Patent Grant
9139708
1. Field
The invention relates to foamed and nonfoamed polymeric material, and more particularly polyurethane composite materials, and methods for extruding the same.
2. Description of the Related Technology
Polymeric composite materials that contain organic or inorganic filler materials have become desirable for a variety of uses because of their excellent mechanical properties, weathering stability, and environmental friendliness.
These materials can be are relatively low density, due to their foaming, or high density when unfoamed, but are extremely strong, due to the reinforcing particles or fibers used throughout. Their polymer content also gives them good toughness (i.e., resistance to brittle fracture), and good resistance to degradation from weathering when they are exposed to the environment. This combination of properties renders some polymeric composite materials very desirable for use in building materials, such as roofing materials, decorative or architectural products, outdoor products, insulation panels, and the like.
Described herein are extrusion processes as related to polymeric composite materials. More particularly, the extrusion processes related to polyurethane composite materials. In some embodiments, highly filled polyurethane composite materials are extruded. Such materials may then be shaped and formed into solid surface articles. Articles comprising the polyurethane composite material as described herein are suitable for structure, building, and outdoor applications.
In one embodiment, a method of forming a polymeric composite material includes introducing at least one polyol and inorganic filler to a first conveying section of the extruder, transferring the at least one polyol and inorganic filler to a first mixing section of an extruder, mixing the at least one polyol and the inorganic filler in the first mixing section, transferring the mixed at least one polyol and inorganic filler to a second conveying section of the extruder, introducing a di- or poly-isocyanate to the second conveying section, transferring the mixed at least one polyol and inorganic filler and the di- or poly-isocyanate to a second mixing section, mixing the mixed at least one polyol and inorganic filler with the di- or poly-isocyanate in the second mixing section of the extruder to provide a composite mixture; and transferring the composite mixture to an output end of the extruder.
In some embodiments, the composite mixture includes about 40 to about 85 weight percent of the inorganic filler. In some embodiments, the composite mixture includes about 60 to about 85 weight percent of the inorganic filler. In some embodiments, the composite mixture includes about 65 to about 80 weight percent of the inorganic filler. The inorganic filler may include many different types of filler. One preferred filler includes fly ash.
In certain embodiments, the conveying sections and mixing sections are defined in terms of the screw segments and screw elements contained within the conveying or mixing section. In one embodiment, the first conveying section includes one or more transfer screws. In one embodiment, the first mixing section includes a slotted screw. In another embodiment, the first mixing section includes a lobal screw. In one embodiment, the first mixing section includes a lobal screw and a slotted screw.
In some embodiments, the second conveying section is located downstream of a first conveying section. In some embodiments, the second conveying section is located downstream of a first mixing section. In some embodiments, the section conveying section includes one or more transfer screws.
In some embodiments, a second mixing section is located downstream of a first mixing section. In some embodiments, a second mixing section is located downstream of the second conveying section. In certain embodiments, the second mixing section is adjacent to the output end of the extruder. In certain embodiments, the second mixing station includes a reverse screw. In certain embodiments, the reverse screw includes a reverse slotted screw.
In some embodiments, the method may further include adding one or more components of the composite mixture in the first conveying section of the extruder. Such additional components are further described herein. In one embodiment, the one or more components is selected from the group consisting of a catalyst, a surfactant, and a blowing agent. In other embodiments, the one or more components may include one or more of a cross linker, a chain extender, and a coupling agent. In certain of these embodiments, the method further includes blending the one or more components with the at least one polyol prior to introduction to the first conveying section.
In some embodiments, the method further includes mixing the mixed at least one polyol and inorganic filler and the di- or poly-isocyanate in a third mixing section subsequent to the second conveying section and prior to the second mixing section. In some embodiments, the third mixing section includes a reverse screw. Certain embodiments, further include introducing fibrous material in the third conveying section. In certain embodiments, the third conveying section is located between the second mixing section and the third mixing section.
As described herein, one or more fibrous materials may be extruded with the polymeric composite material. In one embodiment, the method further includes introducing fibrous material in the second conveying section. In certain embodiments, the method includes mixing the fibrous material with the mixed at least one polyol and inorganic filler and the di- or poly-isocyanate in the second mixing section.
Thermosetting polymeric composite materials may be made using an extruder. Such a process allows for thorough mixing of the various components of the polymeric composite material in the extruder. The screw and screw elements may be configured in various ways within an extruder to provide a substantially homogeneous mixture of the various components of the polymeric composite material. In addition, friction and other forces may promote the reaction of various monomers and other additives that create a polymeric matrix in the polymeric composite material. Moreover, the various components of a polymeric composite material may be added in different orders and at different positions in an extruder. Thus, extrusion of polymeric composite material is a desirable method for providing a medium for reaction, controlling reaction ingredients and conditions, and mixing the various components.
An extruder having one or more material inputs may be used to form such polymeric composite materials. In accordance with certain embodiments, a single screw extruder or a twin screw extruder may be used. Each screw of the extruder is mounted on a single shaft that transmits rotary motion to the screw. In embodiments of a twin screw extruder, each screw may be counter rotary to the other screw. The screw may comprise one or more screw elements mounted on the rotating shaft. The screw may alternatively be assembled from several separate screw elements, each of which forms a portion of the screw operated within the extruder. Screw elements may be rotatably disposed in an appropriate sequence of the axial shaft to form multiple segments of the screw. Various screw elements may include one or more of transport screw elements, lobal screw elements, reverse screw elements, slotted screw elements, and kneading block elements. Various screw elements are described in U.S. Pat. Nos. 5,728,337, 6,136,246 and 6,908,573, which are hereby incorporated by reference.
Referring to
In some embodiments, transport screw elements have a flight that is helically wound around the screw. The flight of the transport screw has a positive pitch and therefore transfers materials in the extruder barrel from the feed end to the output end. According to some embodiments, the flight of the transport screw may be made faster or slower, depending on the pitch of the threads of the transport screw element. In a transport screw, a greater pitch (i.e., threads/per unit of length) will result in slower transport of the material, while a lower pitch will result in faster transport of the material. Many different varieties of transport screw elements may be used. In some embodiments, utilizing a twin screw extruder, each screw may contain transport screw elements that are intermeshed. While transport screw elements mix some composite material, the primary function is conveying materials downstream in the extruder.
In some embodiments, the extruder may comprise one or more reverse screw element 45. These are generally utilized to reverse the flow of the composite materials toward the feed end of the extruder. As such, a reverse screw element 45 blocks the flow of components of the composite mixture, thus acting as a temporary seal and promotes added blending of the components and dispersion of fillers and other additives. In some embodiments, such components of the composite mixture may pass the reverse screw element after another shearing force or pressure allows the components to pass the reverse screw element. In some embodiments, the reverse screw element allows for substantial mixing of filler and other polymer composite materials.
As shown in
Lobal screw elements are generally a longer screw element. In some embodiments, a lobal screw element has 2 or 3 or more faces. In some embodiments, the lobal screw may be polygonal. Lobal screw elements do not comprise a plurality of discs like kneading blocks. Instead, lobal screw elements are generally a single structure. However, lobal screw elements may have one or more axial twists. In some embodiments, the axial twist of a lobal screw element is less than 180°. In some embodiments, the axial twist of a lobal screw element is less than 140°. In some embodiments, the axial twist of a lobal screw element is less than 90°. In some embodiments, the axial twist of a lobal screw element is less than 45°. In some embodiments, the axial twist of a lobal screw element is substantially 0°. One purpose of a lobal screw element is to squeeze various composite material in a defined space. Such lobal screw elements cause very high shear in the defined area. It has been discovered that lobal screw elements may force liquids to mix intimately with one another. In additionally embodiments, lobal screw element can provide substantial wetting of inorganic materials such as fibers and fillers by liquid components of the polymeric composite material, such as melted resins or liquid monomers. Lobal screw elements may be neutral or forward moving elements. Lobal screw elements are typically self-wiping in a twin screw extruder configuration as shown in
Slotted screw elements 55 may include a plurality of blades on all sides of the screw elements. In some embodiments, the blades may be disposed in line with other blades, such as a transfer screw element with spaces or slots between the helically wound flight. However, there is no requirement for the blades to be uniform or to have positive pitch. In some embodiments, a slotted screw blade includes angled ends. In some embodiments, the slotted screws have positive, negative, and neutral pitch (i.e., they may convey or block the composite material according to the type and arrangement of blades). However, some blades with angles ends may produce less conveying effect than a screw such as a transfer screw. In some embodiments, slotted screws are partially self-wiping. In some embodiments, slotted screws are not self wiping in a twin screw arrangement. In some embodiments, the slots of the slotted screw element may be filled with one or more composite materials, such as a hardened urethane. As a result, such slotted screw elements may produces substantial amount of mixing of various components of the mixture and also knead the mixture. In particular embodiments, slotted screws may be placed toward the feed end of an extruder which allows slots not to fill with polymeric resin, such as hardened polyurethane. Example of slotted screw elements may be found in U.S. Pat. No. 6,136,246.
Advantageously, these screw elements may be used to produce a desired amount of blending of components of the polymeric composite system. In certain embodiments, each screw element defines a segment of the extruder. In some embodiments, the segments may have substantially the same length. However, certain segments may have longer lengths than other segments and segments may also contain more than one screw element. In certain embodiments, the extruder may have up to nine extruder segments. However, the extruder may container more or less segments depending on the desired composite material characteristics. In some embodiments, the extruder includes 1, 2, 3, 4, 5, 6, 7, 8, or 9 segments.
Various segments of the extruder may be air or water cooled. Often, exothermic reactions during the production of the polymeric composite material may require sufficient cooling to prevent runaway exotherms. Such temperatures and cooling may be controlled by various means known to persons having ordinary skill in the art.
One or more components of the polymeric composite material may be introduced into one or more segments of the extruder through hoppers, feed chutes, or side feeders. One or more components may also be metered into the extruder through various means. Continuous feeding of the respective components of the polymeric composite material results in a continuous process of extruding the polymeric composite material.
Depending on the exact arrangement of the screw elements, the segments may further be classified into broader sections such as conveying sections and mixing sections. For example, a first composite component may be introduced in a first segment having a first transport screw, and a second composite component may be introduced in a second segment have a second transport screw. If such first and second segments are adjacent to each other, then the first and second segment may be classified as a conveying section. However, classification as a conveying section does not preclude mixing, even intimate mixing, of the various components of the polymeric composite material.
Such composite components may then be further transferred into other segments or sections. The components generally are transferred by the screws from the feed end to the discharge end of the extruder. In one embodiment, components are transferred into a mixing section. A mixing section may include a kneading blocks or reverse screws. Reverse screws have negative pitch. Thus, the reverse screws may block the materials until sufficient shearing forces the various components of the composite material through this barrel segment. Generally, this results in substantial mixing of the various components of the composite material.
It has been discovered that certain embodiments of extruders are able to produce highly filled polyurethane composite materials. Various components of the polymer composite material may include one or more of the following: at least polyol, at least one monomer or oligomeric di- or poly-isocyanates, an inorganic filler, fibrous materials, at least one catalyst, surfactants, colorants, and other various additive. Such components are further described herein.
Described herein are polymeric composite materials. In particular embodiments, the polymeric composite material include polyurethane composite materials. While the embodiments described herein are specifically related to polyurethane composite materials, the technology may also be applicable to many other polymeric resins, particularly those related to highly filled thermosetting polymers. Generally, a polyurethane is any polymer consisting of a chain of organic units joined by urethane linkages. Typically, a polyurethane may be formed by reaction of one or more monomeric or oligomeric poly- or di-isocyanates (sometimes referred to as “isocyanate”) and at least one polyol, such as a polyester polyol or a polyether polyol. These reactions may further be controlled by various additives and reaction conditions. For example, one or more surfactants may be used to control cell structure and one or more catalysts may be used to control reaction rates. Advantageously, the addition of certain polyol and isocyanate monomers and certain additives (e.g., catalysts, crosslinkers, surfactants, blowing agents), may produce a polyurethane material that is suitable for commercial applications.
As is well known to persons having ordinary skill in the art, polyurethane materials may also container other polymeric components by virtue of side reactions of the polyol or isocyanate monomers. For example, a polyisocyanurate may be formed by the reaction of optionally added water and isocyanate. In addition, polyurea polymers may also be formed. In some embodiments, such additional polymer resins may have an effect on the overall characteristics of the polyurethane composite material.
It has further been found that some portion of the polymeric component of polyurethanes may be replaced with one or more fillers such as particulate material and fibrous materials. With the addition of such fillers, the polyurethane composite materials may still retain good chemical and mechanical properties. These properties of the polyurethane composite material allows for its use in building materials and other structural applications. Advantageously, the polyurethane composite material may contain large loadings of filler content without substantially sacrificing the intrinsic structural, physical, and mechanical properties of the polymer. Such building materials would have advantages over composite materials made of less or no filler. For example, the building materials may be produced at substantially decreased cost. Furthermore, decreased complexity of the process chemistry may also lead to decreased capital investment in process equipment.
In one embodiment, the composite materials have a matrix of polymer networks and dispersed phases of particulate or fibrous materials. The polymer matrix includes a polyurethane network formed by the reaction of a poly- or di-isocyanate and one or more polyols. The matrix is filled with a particulate phase, which can be selected from one or more of a variety of components, such as fly ash particles, axially oriented fibers, fabrics, chopped random fibers, mineral fibers, ground waste glass, granite dust, slate dust or other solid waste materials.
Such polyurethane composite materials may be formed with a desired density, even when foamed, to provide structural stability and strength. In addition, the polyurethane composite materials can be easily tuned to modify its properties by, e.g., adding oriented fibers to increase flexural stiffness, or by adding pigment or dyes to hide the effects of scratches. Also, such polyurethane composite materials may also be self-skinning, forming a tough, slightly porous layer that covers and protects the more porous material beneath. Such tough, continuous, highly adherent skin provides excellent water and scratch resistance. In addition, as the skin is forming, an ornamental pattern (e.g., a simulated wood grain) can be impressed on it, increasing the commercial acceptability of products made from the composite.
Described herein are certain improvements that may be used in the production of polyurethane composite materials. Some previously described polyurethane composite material systems are included in U.S. patent application Ser. No. 10/764,012, filed Jan. 23, 2004, and entitled “FILLED POLYMER COMPOSITE AND SYNTHETIC BUILDING MATERIAL COMPOSITIONS,” now published as U.S. Patent Application Publication No. 2005-163969-A1, and U.S. patent application Ser. No. 11/190,760, filed Jul. 27, 2005, and entitled “COMPOSITE MATERIAL INCLUDING RIGID FOAM WITH INORGANIC FILLERS,” now published as U.S. Patent Application Publication No. 2007-0027227 A1, which are both hereby incorporated by reference in their entireties. However, in now way, are such polyurethane composite material systems intended to limit the scope of the improvements described in the present application.
The various components and processes of preferred polyurethane composite materials are further described herein:
Monomeric or Oligomeric Poly or Di-Isocyanates
As discussed above, one of the monomeric components used to form a polyurethane polymer of the polyurethane composite material is one or more monomeric or oligomeric poly or di-isocyanates. The polyurethane is formed by reacting a poly- or di-isocyanate. In some embodiments, an aromatic diisocyanate or polyisocyanate may be used.
