminates the need for a second, subsequent film forming resin coating.

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

As is known in the art, it is conventional practice to select resin compatible with the matrix resin to be used in making the ultimately produced fiberglass composite when selecting the film-forming resin to be used in the initial sizing agent or binder sizing agent. For example, if a particular fiberglass composite is made of an epoxy resin matrix, commercially available epoxy resins will usually be selected as film-forming resins for glass fiber sizing. Such conventional practice follows in accordance with the present invention, that is, the film-forming resin used in the sizing agent containing the core-shell rubber nanoparticles of the present invention preferably has a matrix resin of the fiberglass reinforced polymer composite to be produced As shown in FIG.

As further indicated above, the present invention finds particular use in producing fiberglass reinforced polymer composites from epoxy resins due to their excellent physical properties (e.g., tensile strength) and chemical resistance. For this purpose, in some exemplary embodiments, it is desirable to select a linear bisphenol A type epoxy resin of suitable molecular weight as a film forming resin in a sizing agent containing core-shell rubber particles. In this context, "moderate molecular weight" means a weight average molecular weight of about 10,000 to 250,000. A weight average molecular weight of 15,000 to 100,000 or even 20,000 to 50,000 is preferred. Linear bisphenol A type epoxy is preferred because many fiberglass reinforced polymer composites and those requiring particularly high strength and good chemical resistance are made from linear bisphenol A type epoxy matrix resins. If the molecular weight is too high, the epoxy resin will not effectively form a film, and if the molecular weight is too low, it will undergo undesired crystallization in the coating equipment, so the molecular weight is preferred

In addition to the linear bisphenol A type epoxy, modified epoxy resins may also be used. For example, epoxy novolac may also be used.

Specific examples of commercially available epoxy resins useful as film forming resins to be used with the core-shell rubber nanoparticles of the present invention include AD-502 epoxy aqueous emulsion from AOC, Neoxil 962 / D aqueous emulsion from DSM, Momentive EpiRez 5003 from Momentive, EpiRez 3511 epoxy emulsion from Momentive. Mixtures, especially AD-502 + EpiRez 5003 at a ratio of 95: 5, are also effective.

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

Combination  Having particles Sizing agents

As indicated above, the aqueous sizing agent containing the core-shell rubber nanoparticles of the present invention may also contain a film-forming resin. In a particularly interesting embodiment of the present invention, these components are combined together in the emulsion particles contained in the aqueous size composition, although each of the components may be separately supplied and contained in the aqueous size composition.

Core-shell rubber nanoparticles are commercially available in a variety of different forms. One such form is an organic emulsion of rubber nanoparticles dispersed in a neat (i.e., solvent free) liquid epoxy resin. Examples of these products include the Kane Ace (TM) MX line of CSR liquid epoxy emulsions available from Kaneka Belgium NV. The liquid epoxy / rubber nanoparticle emulsion may be selected from the group consisting of a bisphenol-A type liquid epoxy resin, a bisphenol-F type liquid epoxy resin, an epoxidized phenol novolak type liquid epoxy resin, a triglycidyl p-aminophenol type liquid epoxy resin, (Core-shell rubber nanoparticles) of about 25-40 wt.% In various different types of liquid epoxy resin systems, including alicyclic epoxy resins, cyclic methylene dianiline type liquid epoxy resins, and alicyclic type liquid epoxy resins. It is a well-known commercial article previously used to strengthen other matrix resins, including matrix resins used to form fiberglass reinforced polymer composites such as epoxy, and filament winding pipes and the like.

In this respect, a major difference between the present invention and the prior art for producing fiberglass-reinforced composites containing core-shell rubber nanoparticles is that in the present invention, before the glass-reinforced fibers are combined with the matrix resin forming the body of the composite It should be noted that the core-shell rubber nanoparticles are coated on the glass-reinforced fibers of the composite. This is completely different from the prior art in which core-shell rubber nanoparticles are dispersed throughout the mass of the matrix resin. Thus, the difference between the present invention and the prior art in relation to the use of such commercially available liquid epoxy core-shell rubber nanoparticle emulsions is that in the present invention, the initial size, in which the glass fibers are coated with glass fibers before being combined with the matrix resin These emulsions are used to form the agent. On the other hand, in the prior art, these emulsions are used to form the matrix resin itself.

These commercially available liquid epoxy / rubber nanoparticle emulsions, because they already contain the two major components of the initial size of the present invention, namely core shell rubber particles and epoxy resin film former, - A convenient source of shell rubber nanoparticles.