In certain embodiments methylene diphenyl diisocyanate (MDI) is used. The MDI can be MDI monomer, MDI oligomer, or mixtures thereof. The particular MDI used can be selected based on the desired overall properties, such as the amount of foaming, strength of bonding to the inorganic particulates, wetting of the inorganic particulates in the reaction mixture, strength of the resulting composite material, and stiffness (elastic modulus). Although toluene diisocyanate can be used, MDI is generally preferable due to its lower volatility and lower toxicity. Other factors that influence the particular MDI or MDI mixture are viscosity (a low viscosity is desirable from an ease of handling standpoint), cost, volatility, reactivity, and content of 2,4 isomer. Color may be a significant factor for some applications, but does not generally affect selection of an MDI for preparing an article.
Light stability is also not a particular concern for selecting MDI for use in the composite material. According to some embodiments, the composite material allows the use of isocyanate mixtures not generally regarded as suitable for outdoor use, because of their limited light stability. When used in to form the polyurethane composite material, such materials surprisingly exhibit excellent light stability, with little or no yellowing or chalking. Suitable MDI compositions include those having viscosities ranging from about 25 to about 200 cp at 25° C. and NCO contents ranging from about 30% to about 35%. Generally, isocyanates are used that provide at least 1 equivalent NCO group to 1 equivalent OH group from the polyols, desirably with about 5% to about 10% excess NCO groups. Useful polyisocyanates also may include aromatic polyisocyanates. Suitable examples of aromatic polyisocyanates include 4,4-diphenylmethane diisocyanate (methylene diphenyl diisocyanate), 2,4- or 2,6-toluene diisocyanate, including mixtures thereof, p-phenylene diisocyanate, tetramethylene and hexamethylene diisocyanates, 4,4-dicyclohexylmethane diisocyanate, isophorone diisocyanate, mixtures of 4,4-phenylmethane diisocyanate and polymethylene polyphenylisocyanate. In addition, triisocyanates such as, 4,4,4-triphenylmethane triisocyanate 1,2,4-benzene triisocyanate; polymethylene polyphenyl polyisocyanate; and methylene polyphenyl polyisocyanate, may be used. Isocyanates are commercially available from Bayer USA, Inc. under the trademarks MONDUR and DESMODUR. Suitable isocyanates include Bayer MRS-4, Bayer MR Light, Dow PAPI 27, Bayer MR5, Bayer MRS-2, and Huntsman Rubinate 9415.
In certain embodiments, the average functionality of the isocyanate component is between about 1.5 to about 4. In other embodiments, the average functionality of the isocyanate component is about 3. In other embodiments, the average functionality of the isocyanate component is less than about 3, including, about 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, and 2.9. In some embodiments, the isocyanate has a functionality of about 2. Some of these embodiments produce polyurethane composite materials with higher mechanical strengths and lower costs than polyurethane composite material comprising more than about 2.
As indicated above, the isocyanate used in the invention is reacted with one or more polyols. In general, the ratio of isocyanate to polyol (isocyanate index), based on equivalent weights (OH groups for polyols and NCO groups for isocyanates) is generally in the range of about 0.5:1 to about 1.5:1, more particularly from about 0.8:1 to about 1.1:1, and in another embodiment, from about 0.8:1 to about 1.2:1. Ratios in these ranges provide good foaming and bonding to inorganic particulates, and yields low water pickup, fiber bonding, heat distortion resistance, and creep resistance properties. However, precise selection of the desired ratio will be affected by the amount of water in the system, including water added per se as a foaming agent, and water introduced with other components as an “impurity.”
In some embodiments, an isocyanate may be selected to provide a reduced isocyanate index. It has been discovered that the isocyanate index can be reduced without compromising the polyurethane composite material's chemical or mechanical properties. It is additionally advantageous according to some embodiments to use an isocyanate with a reduced isocyanate index as isocyanates are generally higher priced than polyols. Thus, a polyurethane system formed by an isocyanate monomer with a reduced isocyanate index may result in reduced cost of producing the total system.
Polyols
According to some embodiments, the polyurethane polymer is a reaction product of one or more polyols with an isocyanate. The one or more polyols used may be single monomers, oligomers, or blends. Mixtures of polyols can be used to influence or control the properties of the resulting polymer network and composite material. The properties, amounts, and number of polyols used may be varied to produce a desired polyurethane composite material.
It is generally desirable to use polyols in liquid form, and generally in the lowest viscosity liquid form available, as these can be more easily mixed with the inorganic particulate material. So-called “EO” tipped polyols can be used; however their use is generally avoided where it is desired to avoid “frosting” of the polymer material when exposed to water.
In some embodiments, the at least one polyol include a polyester or polyether polyol. Polyether polyols are commercially available from, for example, Bayer Corporation under the trademark MULTRANOL. In general, desirable polyols include polyether polyols, such as MULTRANOL (Bayer), including MULTRANOL 3400 or MULTRANOL 4035, ethylene glycol, polypropylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, 2-pentane diol, pentaerythritol adducts, 1trimethylolpropane adducts, trimethylolethane adducts, ethylendiamine adducts, and diethylenetriamine adducts, 2-butyn-1,4-diol, neopentyl glycol, 1,2-propanediol, pentaerythritol, mannitol, 1,6-hexanediol, 1,3-butylene glycol, hydrogenated bisphenol A, polytetramethyleneglycolethers, polythioethers, and other di- and multi-functional polyethers and polyester polyethers, and mixtures thereof. The polyols need not be miscible, but should not cause compatibility problems in the polymeric composite.
In some embodiments, plant-based polyols are used as at least one polyol. These polyols are lower in cost, and not dependent on the price and availability of petroleum. In some embodiments, the plant-based polyols provide a polyurethane system that is substantially identical to that provided by oil-based polyols. In other embodiments, plant-based polyols can be used to replace at least a portion of the oil-based polyols. By employing plant-based polyols, the polyurethane composite material is more environmentally safe and friendly. In addition, certain equipment used to handle and dispose of oil-based polyols may be costly.
In some embodiments, the at least one polyol is a polyester polyol that is substantially resistant to water soaking and swelling. Thus, these polyols can be used in the formation of polyurethane composite materials which, when cured, attracts less water. In certain cases, the polyester polyols absorb less water than polyether polyols. However, in some embodiments, polyester polyols and polyether polyols can be mixed in the formation of polyurethane composite material to provide better water resistance.
Some embodiments of the polyurethane composite material comprise at least one polycarbonate polyol. These embodiments provide higher impact and/or chemical resistance, as compared to polyurethane composite material made from polyester and/or polyether polyols. However, combinations of polycarbonate polyols, polyester polyols, and polyether polyols can be used in systems with high inorganic fillers to provide the desired mechanical and physical property of the polyurethane composite material. In some embodiments, building products comprising the polyurethane composite materials which employ at least one polyester polyol demonstrate improved water resistance.
In some embodiments, at least some phenolic polyols are used to make polyurethane composite materials which have improved flame retardancy as compared to those polyurethane composite materials that are not made from phenolic polyols. Such polyurethane composite materials may also be fire and smoke resistance.
In other embodiments, the polyurethane composite materials are made from at least one acrylic polyol. In some embodiments, the polyurethane composite materials made from the at least one acrylic polyol demonstrate improved weathering as compared to those that are not made from at least one acrylic polyol. In other embodiments, the polyurethane composite materials are made from at least one acrylic polyol exhibit substantially no discoloration when exposed to sunlight.
In one embodiment, a first polyol having a first hydroxyl number and a second polyol having a second hydroxyl number less than the first hydroxyl number may be used. Such combination of polyols form a first polyurethane that is less rigid than a second polyurethane that would be formed by the reaction of the first polyol in the absence of the second polyol. In some embodiments, the first polyol has a hydroxyl number ranging from about 250 to about 500 mg KOH/g. In some embodiments, the first polyol has a hydroxyl number ranging from about 300 to about 450 mg KOH/g. In some embodiments, the first polyol has a hydroxyl number ranging from about 320 to about 400 mg KOH/g. In some embodiments, the first polyol has a hydroxyl number ranging from about 350 to about 500 mg KOH/g. In some embodiments, the first polyol has a hydroxyl number ranging from about 370 to about 600 mg KOH/g. In some embodiments, the second polyol has a hydroxyl number less than the first polyol. In some embodiments, the second polyol has a hydroxyl number ranging from about 20 to about 120 mg KOH/g. In some embodiments, the second polyol has a hydroxyl number ranging from about 20 to about 70 mg KOH/g. In some embodiments, the second polyol has a hydroxyl number ranging from about 30 to about 60 mg KOH/g. In some embodiments, the second polyol has a hydroxyl number ranging from about 50 to about 75 mg KOH/g. In some embodiments, the second polyol has a hydroxyl number ranging from about 40 to about 60 mg KOH/g. In some embodiments, the second polyol has a hydroxyl number ranging from about 30 to about 50 mg KOH/g.
For example, a first polyol such as Bayer's MULTRANOL 4500 may be used in combination with Bayer's ARCOL LG-56 and MULTRANOL 3900. In this case, the first polyol has a hydroxyl number ranging from 365-395 mg KOH/g. For ARCOL LG-56, the second polyol has a hydroxyl number ranging from 56.2 to 59.0 mg KOH/g. For MULTRANOL 3900 has a hydroxyl number ranging from 33.8 to 37.2 mg KOH/g. However, these examples are not intended to be limiting. Any number of polyol as described above may be selected for the hydroxyl number in controlling the flexibility or rigidity of a polyurethane product.
In one embodiment, mixture of polyols can be used to achieve the desired mechanical strength and rigidity of the final polyurethane composite material. In some embodiments, polyols with OH functionality between about 2 to about 7 can be used. In other embodiments, the average functionality of the polyols is between about 4 to about 7. The polyurethane composite materials become less expensive because the amount of isocyanate needed to react with the polyols to substantially form the desired polyurethane decreases. While this in some case may increase the rubberiness, non-brittleness, or flexibility of the polyurethane composite material, the correct balance of these functional polyols with OH functionality, between about 4 to about 8, maintains the mechanical properties of the polyurethane composite material, as compared to a polyurethane composite material made from polyols with an average functionality less than 4.
In some embodiments, the polyurethane composite material is made by using higher functional polyols in place of polyols having an average functionality of 2 or 3. In these embodiments, the polyurethane composite material has more cross linking. Some embodiments have higher impact strength, flexural strength, flexural modulus, chemical resistance, and water resistance as compared to the polyurethane composite material formed by polyols having a functionality of about 2 to about 3.
In some embodiments, the polyurethane composite material is made by using more than one polyol with different OH numbers to give the same weighted average OH number. Such polyurethane composite materials yield a more segmented polymer. By allowing many polyols of different functionality and/or molecular weight to be mixed together to make the needed OH number to balance the number of isocyanate groups, the orderliness of the resulting polymer chain is more segmented and less likely to align together. In some embodiments, the polyurethane composite material comprises three, four, five, or six types of polyols of different functionality and/or molecular weight. For example, a polyurethane system can be made from combination of multiple types of polyols, wherein at least one first polyol has an average functionality of about 2, wherein at least one second polyol has an average functionality of about 4, and wherein at least one third polyol has an average functionality of about 6. In one embodiment, the overall number of hydroxyl groups may be adjusted with varying polyols. In some embodiments, combinations of polyols with great number of hydroxyl groups may be blended with smaller quantities of polyols with less hydroxyl groups in order to produce a desired overall number of hydroxyl groups, which will react with the isocyanate.
In some embodiments, impact strength of the polyurethane composite material is greater than polyurethane composite materials comprising polyols of the same or substantially similar functionality and/or molecular weight. Although the two polyurethane compositions may comprise polyols with substantially similar average functionality and/or molecular weight, the polyurethane composition comprising polyols with substantially different functionality may exhibit improved mechanical properties such as impact strength. In some embodiments, polyurethane composite materials comprising polyols of multiple functionalities are more resistant to stress cracking.
Other embodiments of the polyurethane composite material are made from at least one polyol with a molecular weight from about 2000 to about 8000. These polyurethane composite materials exhibit an integral skin. In some embodiments, the skin is thicker. In other embodiments, the skin is less porous and harder. In some embodiments, the use of at least one polyol with a molecular weight from about 2000 to about 8000 results in the migration of the at least one polyol to migrate to the outer surface of the polyurethane composite material, thus allowing more outer skin to be formed.
In one embodiment, mixtures of two or more polyols may be used. In some embodiments, each polyol of a multi-polyol polyurethane system may be chosen for the various mechanical and chemical properties that result in the polyurethane composite produced as a result of using the polyol. For example, it is known to persons having ordinary skill in the art that polyols are often classified as rigid or flexible polyols based on various properties of the individual polyol and the overall flexibility of a polyurethane polymer produced from the respective polyols. Typically, the rigidity or flexibility of the polyurethane formed from any single polyol may be governed by one or more of the hydroxyl number, functionality, and molecular weight of the polyol. As such, one or more polyols with different characteristics may be used to control the physical and mechanical characteristics of the polyurethane composite material.
In one embodiment, the amount of rigid polyol is carefully controlled in order to avoid making the composite too brittle. In some embodiments, the weight ratio of rigid to flexible polyol ranges from about 0.5 to about 20. In other embodiments, the ratio of rigid to flexible polyol is about 1 to about 15. In other embodiments, the ratio of rigid to flexible polyol is about 4 to about 15. In other embodiments, the ratio of rigid to flexible polyol is about 3 to about 10. In other embodiments, the ratio of rigid to flexible polyol is about 6 to about 12.
If more than one polyol is used to form the polyurethane composition, mixtures of polyols can be used. In certain embodiments, the polyurethane is formed by reaction of a first polyol and a second polyol. In some of these embodiments, the first polyols has a functionality of at least three and a hydroxyl number of about 250 to about 800, and more preferably about 300 to about 400. In some embodiments, the first polyol hydroxyl number is about 350 to about 410. In some of these embodiments, the molecular weight of the first polyol ranges from about 200 to about 1000. In other embodiments, the molecular weight of the first polyol ranges from about 300 to about 600. In other embodiments, the molecular weight of the first polyol ranges from about 400 to about 500. Still, in some embodiments, the molecular weight of the first polyol is about 440.
A second polyol can be used which produces a less rigid polyurethane compared to a polyurethane produced if only the first polyol is used. In some embodiments, the second polyol has a functionality of about 3. In some embodiments, the functionality of the second polyol is not greater than three. In these embodiments, the second polyol can have a molecular weight of about 1000 to about 6000. In other embodiments, the second polyol has a molecular weight of about 2500 to about 5000. In some embodiments, the second polyol has a molecular weight of about 3500 to about 5000. In some embodiments, the molecular weight is about 4800. In other embodiments, the molecular weight of the second polyol is about 3000. In some of these embodiments, the second polyol has a hydroxyl number of about 25 to about 70, and more preferably about 50 to about 60.
Fillers
As discussed above, one or more filler materials may be included in the polyurethane composite material. In some embodiments, it is generally desirable to use particulate materials with a broad particle size distribution, because this provides better particulate packing, leading to increased density and decreased resin level per unit weight of composite. Since the inorganic particulate is typically some form of waste or scrap material, this leads to decreased raw material cost as well. In certain embodiments, particles having size distributions ranging from about 0.0625 inches to below 325 mesh have been found to be particularly suitable. In other embodiments, particles having size distribution range from about 5 μm to about 200 μm, and in another embodiment, from about 20 μm to about 50 μm.