According to some exemplary embodiments, before this commercially available liquid epoxy / rubber nanoparticle emulsion can be used to make the initial sizing agents of the present invention, it is converted to aqueous emulsions. This can be easily accomplished by using a conventional high shear emulsification technique. For example, rubber nanoparticle aqueous sizing compositions in which the weight ratio of rubber nanoparticles to epoxy resin is 25/75 can be prepared using conventional high shear mixing techniques and conventional epoxy-compatible interfaces such as ethylene oxide / propylene oxide block copolymers Can be made by emulsifying an organic emulsion containing 25% by weight of rubber nanoparticles and 75% by weight of liquid epoxy resin using actives.

The amount of core-shell rubber particles to be applied to the glass fiber or filament substrate in accordance with the present invention will typically be from about 0.01 to 25 weight percent of the solids content of the aqueous size compositions containing it. More typically, the amount of core-shell rubber particles will be about 0.1-5 weight percent, about 0.3-2 weight percent, about 0.5-1.5 weight percent, or even about 0.7-1.3 weight percent of the solids. Thus, the rubber nanoparticle aqueous sizing compositions of the present invention will typically be made by combining at least two different aqueous resinous dispersants, wherein the emulsion resin particles of one dispersant comprise a combination of film-forming resin and core-shell rubber nanoparticles And the emulsion resin particles of the other dispersant contain only the film-forming resin.

Additional ingredients

In addition to the film forming resin, aqueous sized compositions containing the core-shell rubber nanoparticles of the present invention may also contain a variety of additional optional ingredients.

For example, these aqueous size compositions may contain from about 5 to 30 weight percent, more typically from about 8 to 20 weight percent, or even from about 10 to 15 weight percent, of the organosilane coupling agent, based on the solids content . For this purpose, any organosilane coupling agent previously used or may be used in the future to improve the bond strength of the film-forming binder resin to the glass fiber substrate may be used in the present invention. In addition, as in the case of binder resins, the organosilane coupling agents should be selected to be compatible with the particular film-forming binder resin used.

Specific examples of useful organosilane coupling agents include Silquest A-1524 ureido silane, Silquest A-1100 aminosilane, Silquest A-1387 silylated polyazimide methanol, Y-1139 silylated polyazimide from Momentive, ethanol , Silquest A-174 methacryloxy silane, Silquest A-187 epoxy silane, Silquest A-1170 trimethoxy bis-silane, Silquest A-11699 triethoxy bis-silane, all available from Momentive and Silquest Al 120 . Mixtures of Silquest A-1387 and Silquest A-1100 as well as Silquest A-1524 are preferred for use with epoxy resin film forming resins.

Another component that may be included in the aqueous sized compositions containing the rubber nanoparticles used in the present invention is a lubricant. Examples of commercially available lubricants suitable for this purpose include cationic lubricants such as Katex 6760 (also known as Emery 6760), PEG 400 monooleate (PEG 400 MO, Emerest 2646), PEG 200 monolaurate (Emerest 2620), PEG 400 monooleate Stearate (Emerest 2640), PEG600 monostearate (Emerest 2662). Cationic lubricants such as Katex 6760 are typically used in amounts of 0.001 to 2 wt.%, More typically 0.2 to 1 wt.%, Or even about 0.5 wt.% Of the size solids. PEG lubricants, on the other hand, are typically used in amounts of from 0.1 to 22 weight percent, more typically from about 1 to 10 weight percent, or even about 7 weight percent of the solids content.

Another conventional lubricant that can be included in the rubber nanoparticle containing aqueous size compositions used in the present invention is wax. Any wax that may or may not be used as the lubricant wax in the glass fiber aqueous sizing composition may be used as the wax in the rubber nanoparticle aqueous size compositions of the present invention. Michelman Michemlube 280 wax is a good example. Concentrations of about 0.1-10% by weight of the size solids are available, with concentrations of about 2-6% or even 4-5% by weight being preferred.

Still other conventional components that may be included in the aqueous-sized compositions containing the rubber nanoparticles of the present invention include acetic acid, citric acid, or other organic acids in an amount sufficient to efficiently hydrolyze the existing silane, -1100 requires a pH of about 4-6. The final sizing agent pH will typically be in the range of 5 to 6.5.