Suitable inorganic particulates can include ground glass particles, fly ash, bottom ash, sand, granite dust, slate dust, and the like, as well as mixtures of these. Fly ash is desirable because it is uniform in consistency, contains some carbon (which can provide some desirable weathering properties to the product due to the inclusion of fine carbon particles which are known to provide weathering protection to plastics, and the effect of opaque ash particles which block UV light, and contains some metallic species, such as metal oxides, which are believed to provide additional catalysis of the polymerization reactions. Ground glass (such as window or bottle glass) absorbs less resin, decreasing the cost of the composite.
In general, fly ash having very low bulk density (e.g., less than about 40 lb/ft3) and/or high carbon contents (e.g., around 20 wt % or higher) are less suitable, since they are more difficult to incorporate into the resin system, and may require additional inorganic fillers that have much less carbon, such as foundry sand, to be added. Fly ash produced by coal-fueled power plants, including Houston Lighting and Power power plants, fly and bottom ash from Southern California Edison plants (Navajo or Mohave), fly ash from Scottish Power/Jim Bridger power plant in Wyoming, and fly ash from Central Hudson Power plant have been found to be suitable for use in the invention.
Some embodiments of the polyurethane composite materials additionally comprise blends of various fillers. In some of these embodiments, the polyurethane composite materials exhibit better mechanical such as impact strength, flexural modulus, and flexural strength. One advantage in using blends of such systems is higher packing ability of blends of fillers. For example, a 1:1 mixture of coal fly ash and bottom ash has also been found to be suitable as the inorganic particulate composition.
Example in Table 1: The examples below were all mixed in a thermoset aromatic polyurethane system made with Hehr 1468 polyether polyol (15% of the total weight of the non-ash portion), water (0.2%), Air Products DC-197 (1.5%), Air Products 33LV amine catalyst (0.06%), Witco Fomrez UL28 tin catalyst (0.02%), and Hehr 1426A isocyanate (15%). 1.5×3.5×24 inch boards were made.
Thus, embodiments of the polyurethane composite material which comprise bottom and fly ash exhibit increased flexural strength and flexural modules as compared to polyurethane composite material comprising bottom ash alone. Some of these embodiments have a density of about 65 lbs/ft3 to about 85 lbs/ft3, including about 65, 67, 69, 71, 73, 75, 77, 79, 81, 83, or 85 lbs/ft3.
In some of embodiments, the polyurethane composite material comprising about 65% ash filler of which about 32.5 wt % was bottom ash and about 32.5% was fly ash had a flexural strength of at least about 2300 psi, more preferably at least about 2400 psi, and even more preferably at least about 2500 psi. In some of embodiments, the polyurethane composite material comprising about 75% ash filler of which about 37.5 wt % was bottom ash and about 37.5% was fly ash had a flexural strength of at least about 2400 psi, more preferably at least about 2500 psi, and even more preferably at least about 2650 psi.
In some of embodiments, the polyurethane composite material comprising about 65% ash filler of which about 32.5 wt % was bottom ash and about 32.5% was fly ash had a flexural modulus of at least about 400 Ksi, more preferably at least about 440 Ksi, and even more preferably at least about 460 Ksi. In some of embodiments, the polyurethane composite material comprising about 75% ash filler of which about 37.5 wt % was bottom ash and about 37.5% was fly ash had a flexural modulus of at least about 640 Ksi, more preferably at least about 660 Ksi, and even more preferably at least about 690 Ksi.
In some embodiments, slate dust can be added to the polyurethane composite material to provide UV protection to the polyurethane composite material. Some of these embodiments additionally comprise one or more of pigments, light stabilizers, and combinations thereof. In some embodiments, polyurethane composite materials comprising slate dust exhibit substantially improved weathering. In some embodiments, the polyurethane composite material comprises a dust. A dust may be selected from at least one of slate dust, granite dust, marble dust, other stone-based dusts, and combinations thereof. In some embodiments, the polyurethane composite material comprises about 0.2 to about 70 wt % dust. In other embodiments, the polyurethane composite materials comprise about 10 to about 50 wt % of dust. In other embodiments, the polyurethane composite materials comprise about 20 to about 60 wt % of dust. In other embodiments, the polyurethane composite materials comprise about 30 to about 55 wt % of dust. In some embodiments, dust may be added to the composite material as additional filler. In this embodiment, the filler that is not dust may be present in the composite in amounts from about 10 to about 70 weight percent and the dust may be added in amounts of about 5 to about 35 weight percent.
The following is an example of a polyurethane composite material that comprises dust. The example should be in no way limiting, as other embodiments will be readily understood by a person having ordinary skill in the art.
Example from Table 2: In a blend of Cook Composites 5180 MDI (13.1% by weight), 5205 polyol (3.91%), Dow DER (1.98%), antimony trioxide flame retardant (3.52%), with Air Products DC-197 silicone surfactant (0.23%), benzoyl peroxide (0.55%), and chipped slate (59.5%), with the added pigments, carbon black and slate dust, all acting as UV inhibitors. The light exposure was to a high fusion (UV light) chamber at AlliedSignal Aerospace. Usually a 10 minute exposure in this chamber would deeply discolor this resin system due to the yellowing of the MDI-based ingredients in the resin system.
In the above test, clearly slate dust provided better light stability than coal ash, and the combination of slate dust plus carbon black provided the best UV resistance, and had not failed yet in the 20 minute test (the only sample to not fail). The effect of the slate dust was far more influential for UV stability then the various pigments tested, including carbon black plus fly ash.
In some embodiments, the polyurethane composite material composition comprises about 20 to about 95 weight percent of inorganic filler, which includes, for example, approximately 20, 25, 30, 35, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, or 94 weight percent of filler. These amounts may be based on the total of all of the fillers, such as one or more of fly ash, dust, and fibrous material. However, the filler values may also be representative of only one type of filler, e.g, fly ash. In certain embodiments, the polymeric composite material may contain the filler in an amount within a range formed by the two of the foregoing approximate weight percent. In other embodiments, the polyurethane composite material comprises about 40 to about 85 weight percent of the filler. In other embodiments, the polyurethane composite material comprises about 55 to about 80 weight percent of the filler. In other embodiments, the polyurethane composite material comprises about 65 to about 85 weight percent of the filler. In other embodiments, the polyurethane composite material comprises about 40 to about 60 weight percent of the filler. In other embodiments, the polyurethane composite material comprises about 55 to about 70 weight percent of the filler. Here, the unit “weight percent” refers to the relative weight of the filler component compared to the total weight of the composite material.
Fibers
In some embodiments, reinforcing fibers can also be introduced into the polyol mixture prior to introduction of the isocyanate. In some embodiments, reinforcing fibers may be introduced after the at least one polyol and the isocyanate are mixed. These can include fibers per se, such as chopped fiberglass (chopped before or during mixing process such as extrusion), or fabrics or portions of fabrics, such as rovings or linear tows, or combinations of these. Typically, the reinforcing fibers range from about 0.125 in. to about 1 in, more particularly from about 0.25 in to about 0.5 in. The reinforcing fibers give the material added strength (flexural, tensile, and compressive), increase its stiffness, and provide increased toughness (impact strength or resistance to brittle fracture). Fabrics, rovings, or tows increase flexural stiffness and creep resistance. The inclusion of the particular polyurethane networks of the invention, together with the optional surfactants, and the inorganic particulate sizes used make the composite of the invention particularly and surprisingly well suited for inclusion of reinforcing fibers in foamed material, which normally would be expected to rupture or distort the foam bubbles and decrease the strength of the composite system.
In addition to inclusion of reinforcing fibers into the polyol mixture prior to polymerization, oriented axial fibers can also be introduced into the composite after extrusion, as the polymer exits the extruder and prior to any molding. The fibers (e.g., glass strings) can desirably be wetted with a mixture of polyol (typically a higher molecular weight, rigid polyol) and isocyanate, but without catalyst or with a slow cure catalyst, or with other rigid or thermosetting resins, such as epoxies. This allows the wetted fiber to be incorporated into the composite before the newly added materials can cure, and allows this curing to be driven by the exotherm of the already curing polymer in the bulk material.
Whether added before or after polymerization and/or other mixing processing such as extrusion, the dispersed reinforcing fibers may be bonded to the polymeric matrix phase, thereby increasing the strength and stiffness of the resulting material. This enables the material to be used as a structural synthetic lumber, even at relatively low densities (e.g., about 20 to about 60 lb/ft3).
According to certain embodiments, many types of fibers may be suitable for use in the polyurethane composite material. In some embodiments, the polyurethane composite materials comprise at least one of basalt, Wollastinite, other mineral fibers, or combinations thereof. In some embodiments, these components may be used in place of or in combination with glass fibers
Example from Table 3: In a mixture of Hehr 1468 polyether polyol (500 grams), Hehr 1468 MDI (432 g), water (3 g), Air Products 33LV amine catalyst (1 g), Mohave coal fly ash (800 g), and the following reinforcing fibers, all made in 1.5×3.5×24 inch lumber samples:
In some embodiments, basalt fibers provide more flexural strength, and flexural modulus to the highly-filled polyurethane composite materials than fiberglass, and the combination of the two fibers gives a synergistic effect on both measured properties.
In some of embodiments, the polyurethane composite material comprising about 1.25% of chopped fiber glass and about 1.25% of basalt had a flexural strength of at least about 2650 psi, more preferably at least about 2700 psi, and even more preferably at least about 2730 psi.
Axial fibers or fabrics can also be added to the polyurethane composite material. These fiber and/or fabric typically increase the rigidity of the polyurethane composite material, and increase the mechanical strength. Using thicker fibers, rovings, tows, fabrics or rebar in the axial or stressed direction of the product can eliminate or reduce the tendency of the plastic to creep with time or higher temperature. These reinforcements also give higher initial tensile and flexural strength, and higher flexural and tensile stiffness of the polyurethane composite material. One advantage of using axial fibers or fabrics is that the fibers or fabrics are oriented in a direction that supports the polyurethane composite material. Unlike axial fibers, randomly chopped fibers are less structurally supportive.
In some embodiments, the axial fibers or fabrics may be added while dry (no resin on them). In other embodiments, the fibers or fabrics may be “wet” with resin when mixed with the polyurethane composite material. In some embodiments, the axial fibers or fabrics are added to the polyol and catalyst premix. In other embodiments, the axial fibers or fabrics are added to the isocyanate premix. Still, other embodiment may include adding the axial fibers of fabric together with a slow or delayed reaction polyol, catalyst, and isocyanate. Thus, the axial fibers can be added with multiple components of the polyurethane composite material.
In some embodiments, the axial fibers or fabrics may be added to the polyurethane composite material under tension, as is done with steel rebar in structural concrete. This provides additional strength in the tension direction, and in bending, as well as higher stiffness in the tension and bending directions.
Example in Table 4: Glass and basalt fibers were implanted in a highly-filled coal ash-thermosetting polyurethane mixture while still uncured, and the fibers laid lengthwise down the urethane in a box mold, and only on the top of the board (on one face). The fibers were laid in the urethane mixture about ⅛ inch below the surface of the mix, but frequently the fibers moved during the subsequent foaming and cure in the closed box mold, and sometimes showed on the board surface.
The flexural properties were unaffected by this fiber movement. The glass fibers from rovings were 0.755 g/ft, the basalt rovings from Ahlstrom (Canada) were 0.193 g/ft. The boards were 1.5×3.5×24 inches. During flexural testing the boards were tested so that the rovings were on the tensile side of the boards (not the compression side). Some of the rovings were pre-wetted with the same resin system as in the boards, but without the coal ash filler. The resin system was: Bayer Multranol 4035 polyether polyol (16.6% by weight), Bayer Multranol 3900 polyether polyol (5.5%), Air products DC-197 silicone surfactant (0.16%), water (0.07%), Witco Fomrez UL-28 tin catalyst (0.03%), Air Products 33LV amine catalyst (0.10%), Coal fly ash (49%), Bayer MRS4 MDI isocyanate (20.4%).
By wetting the glass fibers with uncured resin or cured resin, the boards are considerably stronger—even stronger than basalt reinforced boards with the same weight of fiber. By wetting the glass roving with polyurethane resin, the strength of the glass roving exceeds that of the unwetted basalt fiber.
In some embodiments, polyurethane composite materials comprising less than about 1.5 wt % of glass fiber rovings prewet with resin had a flexural strength of at least about 3500 psi and more preferably at least about 4000 psi. In embodiments wherein the prewet glass fiber rovings were procured with the polyurethane resin, the flexural strength was at least about 150 Ksi, and more preferably at least about 180 Ksi.
Chain Extenders & Cross Linkers
In some embodiments of the polyurethane composite material, low molecular weight reactants such as chain extenders or cross linkers provide a more polar area in the polyurethane composite material. These reactants allow the polyurethane system to more readily bind the inorganic filler and/or inorganic or organic fibers in the polyurethane composite material.
In some embodiments, the polyurethane composite material comprises one or more selected from chain extenders, crosslinkers, and combinations thereof. In some embodiments, the chain extenders can be selected one or more from the group comprising ethylene glycol, glycerin, 1,4-butane diol, trimethylolpropane, glycerol, or sorbitol. In some embodiments, at least one cross linker may be used to replace at least a portion of the at least one polyol in the polyurethane composite material. In some cases, this results in reduced costs of the overall product.
In some embodiments which comprise chain extenders, the mechanical properties of the polyurethane composite material are improved. In some embodiments, chain extenders are not blocked from reacting with the isocyanate by the filler. This is due to the molecular size of the chain extenders. In some embodiments, the chain extenders result in better mechanical properties as compared to polyurethane composite materials with high filler inorganic loads, which do not use chain extenders. These mechanical properties include flexural strength and modulus, impact strength, surface hardness, and scratch resistance.
In other embodiments, polyurethane composite material comprising chain extenders traps metals and metal oxides. This is advantageous in highly filled polyurethane composite materials when the filler is coal or other ashes, including fly ash and bottom ash, which can contain hazardous heavy metals. In some embodiments, the polyurethane composite material substantially prevents leaching of heavy metals in the polyurethane composite material.
In some embodiments, a highly filled polymer composition comprising chain extenders provides faster curing and less need for post-curing of the polyurethane composite materials. In some embodiments, the chain extenders provide better water resistance for the polyurethane composite material. These chain extenders include diamine chain extenders, such as MBOCA and DETDA. However, other embodiments of the polyurethane composite material may comprise glycol extenders.
Blowing Agents
Foaming agent may also be added to the reaction mixture if a foamed product is desired. While these may include organic blowing agents, such as halogenated hydrocarbons, hexanes, and other materials that vaporize when heated by the polyol-isocyanate reaction, it has been found that water is much less expensive, and reacts with isocyanate to yield CO2, which is inert, safe, and need not be scrubbed from the process. In addition, CO2 provides the type of polyurethane cells desirable in a foamed product (i.e., mostly closed, but some open cells), is highly compatible with the use of most inorganic particulate fillers, particularly at high filler levels, and is compatible with the use of reinforcing fibers.
If water is not added to the composition, some foaming may still occur due to the presence of small quantities of water (around 0.2 wt %, based on the total weight of the reaction mixture) introduced with the other components as an “impurity.” Such water-based impurities may be removed by drying of the components prior to blending. On the other hand, excessive foaming resulting from the addition of too much water (either directly or through the introduction of “wet” reactants or inorganic particulate materials) can be controlled by addition of an absorbent, such as UOP “T” powder.
The amount of water present in the system will have an important effect on the density of the resulting composite material. This amount generally ranges from about 0.10 wt % to about 0.40 wt %, based on the weight of polyol added, for composite densities ranging from about 20 lb/ft3 to about 90 lb/ft3. However, polyurethane composite material densities may be controlled by varying one or more other components as well. In some embodiments, the overall density of the polyurethane composite material may range from about 30 lb/ft3 to about 80 lb/ft3. In some embodiments, the overall density of the polyurethane composite material may range from about 40 lb/ft3 to about 60 lb/ft3.
In some embodiments, the addition of excess blowing agent or water above what is needed to complete the foam reaction adds strength and stiffness to the polyurethane composite material, if the material is restrained during the forming of the composite material. Typically, excess blowing agent may be added to the polyol premixture. Such excessive blowing agent may produce a vigorously foaming reaction product. To contain such reaction product, a forming device that contains the pressure or restrains the materials from expanding may be used. Such forming devices are further described herein. The restraint of the material or the higher pressure created by a mold or restraining forming belts, causes higher pressure within the material which modifies the foam cell structure, thus allowing higher mechanical properties of the resulting cured material.
According to certain embodiments, use of excess blowing agent in formation of the polyurethane composite material may also improves the water resistance of the polyurethane composite material. In some embodiments, use of excessive blowing agent may also increase the thickness and durability of the outer skin of the self skinning polyurethane composite material.
Solvents
The addition of solvents to the reaction mixture may also provide certain advantages. In some embodiments of the polyurethane composite materials, solvents can be added to the polyol premix prior to or during the formation of the polyurethane. While it is described that solvents are added to the polyol premix, solvents may also be added at other stages of mixing of various components of the polyurethane composite material. In some embodiments, the solvent may be added with any one or more components of the reaction mixture which produces the polyurethane composite material.
In some embodiments, addition of a solvent to a polyol premix results in a polyurethane composite material that is more scratch and mar resistance as compared to the same polyurethane composition made without the solvent added to the polyol premix. Additional properties that result in some embodiments include a harder skin. In addition, solvents may cause a higher concentration of resin material to be in the self skinning layer, as opposed to the fillers and reinforcing fibers. In some materials, this provides a polyurethane composite material having a higher concentration of ultraviolet stabilizers, antioxidants, and other additives are closer to the outside of the composite material. In some embodiments, use of solvent produces a polyurethane composite material with an increases skin thickness. In other embodiments, the skin density may also be increased. Still, in other embodiments, the addition of solvents may decrease the interior density of the polyurethane composite material.
In some embodiments, the addition of solvent to the polyol premix substantially improves the weathering of the polyurethane composite material due to the higher density and thickness of the outer skin, which can contain more concentrated antioxidants, pigments, fillers and UV inhibitors. In other embodiments, the addition of the solvent to the polyol premix substantially prevents discoloration of the polyurethane composite material when a sample of the material is exposed to sunlight or UV radiation. In other embodiments, the addition of the solvent to the polyol premix provides a polyurethane composite material (upon mixing of the rest of the components) which has improved anti-static properties.
For example, the addition of about 2 to about 10 wt % of a solvent selected from the group consisting of a hydrocarbon solvent (pentane, hexane), carbon tetrachloride, trichloroethylene, methylene chloride, chloroform, methyl chloroform, perchloroethylene, or ethyl acetate to a polyol premix, the resulting self-skinning polyurethane composite material has a thicker skin as compared to polyurethane composite materials which are not create by the addition of a solvent to the polyol premix. As a result, the outer skin is much thicker, including greater than about 100, 200, 500, and about 1500% thicker as compared to a polyurethane made without adding solvent to the polyol premix. In some embodiments, the polyurethane composite material made by the addition of solvent to the polyol premix may have an increase outer density skin, thus making the skin harder, where the skin is greater than about 50, 75 and about 150% harder as compared to a polyurethane made without adding the solvent to the polyol premix. Furthermore, some embodiments of the polyurethane composite material have an interior density that is less than between about 10 and about 50% as compared as compared to a polyurethane made without adding the solvent to the polyol.
Additional Components
The polyurethane composite materials can contain one or more compounds or polymers in addition to the foregoing components. Additional components or additives may be added to provide additional properties or characteristics to the composition or to modify existing properties (such as mechanical strength or heat deflection temperature) of the composition. For example, the polyurethane composite material may further include a heat stabilizer, an anti-oxidant, an ultraviolet absorbing agent, a light stabilizer, a flame retardant, a lubricant, a pigment and/or dye. One having ordinary skill in the art will appreciate that various additives may be added to the polymer compositions according to embodiments of the invention. Some of these additional additives are further described herein.
UV Light Stabilizers, Antioxidants, Pigments
Ultraviolet light stabilizers, such as UV absorbers, can be added to the polyurethane composite material prior to or during its formation. Hindered amine type stabilizers, and opaque pigments like carbon black powder, can greatly increase the light stability of plastics and coatings. In some embodiments, phenolic antioxidants are provided. These antioxidants provide increased UV protection, as well as thermal oxidation protection.
In some embodiments, the polyurethane composite material comprises one or more selected from the group consisting of light stabilizers and antioxidants. In combination, the light stabilizers and antioxidants provide a synergistic effect of reducing the detrimental effects of UV light as compared to either component used alone in the polyurethane composite material. According to certain embodiments, the effect is non-additive.
For example, in aromatic thermosetting polyurethanes, using 0.5 wt % Tinuvin 328 light absorber alone provides some resistance to UV, such as reduced yellowing, less chalking, and less embrittlement. Adding Irganox 1010 antioxidant at 0.5 wt % greatly improves the resistance to UV, and even using 0.2 wt % of each provides better stability than either of the stabilizers at 0.5 wt % alone.
Pigment or dye can be added to the polyol mixture or can be added at other points in the process. The pigment is optional, but can help make the composite material more commercially acceptable, more distinctive, and help to hide any scratches that might form in the surface of the material. Typical examples of pigments include iron oxide, typically added in amounts ranging from about 2 wt % to about 7 wt %, based on the total weight of the reaction mixture.
Surfactants and Catalysts
One or more catalysts are generally added to control the curing time of the polymer matrix (upon addition of the isocyanate), and these may be selected from among those known to initiate reaction between isocyanates and polyols, such as amine-containing catalysts, such as DABCO and tetramethylbutanediamine, tin-, mercury- and bismuth-containing catalysts. To increase uniformity and rapidity of cure, it may be desirable to add multiple catalysts, including a catalyst that provides overall curing via gelation, and another that provides rapid surface curing to form a skin and eliminate tackiness. For example, a liquid mixture of 1 part tin-containing catalyst to 10 parts amine-containing catalyst can be added in an amount greater than 0 wt % and below about 0.10 wt % (based on the total reaction mixture) or less, depending on the length of curing time desired. Too much catalyst can result in overcuring, which could cause buildup of cured material on the processing equipment, or too stiff a material which cannot be properly shaped, or scorching; in severe cases, this can lead to unsaleable product or fire. Curing times generally range from about 5 seconds to about 2 hours.
A surfactant may optionally be added to the polyol mixture to function as a wetting agent and assist in mixing of the inorganic particulate material. The surfactant also stabilizes and controls the size of bubbles formed during foaming (if a foamed product is desired) and passivates the surface of the inorganic particulates, so that the polymeric matrix covers and bonds to a higher surface area. Surfactants can be used in amounts below about 0.5 wt %, desirably about 0.3 wt %, based on the total weight of the mixture. Excess amount of surfactant can lead to excess water absorption, which can lead to freeze/thaw damage to the composite material. Silicone surfactants have been found to be suitable for use in the invention. Examples include DC-197 and DC-193 (silicone-based, Air Products), and other nonpolar and polar (anionic and cationic) products.
Other Additives
In some embodiments, the filled polyurethane composite material additionally comprises at least one coupling agent. Coupling agents and other surface treatments such as viscosity reducers or flow control agents can be added directly to the filler or fiber, and incorporated prior to, during, and after the mixing and reaction of the polyurethane composite material. In some embodiments, the polyurethane composite materials comprise pre-treated fillers and fibers.
In some embodiments, the coupling agents allow higher filler loadings of an inorganic filler such as fly ash. In embodiments, these ingredients may be used in small quantities. For example, the polyurethane composite material may comprises about 0.01 wt % to about 0.5 wt % of at least one coupling agent. In some of these embodiments, the polyurethane composite materials exhibit greater impact strength, as well as greater flexural modulus and strength, as compared to those materials without at least one coupling agent. Coupling agents reduce the viscosity of the resin/filler mixture. In some embodiments, coupling agents increase the wetting of the fibers and fillers by the resin components during the mixing the components.
In other embodiments, coupling agents reduce the need for colorants by improving the dispersion of the colorants, and the break up of colorant clumps. Thus, the polyurethane composite material which comprises coupling agents and a colorant may exhibit substantially uniform coloration throughout the polyurethane composite material.
Example in Table 5: The following flow control agents were tested in a urethane polyol with a high loading of filler, such that the combination would flow through a Zahn #5 cup viscometer. The polyol was Bayer Multranol 4035 polyether used at 70 g, with 30 g of two different fillers—tested separately. The polyol+filler were hand mixed and put into the Zahn Cup with the bottom port closed with tape. When the Zahn cup was full, the tape was removed and the time for the mixture to flow out of the Cup was measured. All tests at 65° F. (18° C.). The agents were: Air Products DABCO DC197 silicone-based surfactant, Kenrich Petrochemicals Ken-React LICA 38, and Ken-React KR 55 organo-titanates, Shin-Etsu Chemical KBM-403 organo-silane.
These tests show that even 0.1% of the flow control agent on the weight of the filler can markedly improve the flow of the mixture. This flow improvement allows higher levels of filler to be used in urethane mixtures, better wetting of the filler by the polyol, and more thorough mixing of all the components. The DC-197 surfactant works well, but only at much higher concentrations.
Ratios of the Components Used to Make the Polyurethane Composite Material
Variations in the ratio of the at least one polyol to the isocyanate have various changes on the overall polyurethane product and the process for making the polyurethane composites with high inorganic filler loads. High filler in such systems typically inhibit or physically block the reaction or action of the various polyurethane composite components, including the at least one polyol, the di- or polyisocyanate, the surfactants, flow modifiers, cell regulators and the catalysts. In addition, the heat that is released during the course of the exothermic reaction in forming the polyurethane composite is much higher in an unfilled polyurethane system. A larger isocyanate index gives higher temperature exotherms during the process of making the polyurethane composite material. By adding, 5 to 20 wt % excess, and more preferably 5 to 10 wt % excess, of the isocyanate to the otherwise chemically balanced at least one polyol that may comprise chain extenders with additional OH groups (thus, measuring the balance by the overall OH numbers).
Higher temperature exotherms result in more cross linking of the polyol and isocyanate, and/or a more complete reaction of the hydroxyl groups and isocyanate groups. In some embodiments, a higher isocyanate index also causes much higher cross link densities. In other embodiments, the higher isocyanate index provides a more “thermoset” type of polyurethane composite. In other embodiments, the higher isocyanate index provides a polyurethane with a more chemically resistant polyurethane composite material when exposed to chemicals. In some cases, these chemicals are solvents and water. In certain embodiments, the higher isocyanate index provides a polyurethane composite system with a higher heat distortion temperature. The heat distortion temperature or its effects may be determined by elevated temperature creep tests, standard ASTM heat distortion testing, surface hardness variations with increased temperature, for example, in an oven, and changes in mechanical properties at increasing temperature.
Representative suitable compositional ranges for synthetic lumber, in percent based on the total composite composition, are provided below:
At least one polyol: about 6 to about 28 wt %
Surfactant: about 0.2 to about 0.5 wt %
Skin forming catalyst about 0.002 to about 0.01 wt %
Gelation catalyst about 0.02 to about 0.1 wt %
Water 0 to about 0.5 wt %
Chopped fiberglass 0 to about 10 wt %
Pigments 0 to about 6 wt %
Inorganic particulates about 60 to about 85 wt %
Isocyanate about 6 to about 20 wt %
Axial tows 0 to about 6 wt %.
Additional components described herein can be added in various amounts. Such amount may be determined by persons having ordinary skill in the art.
Mixing and Reaction of the Components of the Polyurethane Composite Material
The polyurethane composite material can be prepared by mixing the various components described above including the isocyanate, the polyol, the catalyst, the inorganic filler, and various other additives. In some embodiments, one or more other additives may be mixed together with the components of the polyurethane composition. One or more component resins can be heated to melt prior to the mixing or the composition may be heated during the mixing. However, the mixing can occur when each components is in a solid, liquid, or dissolved state, or mixtures thereof. In one embodiment, the above components are mixed together all at once. Alternatively, one or more components are added individually. Formulating and mixing the components may be made by any method known to those persons having ordinary skill in the art, or those methods that may be later discovered. The mixing may occur in a pre-mixing state in a device such as a ribbon blender, followed by further mixing in a Henschel mixer, Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder, or a cokneader.
In some preferred embodiments, the polyurethane composite material can be prepared by mixing the polyols together (if multiple polyols are used), and then mixing them with various additives, such as catalysts, surfactants, and foaming agent, and then adding the inorganic particulate phase, then any reinforcing fiber, and finally the isocyanate. While mixing of some of the components can occur prior to extrusion, all of the components may alternatively be mixed in a mixer such as an extruder.
In one embodiment, it has been found that this order of blending results in the manufacture of polyurethane composite materials suitable for building material applications. Thus, it has been discovered that the order of mixing, as well as other reaction conditions may impact the appearance and properties of the resulting polyurethane composite material, and thus its commercial acceptability.
One particular embodiment relates to a method of producing a polymer matrix composite, by (1) mixing a first polyol and a second polyol with a catalyst, optional water, and optional surfactant; (2) optionally introducing reinforcing fibrous materials into the mixture; (3) introducing inorganic filler into the mixture; (4) introducing poly- or di-isocyanate into the mixture; and (5) allowing the exothermic reaction to proceed without forced cooling except to control runaway exotherms.
The process for producing the composite material may be operated in a batch, semibatch, or continuous manner. Mixing may be conducted using conventional mixers, such as Banbury type mixers, stirred tanks, and the like, or may be conducted in an extruder, such as a twin screw, co-rotating extruder. When an extruder is used, additional heating is generally not necessary, especially if liquid polyols are used. In addition, forced cooling is not generally required, except for minimal cooling to control excessive or runaway exotherms.
For example, a multi-zone extruder can be used, with polyols and additives introduced into the first zone, inorganic particulates introduced in the second zone, and chopped fibers, isocyanate, and pigments introduced in the fifth zone. A twin screw, co-rotating, extruder (e.g. 100 mm diameter, although the diameter can be varied substantially) can be used, with only water cooling (to maintain substantially near room temperature), and without extruder vacuum (except for ash dust). Liquid materials can be pumped into the extruder, while solids can be added by suitable hopper/screw feeder arrangements. Internal pressure build up in such an exemplary arrangement is not significant.
Although gelation occurs essentially immediately, complete curing can take as long as 48 hours, and it is therefore desirable to wait at least that long before assessing the mechanical properties of the composite, in order to allow both the composition and the properties to stabilize.