Other additives, such as Coatosil MP 200 polyfunctional epoxy oligomers, aqueous urethane polymers such as Michelman U6-01 or Baybond PU-403 from Bayer, Witco W-296 or W-298 from Chemtura, May also be included in the rubber nanoparticle containing aqueous size compositions of the present invention for known functions of the invention.

Moisture content and loading

The rubber nanoparticle-containing aqueous sizing compositions of the present invention are applied to glass fiber and / or filament substrates in a conventional manner using conventional coating equipment. Thus, the compositions are combined with a sufficient amount of water such that the rheological properties of the compositions are essentially the same as, or at least similar to, the rheological properties of conventional aqueous sizing agents. These aqueous-sized compositions therefore typically contain a total solids content of from about 2 to 10% by weight, more usually from 4 to 8% by weight, or even from 5 to 7% by weight, based on the total weight of the aqueous- will be.

In addition, these nanoparticle containing aqueous size compositions are also applied to their glass fiber and / or filament substrates in conventional amounts. For example, these size compositions will usually be applied in amounts such that the LOI (ignition loss) of the sized glass fibers and filaments obtained is about 0.2 to 1.5%, more typically 0.4 to 1.0% or even 0.5 to 0.8% . Considering that the concentration of core-shell rubber nanoparticles in these sizing agents is on the order of dry solids, typically about 0.3-2 wt%, about 0.5-1.5 wt%, or even about 0.7-1.3 wt% , Which means that the amount of these core-shell rubber nanoparticles to be applied to glass fiber and / or filament substrates in terms of LOI is usually from about 0.001 to 0.015%, more typically from about 0.002 to 0.010% or even from about 0.0025 to 0.0080% it means.

Examples

In order to more fully describe the present invention, the following examples are provided.

Example  1 and Comparative Example  A

The two fiberglass mats were prepared by a conventional wet laid coating process in which wet-cut glass fibers were coated with an aqueous dispersion of a resin binder and then dried and cured, after being immersed in a transfer screen from an aqueous slurry. Resin binders applied to both webs were prepared using commercially available acrylic latex (Rhoplex GL 720 available from Dow Chemical) and commercially available urea formaldehyde resin latex (FG 654A available from Momentive). The weight ratio of acrylic resin to urea formaldehyde resin in both binders was the same on a dry solids basis (15/85) and the amount of resin applied was chosen so that the total amount of binder applied to each web was essentially the same. The resin binder of Example 1 contained 1.7 percent by weight based on the combined weight of urea formaldehyde and acrylic resin in the binder, commercially available rubber core-shell nanoparticles, especially those sold by Kenaka Corporation of Pasadena, Tex. Lt; RTI ID = 0.0 > Kane Ace < / RTI > MX-113 rubber core-shell nanoparticles.

The fiberglass mats thus obtained were then tested for tensile strength and tear strength in the transverse or transverse direction. Since fiberglass mats and their associated asphalt roofing boards are generally weaker in the transverse direction than in the longitudinal direction, the tensile strength and tear strength in the transverse direction better represent the overall strength of the product.

In addition to these tests, the tear strength of these fiberglass mats in the transverse direction was also determined by a mat performance test with a mortar. In this test, each mat was first sprayed with the same amount of powdered rock and then measured for tear strength in the transverse direction. This test was used because it provides a good simulation of the adverse effects on the fiberglass mat properties that can be caused by the inorganic particulate fillers contained in the asphalt coatings to be applied later. This hammer mat performance test was performed three times for each sample, and the average values obtained for each test are reported below.

The obtained results are described in the following Table 1:

In the above table, "BW" refers to a basis weight which is the weight of a cured mat (fiberglass + cured binder) pounds per 100 square feet. On the other hand, "LOI " refers to the ignition loss which is the standard metric in the industry, which represents the portion of the aqueous binder originally applied to the web, which remains in the web after the binder has dried and cured. The total amount of binder applied to the web on a dry solids basis, i. E. After drying and curing, can be determined by multiplying BW by LOI.

As can be seen in Table 1, the presence of rubber core-shell nanoparticles in the binder of Example 1 had essentially no effect on the tensile strength of the fiberglass mat made with this binder (the differences in Table 1 are within the experimental error) , The tear strength of this mat was increased in the transverse direction relative to the control fiberglass mat of Comparative Example A. In addition, Table 1 also shows that cancer differentiation caused a significant reduction in the tear strength of both mats, and this reduction was more pronounced in the case of Comparative Example A. Specifically, Table 1 shows that the presence of these rubber core-shell nanoparticles can cause the mat of Example 1 to retain 77% of the original tear strength, while the mat of Comparative Example A Shows only 66% of the original tear strength.