Extrusion
As discussed above, particular methods related to extruding polyurethane composite materials. One particular method includes extruding the polyurethane composite materials as described herein through an extruder having various segments and multiple screw elements
Referring to
In a first segment of the extruder, the at least one polyol may be introduced to the extruder. In some embodiments, the at least one polyol may include a blend of one or more polyols. Additionally, the at least one polyol may be blended with one or more of the catalyst, surfactants, blowing agents and other components described herein. In some embodiment, each components may be added individually or together. In some embodiments, the components are preblended prior to introduction to the extruder. As shown in
In a second segment of the extruder, inorganic filler material such as ash may be introduced to the extruder. The inorganic filler material is blended with the components from the first segment. As shown in
Components inputted in a first or second segment may be transferred to a third segment of the extruder by the screw. In a third segment of the extruder, previously inputted components may be mixed further by slotted screws. A third segment may also include lobal screws. In some embodiments, the mixing provides a substantially uniform mixture of one or more of least one polyol, at least one catalyst, a surfactant, an optional blowing agent, pigment, and filler. These components experience more shearing forces created by the slotted screw. The previous introduced components may then be further transferred toward the output end of the extruder. In some embodiments, the components are transferred to a fourth segment of the extruder. As shown in
In some embodiments, the isocyanate components may be introduced subsequent to the polyol component. As shown in
As shown in
In a sixth barrel segment or in the second mixing section, a reverse screw provides a substantial amount of mixing to the previous added components of the composite mixture. In some embodiments, substantial shearing is provided to the composite mixture. As a reverse screw has negative pitch, the components of the composite material may be block from being transferred through such a segment until sufficient shearing forces and pressure allow the mixture to pass through this segment. In some embodiments, the reverse screw is configured to block the mixture back to a subsequent segment or section. For example, the entire mixture may be blocked to one or more of the first segment, second segment, third segment, fourth segment, or fifth segment. In another embodiment, the components of the mixture are blocked to one or more of the first conveying section, second conveying section, or the first mixing section. Such shearing together with the exothermic reaction of the polyol and the isocyanate may require cooling in the segment or section.
Vents may be disposed on either side of the second mixing section. As large amounts of mixing may release entrained air in the one or more components of the polyurethane composite mixture, such air must be released. Additionally, gas produced by the blowing agent may be required to be released. In some embodiments, a vacuum may be used to remove the entrained air and/or gas from the blowing agent. In some embodiments, the removed air or gas results in the formation of a more dense and uniform polyurethane composite material.
In optional embodiments, fiber rovings may be added to the composite mixture in a subsequent segment. This segment may be found in a third conveying section. As shown in
In subsequent segments, the mixture may be further mixed and transported toward the output end of the extruder. Such subsequent segments may constitute a second or third mixing section, depending on the embodiment. For example, in an eighth segment, lobal screws may provide further mixing to the composite mixture. In addition, a reverse screw may be provided in this or subsequent segments to provide substantial mixing and/or shearing of the components of the composite mixture.
As mentioned above a mixing section adjacent to the output end of the extruder may include one or more reverse screws and lobal screws. In some embodiments, a reverse screw is in the last segment of the extruder. In some embodiments, the reverse screw is a reverse slotted screw. As enough shearing forces and/or pressure transfer the mixture past the reverse screw, the mixture is extruded through a die.
In some embodiments, the extruder has a L/D of about 10 to about 40. In some embodiments, the extruder has a L/D of about 10 to about 15. In some embodiments, the extruder has a L/D of about 20 to about 40. In some embodiments, the extruder has a L/D that is greater than about 24. In some embodiments, the extruder may operate from between about 200 to about 2000 rpm.
In accordance with some embodiments, foaming of the polyurethane composite materials occurs after the die. In some embodiments, some foaming and reaction of the composite mixture may occur prior to or during extrusion.
Other alternatives may be used when providing the mixed polyurethane composite material. For example the extruder may have more than or less than nine barrel segments. In some embodiments, certain types of screws can be replaced by a different type of screw. These variations should be apparent to a person having ordinary skill in the art.
Forming
In some embodiments, the process of forming the highly filled polyurethane composite material comprises providing the components of the polyurethane composite material, mixing the components together, extruding the components through a die, adding any other additional components after the extrusion, and forming a shaped article of the polyurethane composite material. As the polyurethane composite material exits the die, the composite material may be placed in a mold for post-extrusion curing and shaping. In one embodiment, the composite material is allowed to cure in a box or bucket.
In one embodiment the formation of the shaped articles comprises injecting the extruded polyurethane composite material in a mold cavity and curing the shaped article. However, some embodiments require that the extruded polyurethane composite material be placed in a mold cavity secured on all sides, and exerting pressure on the polyurethane composite material. In some of these embodiments, the polyurethane composite material will be foaming or will already be foamed. However, it is preferred that the material is placed under the pressure of the mold cavity prior to or at least during at least some foaming of the polyurethane composite material.
A shaped article can be made using the polyurethane composite materials according to the foregoing embodiments. In some embodiments, this article is molded into various shapes. In some embodiments, the polyurethane composite material is extruded, and then injected into a continuous production system. Suitable systems for forming the composite materials of some embodiments are described in U.S. patent application Ser. No. 10/764,013 filed Jan. 23, 2004 and entitled “CONTINUOUS FORMING SYSTEM UTILIZING UP TO SIX ENDLESS BELTS,” now published as U.S. Patent Application Publication No. 2005-0161855-A1, and U.S. patent application Ser. No. 11/165,071, filed Jun. 23, 2005, entitled “CONTINUOUS FORMING APPARATUS FOR THREE-DIMENSIONAL FOAMED PRODUCTS,” now published as U.S. Patent Application Publication No. 2005-0287238-A1, both of which are hereby incorporated by reference in their entireties.
The polyurethane composite material of certain embodiments may exert certain pressures on the walls of any mold, such as that found in the forming devices as described above. While the amount of pressure may vary according to the amount of foaming and gas production, it is preferred that such forming devices may exert or hold pressures by the mold cavity ranging from about 35 to about 75 psi. In some embodiments, the pressure is from about 45 to about 65 psi. In some embodiments, the pressure is about 50 psi. However, mold pressures in any embodiment of a method of making the polyurethane composite material can be higher than or less than the specified values. The exact pressure required in the formation of the desired shaped article depends on the density, color, size, shape, physical properties, and the mechanical properties of the article comprising the polyurethane composite material.
When foaming polyurethane is formed by belts into a product shape, the pressure that the belts exert on the foamed part is related to the resulting mechanical properties. For example, as the pressure of the foaming increases and the belt system can hold this pressure without the belts separating, then the product may have higher flexural strength, then if the belts allowed leaking, or pressure drop. In some embodiments, pressures about 50 to about 75 psi have been used to obtain high mechanical properties in the polyurethane composite material. In one example, an increase in the flexural strength of 50 psi results from the higher pressure in the belts, versus using a lower pressure.
In some embodiments, a shaped article comprising the polyurethane composite material as described herein is roofing material such as roof tile shingles, etc., siding material, carpet backing, synthetic lumber, building panels, scaffolding, cast molded products, decking materials, fencing materials, marine lumber, doors, door parts, moldings, sills, stone, masonry, brick products, post, signs, guard rails, retaining walls, park benches, tables, slats and railroad ties.
Other shaped articles may comprise a portion of which comprises the polyurethane composite material. In some embodiments, the polyurethane composite material is coated or molded on one side of an article. For example, the polyurethane composite material may be coated or molded onto one side of a flat or S-shaped clay roof tile, which has been cut thinner than normal, and laid on a conveyor belt, followed by extrusion of the polyurethane composite material onto at least a portion of the tile. Such portion may be shaped by a mold which is adapted to shape the polyurethane composite material deposited on the tile. For example, the forming unit may operate with two mold belts which are adapted to shape the polyurethane composite material on one side of the portion. In some embodiments, the composite material may provide backing to an article. In one embodiment, the composite material may be foamed sufficient to provide insulation to an article.
In some embodiments, the polyurethane composite material can reinforce an article. For example, by placing a coating or molding of the polyurethane composite material on a roof tile, the impact strength of the roof tile is increased. Thus one embodiment comprises a method of substantially reducing the fracture of an article by depositing the polyurethane composite on a solid surface article, shaping the composite on the solid surface article by methods described herein, and curing the composite on the solid surface article. Such method may produce a one or more of a reinforced, backed, or insulated article. Such article may also have increased physical and mechanical properties. Additionally, a reinforcing layer may be used to prevent water weeping, and increases the overall thickness of a solid surface article.
In some embodiments, the polyurethane composite material can bond directly to an article solid surface article such as a tile. Alternatively, an adhesive can be applied to the solid surface article and a shaped polyurethane composite article can be attached thereto. A solid surface article such as a tile may include at least one or more of cement, slate, granite, marble, and combinations thereof; and the polyurethane composite material as described in embodiments herein. Such tiles may be used as roofing or siding tiles.
In some embodiments, the composite material may be used as reinforcement of composite structural members including building materials such as doors, windows, furniture and cabinets and for well and concrete repair. In some embodiments, the composite material may be used to fill any unintended gaps, particularly to increase the strength of solid surface articles and/or structural components. Structural components may formed from a variety of materials such as wood, plastic, concrete and others, whereas the defect to be repaired or reinforced can appear as cuts, gaps, deep holes, cracks.
Optional Additional Mixing Process
One of the most difficult problems in forming polyurethane composite materials which have large amounts of filler is getting intimate mixing—blending the polyols and the isocyanate. In some embodiments, an ultrasound device may be used to cause better mixing of the various components of the polyurethane composite material. In these embodiments, the ultrasound mixing may also result in the enhanced mixing and/or wetting of the components. In some embodiments, the enhanced mixing and/or wetting allows a high concentration of filler, such as coal ash to be mixed with the polyurethane matrix, including about 40, 50, 60, 70, 80, and about 85 wt % of the inorganic filler.
In some embodiments, the ultrasound device produces an ultrasound of a certain frequency. In some embodiments, the frequency of the ultrasound device is varied during the mixing and/or extrusion process. In some embodiments, the components are mixed in a continuous mixer, such as an extruder, equipped with an ultrasound device. In some embodiments, an ultrasound device is attached to or is adjacent to the extruder and/or mixer. In other embodiments, an ultrasound device is attached to the die of the extruder. In other embodiments, the ultrasound device is placed in a port of the mixer. In further embodiments, an ultrasound device provides vibrations at the location where the isocyanate and polyol meet as the screw delivers the polyol to the isocyanate.
In addition, an ultrasound device may provide better mixing for the other components, such as blowing agents, surfactants, catalysts. In embodiments where additional components are added to the polyol prior to mixing the polyol with the isocyanate, the additional components are also exposed to ultrasound vibration. In some embodiments, an ash selected from fly ash, bottom ash, or combinations thereof, is mixed using an ultrasound device. In some embodiments, ultrasound vibrations breaks up filler and fiber bundles to allow more thorough wetting of these components to provide a polyurethane composite material with better mechanical properties, such as flexural modulus and flexural strength, as compared to polyurethane composite materials which are created without the use of ultrasound vibration. The wetting of fibers and fillers could also be increased by the use of ultrasound at or near the die of the extruder, thus forcing resin to coat the fibers and fillers better, and even breaking up fiber bundles and filler lumps. The sound frequency and intensity would be adjusted to give the best mixing, and what frequency is best for the urethane raw materials, may not be best for the filler and fibers.
Unless otherwise noted, all percentages and parts are by weight.
The skilled artisan will recognize the interchangeability of various features from different embodiments. Similarly, the various features and steps discussed above, as well as other known equivalents for each such feature or step, can be mixed and matched by one of ordinary skill in this art to perform compositions or methods in accordance with principles described herein. Although the invention has been disclosed in the context of certain embodiments and examples, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments to other alternative embodiments and/or uses and obvious modifications and equivalents thereof. Accordingly, the invention is not intended to be limited by the specific disclosures of embodiments herein. Rather, the scope of the present invention is to be interpreted with reference to the claims that follow.
This application is a continuation of U.S. patent application Ser. No. 13/687,987, filed Nov. 28, 2012, which is a continuation of U.S. patent application Ser. No. 13/170,932, filed Jun. 28, 2011, which is a continuation of U.S. patent application Ser. No. 12/710,472, filed on Feb. 23, 2010, which is a continuation of U.S. patent application Ser. No. 11/691,456, filed on Mar. 26, 2007, which claims the priority benefit of provisional applications 60/785,726, filed Mar. 24, 2006 and 60/785,749, filed Mar. 24, 2006. All of these documents are hereby incorporated by reference in their entireties.