This data shows that the addition of these rubber core-shell nanoparticles improves the tear strength of the fiberglass mats in the transverse direction under simulated conditions of use as well as (uncoated) conditions of "as manufactured ".

Example  2 and Comparative Example  B

Eight additional mats were prepared, four representing the present invention and four being control groups without the use of rubber core-shell nanoparticles. These mats were made using the same procedures and ingredients as used in Example 1, except that the amount of rubber core-shell nanoparticles included in the binders representing the present invention was 1.85 wt%.

Each fiberglass mat obtained was then formed into an asphalt roofing plank by coating the mat with an asphalt coating composition made of coated asphalt, and the asphalt coating composition also contained 65 wt% calcite inorganic microfine particle based on the asphalt coating composition as a whole It contains a filler.

The tensile strength of each of the roofing construction boards in the longitudinal direction was measured as the tear strength of each of the roofing construction boards in both the longitudinal direction and the lateral direction. In addition, the total tear strength of each roofing construction board was determined by adding together the longitudinal tear strength and the lateral tear strength. Finally, the measured burst strength and tensile strength were normalized by board weight.

The obtained results are described in Table 2 below.

Table 2 shows that adding the rubber core-shell nanoparticles to the binder of the fiberglass mat used to make the asphalt roofing plank imparts essentially the same effect to the board as it imparts to the mat. In particular, Table 2 shows that asphalt boards made of these nanoparticles, like the fiberglass mats of Example 1, exhibit significantly higher tear strength in the transverse direction than the control boards made without these nanoparticles. In addition, Table 2 further shows that these nanoparticles also slightly reduce the tensile strength of these planks, in this case in the longitudinal direction, rather than in the transverse direction, as seen in Example 1 above.

Example 3

In the following examples, filament wound high pressure composite pipes were made by winding glass fibers pre-impregnated with a commercially available aqueous epoxy matrix resin dispersant around the mandrel. The winding thus formed was then heated to cure the epoxy matrix resin and the mandrel was then withdrawn to produce the final product pipe.

The glass fibers used to make each composite were made by a conventional glass fiber manufacturing process as described above, wherein the weakened glass filaments are coated with an initial sizing agent before being combined with the fibers. Three different experiments were performed. In a first experiment showing the prior art, the initial sizing agent did not contain core-shell rubber nanoparticles. In the other two experiments, the initial sizing agent contained 0.5 wt% core-shell rubber nanoparticles and 1 wt% core-shell rubber nanoparticles, respectively.

The amount of initial sizing agent applied to each glass fiber is described in the following Table 3, and the specific composition of each initial sizing agent is described in Table 4 below.

The filament winding composite pipes thus obtained were subjected to two different analytical tests. In the first test, the burst strength of the obtained product pipes was determined. In the second test, the interlaminar shear strength (ILSS) of the product pipes when exposed to boiling water for 500 hours was determined according to the NOL ring test method, accession number AD0449719 of Naval Ordinance Laboratory, Maryland, Maryland. In addition to these analytical tests, the tension generated in the glass fibers used to make the pipes during winding operation during the manufacture of each pipe has been determined and reported. The obtained results are described in Figs. 3-6.

As shown in Figure 3, the burst strength of the product pipes of the present invention was about 8-11% greater than the burst strength of the control pipe. This shows that the core-shell rubber nanoparticles of the present invention significantly improved the mechanical properties of the glass fiber reinforced polymer composites made according to the present invention.

Figure 4, on the other hand, shows that the core-shell rubber nanoparticles of the present invention did not substantially adversely affect the interlaminar strength of the product pipes of the present invention after 500 hours exposure to boiling water. This suggests that the core-shell rubber nanoparticles of the present invention do not adversely affect the chemical resistance of the glass fiber-reinforced polymer composites of the present invention in any way.

Finally, Figure 5 shows that the tension generated in the glass fibers during the winding operation used to form the filament wound composite pipes of the present invention was essentially unaffected by the core-shell rubber nanoparticles of the present invention . This shows that the core-shell rubber nanoparticles of the present invention do not adversely affect the manufacturing process used to produce the glass fiber-reinforced polymer composites of the present invention in any way.

Although only a few embodiments of the present invention have been described, it should be understood that many modifications may be made without departing from the spirit and scope of the invention. For example, it is possible and even desirable in some instances to combine the core-shell rubber nanoparticle technology of the present invention with other techniques for making fiberglass reinforced polymer composites.

For example, the above-cited co-assigned US 5,840,370 discloses a method of making a glass / polymer prepreg in which the application of some or all of the matrix polymer forming the final fiberglass reinforced polymer composite is applied "in-line" The following describes the process. The technique can be combined with the technique of the present invention by first applying the core-shell rubber nanoparticles of the present invention, and then secondly impregnating the thus formed coated glass fibers with the matrix polymer of the polymer composite.

All such modifications are intended to be embraced within the scope of the general inventive concept of the general inventive concept, which is limited only by the scope of the invention and the scope of the following claims.

Claims (20)

As a fiberglass reinforced polymer composite material,
A plurality of individual glass fibers, a fiberglass and a resin binder,
Wherein the rubber core-shell nanoparticles are incorporated within the resin binder of the composite. The method according to claim 1,
Wherein the individual glass fibers form a fiberglass mat held together by the resin binder. The method according to claim 1,
Wherein the resin binder comprises 0.1 to 20 wt% of the rubber core-shell nanoparticles based on the total amount of the resin in the binder. The method according to claim 1,
Wherein the average particle size of the rubber core-shell nanoparticles is 250 nm or less. The method according to claim 1,
Wherein the resin binder is formed from a urea formaldehyde resin, an acrylic resin or a mixture thereof. The method according to claim 1,
Wherein the core of the rubber core-shell nanoparticles is made of a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber, and mixtures thereof. The method according to claim 1,
Wherein the composite is a roofing shingle for asphalt roofing. An improved roof construction mat for use in making planks for asphalt roofing construction,
The improved roof construction mat comprises a fiberglass mat comprising a plurality of glass fibers and a resin binder that holds together the individual glass fibers, wherein the resin binder comprises an improved roof construction mat . 9. The method of claim 8,
Wherein the resin binder comprises 0.1 to 20 wt% of the rubber core-shell nanoparticles based on the total amount of the resin in the binder. 9. The method of claim 8,
Wherein the resin binder is formed from urea formaldehyde resin, acrylic resin or a mixture thereof. 9. The method of claim 8,
Wherein the core of the rubber core-shell nanoparticles is made of a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber, and mixtures thereof. As an improved asphalt roofing construction board,
A fiberglass roof construction mat comprising a plurality of glass fibers and a resin binder for holding individual glass fibers together, and an asphalt coating covering the fiberglass roof construction mat, wherein the asphalt coating comprises an inorganic microfine filler therein, Wherein the asphalt coating further comprises interiorly embedded roofing granules and wherein the resin binder of the fiberglass roofing mat comprises rubber core-shell nanoparticles. 13. The method of claim 12,
Wherein the resin binder comprises 0.1 to 20 wt% of the rubber core-shell nanoparticles based on the total amount of the resin in the binder. 13. The method of claim 12,
Wherein the resin binder is formed from urea formaldehyde resin, acrylic resin or a mixture thereof. 13. The method of claim 12,
Wherein the core of the rubber core-shell nanoparticles is made of a synthetic polymer rubber selected from the group consisting of styrene / butadiene, polybutadiene, silicone rubber (siloxane), acrylic rubber and mixtures thereof. 13. The method of claim 12,
Wherein the asphalt coating comprises 30 to 80 weight percent of an inorganic particulate filler selected from the group consisting of dolomite, silica, slate powder and high magnesium carbonate based on the total weight of the filled asphalt. . As a fiberglass reinforced polymer composite material,
A matrix polymer and glass fibers dispersed in the matrix polymer, wherein the surfaces of the glass fibers carry a coating of rubber core-shell nanoparticles. 18. The method of claim 17,
Wherein the surfaces of the glass fibers carry a coating comprising a mixture of rubber core-shell nanoparticles and a film forming polymer. 18. The method of claim 17,
The glass fibers are made by combining together multiple attenuated glass filaments to form individual fibers and further an incipient size composition is applied to the individual glass filaments before individual glass filaments are combined Applied fiberglass reinforced polymer composites. 18. The method of claim 17,
The surfaces of the glass fibers carry a second coating of a secondary initial size composition applied to the fibers during fiber fabrication after the individual glass filaments are combined and the secondary initial size composition comprises additional rubber core- A film-reinforced polymer composite comprising a film-forming polymer.

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