| Number | Name | Date | Kind |
|---|---|---|---|
| 529535 | Smith | Nov 1894 | A |
| 529538 | Vaughn | Nov 1894 | A |
| 2526033 | Lyon | Oct 1950 | A |
| 2817875 | Harris et al. | Dec 1957 | A |
| 2983693 | Sievers | May 1961 | A |
| 3065500 | Berner | Nov 1962 | A |
| 3071297 | Lee | Jan 1963 | A |
| 3078512 | De Haven | Feb 1963 | A |
| 3223027 | Soda et al. | Dec 1965 | A |
| 3262151 | Oxel | Jul 1966 | A |
| 3269961 | Bruson et al. | Aug 1966 | A |
| 3308218 | Weigand et al. | Mar 1967 | A |
| 3466705 | Richie | Sep 1969 | A |
| 3528126 | Ernst et al. | Sep 1970 | A |
| 3566448 | Ernst | Mar 1971 | A |
| 3619268 | Robertson et al. | Nov 1971 | A |
| 3642964 | Rausch, Jr. et al. | Feb 1972 | A |
| 3644168 | Bonk et al. | Feb 1972 | A |
| 3698731 | Jost et al. | Oct 1972 | A |
| 3726624 | Schwarz | Apr 1973 | A |
| 3736081 | Yovanovich | May 1973 | A |
| 3738895 | Paymal | Jun 1973 | A |
| 3764247 | Garrett et al. | Oct 1973 | A |
| 3768937 | Haga et al. | Oct 1973 | A |
| 3774428 | Derry et al. | Nov 1973 | A |
| 3802582 | Brock | Apr 1974 | A |
| 3816043 | Snelling et al. | Jun 1974 | A |
| 3819574 | Brown et al. | Jun 1974 | A |
| 3824057 | Kornylak et al. | Jul 1974 | A |
| 3830776 | Carsion et al. | Aug 1974 | A |
| 3832429 | Charpentier | Aug 1974 | A |
| 3841390 | DiBenedetto et al. | Oct 1974 | A |
| 3843757 | Ehrenfreund et al. | Oct 1974 | A |
| 3852387 | Bortnick et al. | Dec 1974 | A |
| 3867494 | Rood et al. | Feb 1975 | A |
| 3878027 | Troutner | Apr 1975 | A |
| 3890077 | Holman | Jun 1975 | A |
| 3910179 | Troutner | Oct 1975 | A |
| 3917547 | Massey | Nov 1975 | A |
| 3917774 | Sagane et al. | Nov 1975 | A |
| 3928258 | Alexander | Dec 1975 | A |
| 3963679 | Ullrich et al. | Jun 1976 | A |
| 3981654 | Rood et al. | Sep 1976 | A |
| 3991005 | Wallace | Nov 1976 | A |
| 3999230 | Bruning et al. | Dec 1976 | A |
| 4005035 | Deaver | Jan 1977 | A |
| 4042314 | Bruning et al. | Aug 1977 | A |
| 4051742 | Johansson et al. | Oct 1977 | A |
| 4060579 | Schmitzer et al. | Nov 1977 | A |
| 4065410 | Schäfer et al. | Dec 1977 | A |
| 4073840 | Saidla | Feb 1978 | A |
| 4078032 | Wenner | Mar 1978 | A |
| 4092276 | Narayan | May 1978 | A |
| 4104094 | Peterson | Aug 1978 | A |
| 4107248 | Schlieckmann | Aug 1978 | A |
| 4120626 | Keller | Oct 1978 | A |
| 4127040 | Moore et al. | Nov 1978 | A |
| 4128369 | Kemerer et al. | Dec 1978 | A |
| 4137200 | Wood et al. | Jan 1979 | A |
| 4141862 | Raden | Feb 1979 | A |
| 4143759 | Paradis | Mar 1979 | A |
| 4149840 | Tippmann | Apr 1979 | A |
| 4153768 | Blount | May 1979 | A |
| 4160749 | Schneider et al. | Jul 1979 | A |
| 4163824 | Saidla | Aug 1979 | A |
| 4164439 | Coonrod | Aug 1979 | A |
| 4164526 | Clay et al. | Aug 1979 | A |
| 4165414 | Narayan et al. | Aug 1979 | A |
| 4180538 | Morikawa et al. | Dec 1979 | A |
| 4209605 | Hoy et al. | Jun 1980 | A |
| 4210572 | Herman et al. | Jul 1980 | A |
| 4214864 | Tabler | Jul 1980 | A |
| 4221877 | Cuscurida et al. | Sep 1980 | A |
| 4243755 | Marx et al. | Jan 1981 | A |
| 4247656 | Janssen | Jan 1981 | A |
| 4248975 | Satterly | Feb 1981 | A |
| 4251428 | Recker et al. | Feb 1981 | A |
| 4254002 | Sperling et al. | Mar 1981 | A |
| 4254176 | Müller et al. | Mar 1981 | A |
| 4256846 | Ohashi et al. | Mar 1981 | A |
| 4260538 | Iseler et al. | Apr 1981 | A |
| 4261946 | Goyert et al. | Apr 1981 | A |
| 4272377 | Gerlach et al. | Jun 1981 | A |
| 4275033 | Schulte et al. | Jun 1981 | A |
| 4276337 | Coonrod | Jun 1981 | A |
| 4282988 | Hulber, Jr. | Aug 1981 | A |
| 4284826 | Aelony | Aug 1981 | A |
| 4290248 | Kemerer et al. | Sep 1981 | A |
| 4300776 | Taubenmann | Nov 1981 | A |
| 4330494 | Iwata et al. | May 1982 | A |
| 4331726 | Cleary | May 1982 | A |
| 4338422 | Jackson, Jr. et al. | Jul 1982 | A |
| 4339366 | Blount | Jul 1982 | A |
| 4342847 | Goyert et al. | Aug 1982 | A |
| 4344873 | Wick | Aug 1982 | A |
| 4347281 | Futcher et al. | Aug 1982 | A |
| 4359359 | Gerlach et al. | Nov 1982 | A |
| 4359548 | Blount | Nov 1982 | A |
| 4366204 | Briggs | Dec 1982 | A |
| 4367259 | Fulmer et al. | Jan 1983 | A |
| 4376171 | Blount | Mar 1983 | A |
| 4381352 | McBrayer | Apr 1983 | A |
| 4382056 | Coonrod | May 1983 | A |
| 4383818 | Swannell | May 1983 | A |
| 4390581 | Cogswell et al. | Jun 1983 | A |
| 4395214 | Phipps et al. | Jul 1983 | A |
| 4396791 | Mazzoni | Aug 1983 | A |
| 4397983 | Hill et al. | Aug 1983 | A |
| 4412033 | LaBelle et al. | Oct 1983 | A |
| 4439548 | Weisman | Mar 1984 | A |
| 4450133 | Cafarelli | May 1984 | A |
| 4460737 | Evans et al. | Jul 1984 | A |
| 4465500 | Motsinger et al. | Aug 1984 | A |
| 4483727 | Eickman | Nov 1984 | A |
| 4489023 | Proksa | Dec 1984 | A |
| 4512942 | Babbin et al. | Apr 1985 | A |
| 4514162 | Schulz | Apr 1985 | A |
| 4532098 | Campbell et al. | Jul 1985 | A |
| 4540357 | Campbell et al. | Sep 1985 | A |
| 4568702 | Mascioli | Feb 1986 | A |
| 4576718 | Reischi et al. | Mar 1986 | A |
| 4581186 | Larson | Apr 1986 | A |
| 4595709 | Reischi | Jun 1986 | A |
| 4597927 | Zeitler et al. | Jul 1986 | A |
| 4600311 | Mourrier | Jul 1986 | A |
| 4604410 | Altenberg | Aug 1986 | A |
| 4649162 | Roche et al. | Mar 1987 | A |
| 4661533 | Stobby | Apr 1987 | A |
| 4677157 | Jacobs | Jun 1987 | A |
| 4680214 | Frisch et al. | Jul 1987 | A |
| 4714778 | Burgoyne, Jr. et al. | Dec 1987 | A |
| 4717027 | Laure et al. | Jan 1988 | A |
| 4780484 | Schubert et al. | Oct 1988 | A |
| 4780498 | Goerrissen et al. | Oct 1988 | A |
| 4795763 | Gluck et al. | Jan 1989 | A |
| 4802769 | Tanaka | Feb 1989 | A |
| 4826944 | Hoefer et al. | May 1989 | A |
| 4832183 | Lapeyre | May 1989 | A |
| 4835195 | Rayfield et al. | May 1989 | A |
| 4855184 | Klun et al. | Aug 1989 | A |
| 4892891 | Close | Jan 1990 | A |
| 4895352 | Stumpf | Jan 1990 | A |
| 4948859 | Echols et al. | Aug 1990 | A |
| 4995801 | Hehi | Feb 1991 | A |
| 5001165 | Canaday et al. | Mar 1991 | A |
| 5010112 | Glicksman et al. | Apr 1991 | A |
| 5028648 | Famili et al. | Jul 1991 | A |
| 5051222 | Marten et al. | Sep 1991 | A |
| 5053274 | Jonas | Oct 1991 | A |
| 5091436 | Frisch et al. | Feb 1992 | A |
| 5094798 | Hewitt | Mar 1992 | A |
| 5096993 | Smith et al. | Mar 1992 | A |
| 5102918 | Moriya | Apr 1992 | A |
| 5102969 | Scheffler et al. | Apr 1992 | A |
| 5114630 | Newman et al. | May 1992 | A |
| 5149722 | Soukup | Sep 1992 | A |
| 5149739 | Lee | Sep 1992 | A |
| 5159012 | Doesburg et al. | Oct 1992 | A |
| 5166301 | Jacobs | Nov 1992 | A |
| 5167899 | Jezic | Dec 1992 | A |
| 5185420 | Smith et al. | Feb 1993 | A |
| 5229138 | Carotti | Jul 1993 | A |
| 5252697 | Jacobs et al. | Oct 1993 | A |
| 5271699 | Barre et al. | Dec 1993 | A |
| 5296545 | Heise | Mar 1994 | A |
| 5300531 | Weaver | Apr 1994 | A |
| 5302634 | Mushovic | Apr 1994 | A |
| 5330341 | Kemerer et al. | Jul 1994 | A |
| 5331044 | Lausberg et al. | Jul 1994 | A |
| 5340300 | Saeki et al. | Aug 1994 | A |
| 5344490 | Roosen et al. | Sep 1994 | A |
| 5361945 | Johanson | Nov 1994 | A |
| 5369147 | Mushovic | Nov 1994 | A |
| 5375988 | Klahre | Dec 1994 | A |
| 5424013 | Lieberman | Jun 1995 | A |
| 5424014 | Glorioso et al. | Jun 1995 | A |
| 5432204 | Farkas | Jul 1995 | A |
| 5439711 | Vu et al. | Aug 1995 | A |
| 5453231 | Douglas | Sep 1995 | A |
| 5455312 | Heidingsfeld et al. | Oct 1995 | A |
| 5458477 | Kemerer et al. | Oct 1995 | A |
| 5491174 | Grier et al. | Feb 1996 | A |
| 5495640 | Mullet et al. | Mar 1996 | A |
| 5505599 | Kemerer et al. | Apr 1996 | A |
| 5508315 | Mushovic | Apr 1996 | A |
| 5522446 | Mullet et al. | Jun 1996 | A |
| 5527172 | Graham, Jr. | Jun 1996 | A |
| 5532065 | Gubitz et al. | Jul 1996 | A |
| 5536781 | Heidingsfeld et al. | Jul 1996 | A |
| 5554713 | Freeland | Sep 1996 | A |
| 5562141 | Mullet et al. | Oct 1996 | A |
| 5565497 | Godbey et al. | Oct 1996 | A |
| 5566740 | Mullet et al. | Oct 1996 | A |
| 5567791 | Brauer et al. | Oct 1996 | A |
| 5569713 | Lieberman | Oct 1996 | A |
| 5582840 | Pauw et al. | Dec 1996 | A |
| 5582849 | Lupke | Dec 1996 | A |
| 5604266 | Mushovic | Feb 1997 | A |
| 5611976 | Kiler et al. | Mar 1997 | A |
| 5621024 | Eberhardt et al. | Apr 1997 | A |
| 5631103 | Eschbach et al. | May 1997 | A |
| 5631319 | Reese et al. | May 1997 | A |
| 5643516 | Raza et al. | Jul 1997 | A |
| 5681915 | Lechner et al. | Oct 1997 | A |
| 5688890 | Ishiguro et al. | Nov 1997 | A |
| 5696205 | Muller et al. | Dec 1997 | A |
| 5700495 | Kemerer et al. | Dec 1997 | A |
| 5710231 | Fogg et al. | Jan 1998 | A |
| 5723506 | Glorioso et al. | Mar 1998 | A |
| 5728337 | Yoshikawa et al. | Mar 1998 | A |
| 5759695 | Primeaux, II | Jun 1998 | A |
| 5760133 | Heidingsfeld et al. | Jun 1998 | A |
| 5782283 | Kendall | Jul 1998 | A |
| 5783125 | Bastone et al. | Jul 1998 | A |
| 5783629 | Srinivasan et al. | Jul 1998 | A |
| 5795949 | Daute et al. | Aug 1998 | A |
| 5811506 | Slagel | Sep 1998 | A |
| 5817402 | Miyake et al. | Oct 1998 | A |
| 5836499 | Mullet et al. | Nov 1998 | A |
| 5844015 | Steilen et al. | Dec 1998 | A |
| 5908573 | Chiles et al. | Jun 1999 | A |
| 5908701 | Jennings et al. | Jun 1999 | A |
| 5929153 | Mori et al. | Jul 1999 | A |
| 5934352 | Morgan | Aug 1999 | A |
| 5945460 | Ekart et al. | Aug 1999 | A |
| 5952053 | Colby | Sep 1999 | A |
| 5962144 | Primeaux, II | Oct 1999 | A |
| 5981655 | Heidingsfeld et al. | Nov 1999 | A |
| 6000102 | Lychou | Dec 1999 | A |
| 2019269 | Mullet et al. | Feb 2000 | A |
| 6020387 | Downey et al. | Feb 2000 | A |
| 6040381 | Jennings et al. | Mar 2000 | A |
| 6051634 | Laas et al. | Apr 2000 | A |
| 6055781 | Johanson | May 2000 | A |
| 6062719 | Busby et al. | May 2000 | A |
| 6086802 | Levera et al. | Jul 2000 | A |
| 6096401 | Jenkines | Aug 2000 | A |
| 6103340 | Kubo et al. | Aug 2000 | A |
| 6107355 | Horn et al. | Aug 2000 | A |
| 6107433 | Petrovic et al. | Aug 2000 | A |
| 6120905 | Figovsky | Sep 2000 | A |
| 6136246 | Rauwendaal et al. | Oct 2000 | A |
| 6136870 | Triolo et al. | Oct 2000 | A |
| 6140381 | Rosthauser et al. | Oct 2000 | A |
| 6166109 | Spitler et al. | Dec 2000 | A |
| 6177232 | Melisaris et al. | Jan 2001 | B1 |
| 6180192 | Smith et al. | Jan 2001 | B1 |
| 6180686 | Kurth | Jan 2001 | B1 |
| RE37095 | Glorioso et al. | Mar 2001 | E |
| 6204312 | Taylor | Mar 2001 | B1 |
| 6211259 | Borden et al. | Apr 2001 | B1 |
| 6224797 | Franzen et al. | May 2001 | B1 |
| 6234777 | Sperry et al. | May 2001 | B1 |
| 6252031 | Tsutsumi et al. | Jun 2001 | B1 |
| 6257643 | Young | Jul 2001 | B1 |
| 6257644 | Young | Jul 2001 | B1 |
| 6258310 | Sardanopoli et al. | Jul 2001 | B1 |
| 6258917 | Slagel | Jul 2001 | B1 |
| 6264462 | Gallagher | Jul 2001 | B1 |
| 6284841 | Friesner | Sep 2001 | B1 |
| 6294637 | Braüer et al. | Sep 2001 | B1 |
| 6297321 | Onder et al. | Oct 2001 | B1 |
| 6309507 | Morikawa et al. | Oct 2001 | B1 |
| 6312244 | Levera et al. | Nov 2001 | B1 |
| 6321904 | Mitchell | Nov 2001 | B1 |
| 6329448 | Gutsche et al. | Dec 2001 | B1 |
| 6343924 | Klepsch | Feb 2002 | B1 |
| 6348514 | Calabrese et al. | Feb 2002 | B1 |
| 6383599 | Bell et al. | May 2002 | B1 |
| 6387504 | Mushovic | May 2002 | B1 |
| 6409949 | Tanaka et al. | Jun 2002 | B1 |
| 6429257 | Buxton et al. | Aug 2002 | B1 |
| 6432335 | Ladang et al. | Aug 2002 | B1 |
| 6433032 | Hamilton | Aug 2002 | B1 |
| 6433121 | Petrovic et al. | Aug 2002 | B1 |
| 6455605 | Giorgini et al. | Sep 2002 | B1 |
| 6455606 | Kaku et al. | Sep 2002 | B1 |
| 6458866 | Oppermann et al. | Oct 2002 | B1 |
| 6465569 | Kurth | Oct 2002 | B1 |
| 6467610 | MacLachlan | Oct 2002 | B1 |
| 6469667 | Fox et al. | Oct 2002 | B2 |
| 6485665 | Hermanutz et al. | Nov 2002 | B1 |
| 6486224 | Lin et al. | Nov 2002 | B2 |
| 6534617 | Batt et al. | Mar 2003 | B1 |
| 6541534 | Allen et al. | Apr 2003 | B2 |
| 6552660 | Lisowski | Apr 2003 | B1 |
| 6555199 | Jenkines | Apr 2003 | B1 |
| 6571935 | Campbell et al. | Jun 2003 | B1 |
| 6573309 | Reitenbach et al. | Jun 2003 | B1 |
| 6573354 | Petrovic et al. | Jun 2003 | B1 |
| 6578619 | Wright | Jun 2003 | B2 |
| 6579932 | Schipper et al. | Jun 2003 | B1 |
| 6604848 | Tanaka et al. | Aug 2003 | B2 |
| 6605343 | Motoi et al. | Aug 2003 | B1 |
| 6613823 | Battiste et al. | Sep 2003 | B1 |
| 6613827 | Lundgard et al. | Sep 2003 | B2 |
| 6616886 | Peterson et al. | Sep 2003 | B2 |
| 6617009 | Chen et al. | Sep 2003 | B1 |
| 6624244 | Kurth | Sep 2003 | B2 |
| 6641384 | Bosler et al. | Nov 2003 | B2 |
| 6649084 | Morikawa et al. | Nov 2003 | B2 |
| 6649667 | Clatty | Nov 2003 | B2 |
| 6686435 | Petrovic et al. | Feb 2004 | B1 |
| 6695902 | Hemmings et al. | Feb 2004 | B2 |
| 6706774 | Münzenberger et al. | Mar 2004 | B2 |
| 6767399 | Peev et al. | Jul 2004 | B2 |
| 6769220 | Friesner | Aug 2004 | B2 |
| 6832430 | Ogawa et al. | Dec 2004 | B1 |
| 6849676 | Shibano et al. | Feb 2005 | B1 |
| 6864296 | Kurth | Mar 2005 | B2 |
| 6867239 | Kurth | Mar 2005 | B2 |
| 6871457 | Quintero-Flores et al. | Mar 2005 | B2 |
| 6881763 | Kurth | Apr 2005 | B2 |
| 6881764 | Doesburg et al. | Apr 2005 | B2 |
| 6903156 | Müller et al. | Jun 2005 | B2 |
| 6908573 | Hossan | Jun 2005 | B2 |
| 6916863 | Hemmings et al. | Jul 2005 | B2 |
| 6962636 | Kurth et al. | Nov 2005 | B2 |
| 6971495 | Hedrick et al. | Dec 2005 | B2 |
| 6979477 | Kurth et al. | Dec 2005 | B2 |
| 6979704 | Mayer et al. | Dec 2005 | B1 |
| 6989123 | Lee et al. | Jan 2006 | B2 |
| 6997346 | Landers et al. | Feb 2006 | B2 |
| 7063877 | Kurth et al. | Jun 2006 | B2 |
| 7132459 | Buchel | Nov 2006 | B1 |
| 7160976 | Lühmann et al. | Jan 2007 | B2 |
| 7188992 | Mattingly, Jr. | Mar 2007 | B2 |
| 7196124 | Parker et al. | Mar 2007 | B2 |
| 7211206 | Brown et al. | May 2007 | B2 |
| 7267288 | Wheeler, Jr. et al. | Sep 2007 | B2 |
| 7316559 | Taylor | Jan 2008 | B2 |
| 7491351 | Taylor et al. | Feb 2009 | B2 |
| 7651645 | Taylor | Jan 2010 | B2 |
| 7763341 | Brown | Jul 2010 | B2 |
| 7794224 | Butteriss | Sep 2010 | B2 |
| 7794817 | Brown | Sep 2010 | B2 |
| 20010009683 | Kitahama et al. | Jul 2001 | A1 |
| 20020034598 | Bonk et al. | Mar 2002 | A1 |
| 20020040071 | Lin et al. | Apr 2002 | A1 |
| 20020045048 | Bonk et al. | Apr 2002 | A1 |
| 20020048643 | Bonk et al. | Apr 2002 | A1 |
| 20020086913 | Roels et al. | Jul 2002 | A1 |
| 20020098362 | Mushovic | Jul 2002 | A1 |
| 20020171164 | Halterbaum et al. | Nov 2002 | A1 |
| 20020192456 | Mashburn et al. | Dec 2002 | A1 |
| 20030004232 | Ruede | Jan 2003 | A1 |
| 20030021915 | Rohatgi et al. | Jan 2003 | A1 |
| 20030065045 | Falke et al. | Apr 2003 | A1 |
| 20030083394 | Clatty | May 2003 | A1 |
| 20030090016 | Petrovic et al. | May 2003 | A1 |
| 20030143910 | Mashburn et al. | Jul 2003 | A1 |
| 20030158365 | Brauer et al. | Aug 2003 | A1 |
| 20030232933 | Lagneaux et al. | Dec 2003 | A1 |
| 20040048055 | Branca | Mar 2004 | A1 |
| 20040049002 | Andrews et al. | Mar 2004 | A1 |
| 20040121161 | Shugert et al. | Jun 2004 | A1 |
| 20040144287 | Tardif et al. | Jul 2004 | A1 |
| 20040198900 | Madaj | Oct 2004 | A1 |
| 20040266993 | Evans | Dec 2004 | A1 |
| 20050011159 | Standal et al. | Jan 2005 | A1 |
| 20050031578 | Deslauriers et al. | Feb 2005 | A1 |
| 20050079339 | Riddle | Apr 2005 | A1 |
| 20050131092 | Kurth et al. | Jun 2005 | A1 |
| 20050131093 | Kurth et al. | Jun 2005 | A1 |
| 20050161855 | Brown et al. | Jul 2005 | A1 |
| 20050163969 | Brown | Jul 2005 | A1 |
| 20050171243 | Hemmings et al. | Aug 2005 | A1 |
| 20050182228 | Kurth | Aug 2005 | A1 |
| 20050222303 | Cernohous | Oct 2005 | A1 |
| 20050260351 | Kurth et al. | Nov 2005 | A1 |
| 20050281999 | Hoffman et al. | Dec 2005 | A1 |
| 20050287238 | Taylor | Dec 2005 | A1 |
| 20060014891 | Yang et al. | Jan 2006 | A1 |
| 20060041155 | Casper | Feb 2006 | A1 |
| 20060041156 | Casper et al. | Feb 2006 | A1 |
| 20060045899 | Sarangapani | Mar 2006 | A1 |
| 20060071369 | Butteriss | Apr 2006 | A1 |
| 20060105145 | Brown | May 2006 | A1 |
| 20060115625 | Brown | Jun 2006 | A1 |
| 20060186571 | Brown | Aug 2006 | A1 |
| 20060186572 | Brown | Aug 2006 | A1 |
| 20060217517 | Daly | Sep 2006 | A1 |
| 20060270747 | Griggs | Nov 2006 | A1 |
| 20060273486 | Taylor et al. | Dec 2006 | A1 |
| 20070027227 | Shutov | Feb 2007 | A1 |
| 20070037953 | Geiger et al. | Feb 2007 | A1 |
| 20070052128 | Taylor | Mar 2007 | A1 |
| 20070066697 | Gilder et al. | Mar 2007 | A1 |
| 20070222105 | Brown | Sep 2007 | A1 |
| 20070222106 | Brown | Sep 2007 | A1 |
| 20070225391 | Brown | Sep 2007 | A1 |
| 20070225419 | Brown | Sep 2007 | A1 |
| 20080029925 | Brown | Feb 2008 | A1 |
| 20080132611 | Brown | Jun 2008 | A1 |
| 20090295021 | Brown | Dec 2009 | A1 |
| 20100025882 | Taylor et al. | Feb 2010 | A1 |
| 20100201014 | Taylor | Aug 2010 | A1 |
| 20100230852 | Brown | Sep 2010 | A1 |
| 20100264559 | Brown | Oct 2010 | A1 |
| 20100292397 | Brown | Nov 2010 | A1 |
| 20100296361 | Brown | Nov 2010 | A1 |
| Number | Date | Country |
|---|---|---|
| 2037130 | Jan 2006 | CA |
| 1251596 | Apr 2000 | CN |
| 1052991 | May 2000 | CN |
| 1926282 | Mar 2007 | CN |
| 2351844 | Apr 1975 | DE |
| 1152306 | May 1969 | GB |
| 1246940 | Sep 1971 | GB |
| 2347933 | Sep 2000 | GB |
| 51-89597 | Aug 1976 | JP |
| 55-80456 | Jun 1980 | JP |
| 355080456 | Jun 1980 | JP |
| 58-132533 | Aug 1983 | JP |
| 63-022819 | Jan 1988 | JP |
| 63-202408 | Aug 1988 | JP |
| 05-285941 | Nov 1993 | JP |
| 06-322819 | Nov 1994 | JP |
| 07-076395 | Mar 1995 | JP |
| 07-313941 | Dec 1995 | JP |
| 08-188634 | Jul 1996 | JP |
| 11-171960 | Jun 1999 | JP |
| 2001-326361 | Nov 2001 | JP |
| 2004-131654 | Apr 2004 | JP |
| 2005-138567 | Jun 2005 | JP |
| 2002-0086327 | Nov 2002 | KR |
| 226301 | Mar 1990 | NZ |
| 124156 | Dec 2008 | SG |
| 8103026 | Oct 1981 | WO |
| 8705541 | Sep 1987 | WO |
| 9100304 | Jan 1991 | WO |
| 9207892 | May 1992 | WO |
| 9319110 | Sep 1993 | WO |
| 9324549 | Dec 1993 | WO |
| 9425529 | Nov 1994 | WO |
| 9427697 | Dec 1994 | WO |
| 9711114 | Mar 1997 | WO |
| 9744373 | Nov 1997 | WO |
| 9808893 | Mar 1998 | WO |
| 9939891 | Aug 1999 | WO |
| 0017249 | Mar 2000 | WO |
| 0172863 | Oct 2001 | WO |
| 0201530 | Jan 2002 | WO |
| 2004078900 | Sep 2004 | WO |
| 2004113248 | Dec 2004 | WO |
| 2005053938 | Jun 2005 | WO |
| 2005056267 | Jun 2005 | WO |
| 2005072187 | Aug 2005 | WO |
| 2005072188 | Aug 2005 | WO |
| 2005094255 | Oct 2005 | WO |
| 2005123798 | Dec 2005 | WO |
| 2006012149 | Feb 2006 | WO |
| 2006137672 | Dec 2006 | WO |
| 2007112104 | Oct 2007 | WO |
| 2007112105 | Oct 2007 | WO |
| Entry |
|---|
| Bledzki, Andrzej K., et al., Impact Properties of Natural Fiber-Reinforced Epoxy Foams, Journal of Cellular Plastics, vol. 35, Nov. 1999, pp. 550-562. |
| Brydson, “Plastics Materials,” Butterworth-Heinermann, 7th ed., (1999), pp. 778-809. |
| Certel, G., Editor: Polyurethane Handbook 2nd Edition: 1994: pp. 136-137, 182-183, 252-253; Carl Hanser Verlag, Munich. |
| Chawla, K. K., Excerpts from “Composite Materials: Science and Engineering”, pp. 89-92, Spring Verlag, New York, NY (1987). |
| Elias, H., Excerpts from “An Introduction to Polymer Science”, 1997, pp. 408-409, VCH Publishers, Inc., New York, NY. |
| Frisch, K.C., et al., Hybrid IPN-Foam Composites, Cellular Polymers, Papers from a Three-day International Conference organized by Rapra Technology Limited, Mar. 20-22, 1991. |
| Guo et al., “Polyols and Polyurethanes from Hydroformylation of Soybean Oil,” Journal of Polymers and the Environment 10(1-2):49-52 (Apr. 2002). |
| Guo et al., “Rigid Urethane Foams from a Soy Polyol-Dod Hybrid,” USDA Agricultural Research Service, http://ars.usda.gov/research/publications/publications.htm?SEQ—NO—115=145249 (May 9, 2003). |
| Ionescu, “Chemistry and Technology of Polyols for Polyurethanes,” Rapra Technology Ltd,. (2005), pp. 535-550. |
| Klempner, D., ed., et al., Excerpts from Handbook of Polymeric Foams and Foam Technology, 2d ed., 2004, pp. 121-124, 126, 128, 129, Hanser Publishers, Munich. |
| Krishnamurthi, B, et al., Nano- and Micro-Fillers for Polyurethane Foams: Effect on Density and Mechanical Properties, Symposium, Sep. 30-Oct. 3, 2001, pp. 239-244, Polyurethanes Expo 2001, Columbus, OH. |
| Nosker, Thomas, J., et al., Fiber Orientation and Creation of Structural Plastic Lumber, Plastics Engineering, Jun. 1999, pp. 53-56. |
| Oertel, G., ed., Polyurethane Handbook Second Edition, pp. 136, 182-83, 252-53; Carl Hanser, Verlag, Munich (1994). |
| Petrovic et al., “Industrial Oil Products Program,” AOCS Archives (2007). |
| Pollack, “Soy vs. Petro Polyols a Life-Cycle Comparison,” Omni Tech International, Ltd. (Feb. 2004). |
| Randall et al., Excerpts from “The polyurethanes book”, pp. 1, 166-167, 210-213, 229-231, 263-264, Dunholm Publicity Ltd., United Kingdom (2002). |
| Shutov, F.A., Excerpts from Integral/Structural Polymer Foams: Technology, Properties and Applications, 1986, Pages including preface, 3-4, 8-9, 13, 23-25, 131-134, 153-158, 167, 171, 176-179, 256. |
| Woods, G., Excerpts from “The ICI Polyurethanes Book”, 1987, pp. 119-120, 127, 135-140, 158-159, The Netherlands. |
| Wypych, G., Excerpts from “Fillers”, 1993, pp. 4, 48, 57, ChemTech Publishing, Ontario Canada. |
| “Achieving a Wood Grain Finish Effect,” dated Dec. 11, 2003, http://www.sculpt.com/technogtes/woodgrainfinsih.htm. |
| Bayer AG, Bayferrox Iron Oxide Pigments: Manufacturing, Properties and Application Recommendations (date note available). |
| Bayer Material Science Product Information, ARCOL LG-56, Sep. 2003. |
| Bayer Material Science Product Information, MULTRANOL 3900, Jan. 2006. |
| Bayer Material Science Product Information, MULTRANOL 4035, Jan. 1997. |
| Bayer Material Science, Product Index—Polyurethane Raw Materials Prepolymers and Systems (2006). |
| Cleated Belt Puller, http://www.esi-extrusion.com/cbpuller.htm, Aug. 5, 2002. |
| Custom Downstream Systems, Excerpts from Catalog, 6 pages including cover page (date not available). |
| Deposition of Wade Brown vol. 1, pp. 1-212 (Nov. 17, 2005)—Redacted. |
| Deposition of Wade Brown vol. 2, pp. 1-256 (Nov. 18, 2005)—Redacted. |
| Deposition of Wade Brown vol. 3, pp. 1-302 (Nov. 21, 2005). |
| Deposition of Edward J. Butteriss vol. 1, pp. 1-501 (Dec. 16, 2005). |
| Deposition of Edward J. Butteriss vol. 2, pp. 1-195 (Dec. 28, 2005). |
| Deposition of Thomas E. Jurgensen, pp. 1-407 (Jan. 9, 2006). |
| Deposition of Daniel Klempner, pp. 1-120 (Jan. 6, 2006)—Redacted. |
| Deposition of Fyodor Shutov vol. 1, pp. 1-312 (Dec. 15, 2005)—Redacted. |
| Deposition of Fyodor Shutov vol. 2, pp. 1-182 (Dec. 28, 2005). |
| Deposition of John R. Taylor, pp. 1-388 (Dec. 7, 2005)—Redacted. |
| Deposition of Zachary R. Taylor vol. 1, pp. 1-221 (Dec. 29, 2005)—Redacted. |
| Deposition of Zachary R. Taylor vol. 2, pp. 1-285 (Jan. 5, 2006)—Redacted. |
| Energy Efficient Building Products from Waste Materials, Development and Demonstration Project, Proposal, Sep. 10, 1999, NYS Energy Research & Development Authority. |
| Foamed Recyclables: New Process Efficiently Transforms Solid Waste into Synthetic Building Materials, Jan. 2002, United States Department of Energy, Office of Industrial Technologies, Inventions and Innovations Program. |
| McMaster-Carr, Excerpts from Catalog, pp. 1052-1053 (date not available). |
| National Center for Environmental Research and Quality Assurance, Office of Research and Development, U.S. Environmental Protection Agency, Abstract of “The Use of Multi-Component Waste Products for Use in Roofing Materials,” May 9, 1998. |
| OSi Specialties, “Fomrez Tin Catalysts”, 3 pages (date not available). |
| “PVC Double Wall Corrugated Pipe Manufacturing Plant”, Korea Association of Machinery Industry (date not available). |
| RDN Manufacturing Co., Inc., 140, 148 & 160 Belt Pullers, http://www.rdnmfg.com/products/pull140—160.htm, Aug. 5, 2002. |
| Soyol Polyols and Systems Product Descriptions, www.soyoyl.com (26 pates) downloaded Apr. 26, 2007. |
| Summary of Opinions, Daniel Klempner, pp. 1-11 (Jan. 4, 2006). |
| Tenibac-Graphion, Inc., Texturing Technologists, Brochure, Oct. 1, 1997. |
| Urethane Soy Systems Company, Material Safety Data Sheet, SoyTherm 50 A-side, pp. 1-8, Jul. 29, 2005. |
| Urethane Soy Systems Company, Material Safety Data Sheet, SoyTherm 50 B-side, pp. 1-8, Jul. 29, 2005. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 10/764,012, filed Jan. 23, 2004, entitled Filled Polymer Composite and Synthetic Building Material Compositions. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 10/764,013, filed Jan. 23, 2004 entitled Continuous Forming System Utilizing Up to Six Endless Belts. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 10/952,186, filed Sep. 28, 2004, entitled Apparatus for the Continuous Production of Plastic Composites. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 11/065,171, filed Jun. 23, 2005, entitled Continuous Forming Apparatus for Three-Dimensional Foam Products. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 11/317,494, filed Dec. 22, 2005, entitled Filled Polymer Composite and Synthetic Building Material Compositions. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 11/317,958, filed Dec. 22, 2005, entitled Filled Polymer Composite and Synthetic Building Material Compositions. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 11/407,416, filed Apr. 20, 2006, entitled Filled Polymer Composite and Synthetic Building Material Compositions. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 11/407,661, filed Apr. 20, 2006, entitled Filled Polymer Composite and Synthetic Building Material Compositions. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 11/417,385, filed May 4, 2006, entitled Continuous Forming System Utilizing Up to Six Endless Belts. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 11/593,316, filed Nov. 6, 2006, entitled Method for Molding Three-Dimensional Foam Products Using a Continuous Forming Apparatus. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 11/691,438, filed Mar. 26, 2007, entitled Polyurethane Composite Materials. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 11/691,446, filed Mar. 26, 2007, entitled Extrusion of Polyurethane Composite Materials. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 11/691,449, filed Mar. 26, 2007, entitled Polyurethane Composite Materials. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 11/691,451, filed Mar. 26, 2007, entitiled Polyurethane Composite Materials. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 11/691,456, filed Mar. 26, 2007, entitled Extrusion of Polyurethane Composite Materials. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 11/841,901, filed Aug. 20, 2007, entitled Filled Polymer Composite and Synthetic Building Material Compositions. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 12/361,488, filed Jan. 28, 2009, entitled Continuous Forming System Utilizing Up to Six Endless Belts. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 12/473,138, filed May 27, 2009, entitled Extrusion of Polyurethane Composite Materials. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 12/692,241, filed Jan. 22, 2010, entitled Method for Molding Three-Dimensional Foam Products Using a Continuous Forming Apparatus. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 12/710,472, filed Feb. 23, 2010, entitled Extrusion of Polyurethane Composite Materials. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 12/727,365, filed Mar. 19, 2010, entitled Filled Polymer Composite and Synthetic Building Material Compositions. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 12/786,206, filed May 24, 2010, entitled Extrusion of Polyurethane Composite Materials. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 12/843,265, filed Jul. 26, 2010, entitled Filled Polymer Composite and Synthetic Building Material Compositions. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 13/010,646, filed Jan. 20, 2011, entitled Extrusion of Polyurethane Composite Materials. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 13/112,670, filed May 20, 2011, entitled Continuous Forming System Utilizing Up to Six Endless Belts. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 12/786,203, filed May 24, 2010, entitled Extrusion of Polyurethane Composite Materials. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 13/152,190, filed Jun. 2, 2011, entitled Extrusion of Polyurethane Composite Materials. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 13/155,066, filed Jun. 7, 2011, entitled Extrusion of Polyurethane Composite Materials. |
| Past and present office actions, amendments, arguments, and other relevant documents or materials in the file history of co-pending U.S. Appl. No. 13/170,932, filed Jun. 28, 2011, entitled Extrusion of Polyurethane Composite Materials. |
| Co-pending U.S. Appl. No. 11/417,385, filed May 4, 2006, titled Continuous Forming System Utilizing Up to Six Endless Belts, and assigned to the assignee of this application. |
| Co-pending U.S. Appl. No. 11/593,316, filed Nov. 6, 2006, titled Method for Molding Three-Dimensional Foam Products Using a Continuous Forming Apparatus, and assigned to the assignee of this application. |
| Office Action issued in U.S. Appl. No. 10/764,012 on Nov. 15, 2005. |
| Office Action issued in U.S. Appl. No. 10/764,012 on May 31, 2006. |
| Supplemental Information Disclosure Statement filed in U.S. Appl. No. 10/764,012 on Apr. 19, 2007. |
| Supplemental Information Disclosure Statement filed in U.S. Appl. No. 10/764,012 on Apr. 23, 2007. |
| Final Office Action issued in U.S. Appl. No. 10/764,012 on Jul. 31, 2007. |
| Office Action issued in U.S. Appl. No. 10/764,012 on Jan. 7, 2008. |
| Final Office Action issued in U.S. Appl. No. 10/764,012 on Jan. 13, 2009. |
| Office Action issued in U.S. Appl. No. 10/764,012 on Aug. 20, 2009. |
| Notice of Allowance issued in U.S. Appl. No. 10/764,012 on Apr. 21, 2010. |
| Office Action issued in U.S. Appl. No. 10/764,013 on Dec. 5, 2005. |
| Office Action issued in U.S. Appl. No. 10/764,013 on Jun. 7, 2006. |
| Office Action issued in U.S. Appl. No. 10/952,186 on Oct. 2, 2008. |
| Final Office Action issued in U.S. Appl. No. 10/952,186 on Apr. 16, 2009. |
| Office Action issued in U.S. Appl. No. 10/952,186 on Dec. 10, 2009. |
| Notice of Allowance issued in U.S. Appl. No. 10/952,186 on May 5, 2010. |
| Office Action issued in U.S. Appl. No. 11/165,071 on Aug. 7, 2006. |
| Notice of Allowance issued in U.S. Appl. No. 11/165,071 on Apr. 5, 2007. |
| Supplemental Information Disclosure Statement filed in U.S. Appl. No. 11/165,071 on Apr. 19, 2007. |
| Supplemental Information Disclosure Statement filed in U.S. Appl. No. 11/165,071 on Apr. 23, 2007. |
| Notice of Allowance issued in U.S. Appl. No. 11/165,071 on Aug. 16, 2007. |
| Office Action issued in U.S. Appl. No. 11/317,494 on Mar. 26, 2009. |
| Office Action issued in U.S. Appl. No. 11/317,494 on Sep. 21, 2009. |
| Notice of Allowance issued in U.S. Appl. No. 11/317,494 on May 6, 2010. |
| Notice of Allowance issued in U.S. Appl. No. 11/317,494 on Aug. 6, 2010. |
| Office Action issued in U.S. Appl. No. 11/317,958 on Oct. 6, 2008. |
| Final Office Action issued in U.S. Appl. No. 11/317,598 on May 28, 2009. |
| Office Action issued in U.S. Appl. No. 11/317,598 on Dec. 21, 2009. |
| Office Action issued in U.S. Appl. No. 11/407,416 on Nov. 7, 2008. |
| Office Action issued in U.S. Appl. No. 11/407,416 on Aug. 20, 2009. |
| Final Office Action issued in U.S. Appl. No. 11/407,416 on May 25, 2010. |
| Notice of Allowance issued in U.S. Appl. No. 11/407,416 on Apr. 4, 2011. |
| Office Action issued in U.S. Appl. No. 11/407,661 on Nov. 7, 2008. |
| Office Action issued in U.S. Appl. No. 11/407,661 on Aug. 20, 2009. |
| Final Office Action issued in U.S. Appl. No. 11/407,661 on May 27, 2010. |
| Notice of Allowance issued in U.S. Appl. No. 11/407,661 on Mar. 29, 2011. |
| Office Action issued in U.S. Appl. No. 11/417,385 on Aug. 24, 2007. |
| Final Office Action issued in U.S. Appl. No. 11/417,385 on Jul. 11, 2008. |
| Notice of Allowance issued in U.S. Appl. No. 11/417,385 on Oct. 8, 2008. |
| Office Action issued in U.S. Appl. No. 11/593,316 on Jun. 3, 2008. |
| Final Office Action issued in U.S. Appl. No. 11/593,316 on Feb. 5, 2009. |
| Notice of Allowance issued in U.S. Appl. No. 11/593,316 on Sep. 10, 2009. |
| Office Action issued in U.S. Appl. No. 11/691,438 on Jun. 10, 2009. |
| Final Office Action issued in U.S. Appl. No. 11/691,438 on Jun. 11, 2010. |
| Office Action issued in U.S. Appl. No. 11/691,438 on Feb. 18, 2011. |
| Office Action issued in U.S. Appl. No. 11/691,446 on Jul. 23, 2009. |
| Final Office Action issued in U.S. Appl. No. 11/691,446 on Feb. 24, 2010. |
| Office Action issued in U.S. Appl. No. 11/691,449 on Jun. 30, 2008. |
| Office Action issued in U.S. Appl. No. 11/691,449 on Apr. 17, 2009. |
| Office Action issued in U.S. Appl. No. 11/691,449 on Dec. 30, 2009. |
| Final Office Action issued in U.S. Appl. No. 11/691,449 on Jul. 23, 2010. |
| Office Action issued in U.S. Appl. No. 11/691,449 on Feb. 24, 2011. |
| Office Action issued in U.S. Appl. No. 11/691,449 on Nov. 9, 2011. |
| Winkler, Non-Final Rejection of U.S. Appl. No. 11/691,451, Jun. 27, 2008. |
| Office Action issued in U.S. Appl. No. 11/691,451 on Jul. 27, 2008. |
| Final Office Action issued in U.S. Appl. No. 11/691,451 on May 12, 2009. |
| Office Action issued in U.S. Appl. No. 11/691,451 on Dec. 30, 2009. |
| Office Action issued in U.S. Appl. No. 11/691,451 on Feb. 4, 2011. |
| Office Action issued in U.S. Appl. No. 11/691,456 on Sep. 23, 2009. |
| Office Action issued in U.S. Appl. No. 11/841,901 on Jul. 9, 2009. |
| Final Office Action issued in U.S. Appl. No. 11/841,901 on Mar. 17, 2010. |
| Office Action issued in U.S. Appl. No. 12/361,488 on Jun. 30, 2010. |
| Final Office Action issued in U.S. Appl. No. 12/361,488 on Nov. 23, 2010. |
| Office Action issued in U.S. Appl. No. 12/473,138 on Dec. 8, 2010. |
| Office Action issued in U.S. Appl. No. 12/692,241 on Aug. 5, 2011. |
| Office Action issued in U.S. Appl. No. 12/710,472 on Dec. 29, 2010. |
| Office Action issued in U.S. Appl. No. 12/727,365 on Oct. 21, 2010. |
| Final Office Action issued in U.S. Appl. No. 12/727,365 on Jul. 12, 2011. |
| Office Action issued in U.S. Appl. No. 12/786,206 on Dec. 3, 2010. |
| Office Action issued in U.S. Appl. No. 12/843,265 on Nov. 26, 2010. |
| Final Office Action issued in U.S. Appl. No. 12/843,265 on Jul. 18, 2011. |
| International Preliminary Report on Patentability and Written Opinion of the International Searching Authority issued in International Application No. PCT/US2005/001569 on Aug. 3, 2006. |
| International Search Report for PCT/US05/01570 mailed on Jan. 25, 2006. |
| International Preliminary Report on Patentability and Written Opinion of the International Searching Authority for PCT/US05/01570, mailed Aug. 3, 2006. |
| International Search Report and Written Opinion of the International Searching Authority for International Application No. PCT/US05/22076, mailed Aug. 29, 2006. |
| International Preliminary Report on Patentability and Written Opinion of the International Searching Authority for International Application No. PCT/US05/22076, mailed Jan. 11, 2007. |
| International Search Report and Written Opinion of the International Searching Authority for International Application No. PCT/US2007/007468 mailed Nov. 19, 2007. |
| International Preliminary Report on Patentability and Written Opinion of the International Searching Authority for International Application No. PCT/US2007/007468 mailed Oct. 9, 2008. |
| Partial International Search Report issued in International Application No. PCT/US2007/007470 on Nov. 19, 2007. |
| International Search Report and Written Opinion of the International Searching Authority for International Application No. PCT/US2007/007470, mailed Feb. 26, 2008. |
| International Preliminary Report on Patentability and Written Opinion of the International Searching Authority for International Application No. PCT/US2007/007470, mailed Oct. 9, 2008. |
| Office Action issued in Australian Application No. 2005208713 on May 6, 2009. |
| Office Action issued in Australian Application No. 2005208714 on Jun. 26, 2009. |
| Office Action issued in Australian Application No. 2005267399 on Oct. 6, 2009. |
| Office Action issued in Chinese Application No. 20058000030186 on Apr. 4, 2008. |
| Office Action issued in Chinese Application No. 20058000030186 on Oct. 31, 2008. |
| Office Action issued in Chinese Application No. 20058000030186 on Apr. 24, 2009. |
| Notification of Decision of Rejection issued in Chinese Application No. 20058000030186 on Sep. 11, 2009. |
| Office Action issued in Chinese Application No. 2005800206677 on Aug. 7, 2009. |
| Office Action issued in Chinese Application No. 2005800206677 on Mar. 3, 2011. |
| European Supplemental Search Report for European Application No. 05711595.8 dated Jan. 22, 2009. |
| Office Action issued in European Application No. 05711595.8 on May 11, 2009. |
| European Search Report for EP Patent App. No. 05762651.7 dated Feb. 24, 2009. |
| European Search Report for EP Patent App. No. 05762651.7 dated Mar. 11, 2009. |
| Office Action issued in European Application No. 05762651.7 on Oct. 2, 2009. |
| Extended European Search Report and European Search Opinion for European Patent Application No. 11165942.1 dated Jul. 21, 2011. |
| Office Action issued in Indonesian Application No. W-00 2006 02034 on May 26, 2008. |
| Office Action issued in Japanese Application No. 2006-551203 on Nov. 29, 2010. |
| Office Action issued in New Zealand Application No. 548626 on Feb. 23, 2009. |
| Office Action issued in New Zealand Application No. 548628 on Jan. 26, 2009. |
| Written Opinion issued by the Austrian Patent Office on Jul. 31, 2007 in Singapore Application No. 200604927-4. |
| Examination Report issued by the Austrian Patent Office on Jun. 20, 2008 in Singapore Application No. 200604927-4. |
| Number | Date | Country | |
|---|---|---|---|
| 20140155504 A1 | Jun 2014 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60785749 | Mar 2006 | US | |
| 60785726 | Mar 2006 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13687987 | Nov 2012 | US |
| Child | 14180805 | US | |
| Parent | 13170932 | Jun 2011 | US |
| Child | 13687987 | US | |
| Parent | 12710472 | Feb 2010 | US |
| Child | 13170932 | US | |
| Parent | 11691456 | Mar 2007 | US |
| Child | 12710472 | US |
