WO2013064901A1

WO2013064901A1 - A composite article

Info

Publication number: WO2013064901A1
Application number: PCT/IB2012/002724
Authority: WO
Inventors: David R. Phelps; Brian Hyduk
Original assignee: Basf Se
Priority date: 2011-11-02
Filing date: 2012-11-02
Publication date: 2013-05-10

Abstract

A composite article (10) includes a first layer (12), a second layer (14), and a third layer (16). The first layer (12) includes a polymeric material and has a show surface (18) and a reinforcing surface (20) opposite from the show surface (18). The second layer (14) abuts the reinforcing surface (20) of the first layer (12) and comprises a spray applied rigid polyurethane foam substantially free of reinforcing fillers. The third layer (16) abuts the second layer (14) opposite the first layer (12) and comprises a spray applied rigid polyurethane elastomer substantially free of reinforcing fillers.

Description

A COMPOSITE ARTICLE

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 61/554,535, filed on November 2nd, 2011, which is incorporated herewith by reference in its entirety.

FIELD OF THE INVENTION

[0002] The present invention generally relates to a composite article and more specifically to a composite article including: a first layer comprising a polymeric material; a second layer comprising a spray applied rigid polyurethane foam; and a third layer comprising a spray applied rigid polyurethane elastomer. The present invention also relates to a method of forming the composite article.

DESCRIPTION OF THE RELATED ART

[0003] Composite articles are useful as sanitary ware articles including sinks, bathtubs, and showers. Conventional composite articles generally include a reinforcing substrate to provide structural integrity and an aesthetically pleasing show layer disposed on the reinforcing substrate. For example, a first type of conventional composite articles, such as "claw foot" bathtubs, generally include a reinforcing substrate comprising cast iron and a show layer comprising porcelain disposed on the reinforcing substrate. Although this type of article is traditionally known for having excellent rigidity and strength, these articles also include materials which are both heavy and expensive. Accordingly, substitute materials have been considered to reduce both weight and cost of such articles.

[0004] A second type of conventional composite article comprises thermoplastics, elastomers, foams, and combinations thereof. Similar to the first type of conventional articles described above, the second type of conventional composite articles still include a show layer having a show surface for aesthetic appeal. However, because the show layer is generally selected for aesthetic appeal rather than physical properties, the show layer generally lacks structural integrity. Accordingly, a sanitary ware article comprising only a show layer would lack those physical properties required in sanitary ware articles such as rigidity and strength. A sanitary article comprising only a show layer is generally susceptible to damage, e.g. cracking, and is not suitable for independent use. Therefore, these types of articles generally include a reinforcing layer to improve structural integrity.

[0005] Generally, the reinforcing layer is formed from materials which will reinforce the show material and increase rigidity and strength of the composite article. The reinforcing materials comprise an elastomer and are applied to the show material opposite the show surface thereby forming a reinforcing layer. This type of conventional composite article also includes an insulating layer, e.g. foam, abutting the reinforcing layer opposite the show layer to insulate and reduce noise during use of the composite article. Although this second type of article including elastomers and foams is lighter and less expensive than the first type of article formed from cast iron and porcelain, these second types of article can still lack the requisite rigidity and strength required for use as sanitary ware articles.

[0006] Attempts to improve the physical properties of the second type articles include increasing the thickness of the reinforcing and/or insulating layers, or increasing the number of reinforcing and/or insulating layers. However, these techniques result in composite articles which are heavy and undesirably thick. Therefore, these articles are more difficult to transport and/or install. Other attempts to improve the overall physical properties of conventional composite articles include reversing the order of the reinforcing and insulating layers, such that the resulting composite article includes an insulating layer abutting the show material opposite the show surface and a reinforcing layer abutting the insulating layer opposite the show layer. However, these composite articles require compounding each of the reinforcing and insulating layers with reinforcing filler. Use of reinforcing fillers increase material costs and creates additional processing steps thereby increasing production time and the overall cost associated with such articles.

[0007] Despite various efforts and techniques using different materials such as foams, elastomers, reinforcing fillers, and combinations thereof, to form composite materials for sanitary ware articles, concerns remain regarding the rigidity, strength, overall thickness, ease of transportation and installation, and overall cost of the composite materials, especially for use as sanitary ware articles. Accordingly, there remains an opportunity to provide improved composite articles and methods of making the same.

SUMMARY OF THE INVENTION AND ADVANTAGES

[0008] The present invention provides a composite article. The composite article includes a first layer, a second layer, and a third layer. The first layer comprises a polymeric material and has a show surface and a reinforcing surface opposite from the show surface. The second layer abuts the reinforcing surface and comprises a spray applied rigid polyurethane foam substantially free of reinforcing fillers. The third layer abuts the second layer opposite the first layer and comprises a spray applied rigid polyurethane elastomer substantially free of reinforcing fillers. [0009] The present invention also provides a method of forming the composite article. The second layer is formed from a first reaction mixture which is substantially free of reinforcing fillers and comprises a first isocyanate and a first isocyanate-reactive component. The third layer is formed from a second reaction mixture which is substantially free of reinforcing fillers and comprises a second isocyanate and a second isocyanate-reactive component. The method of forming the composite article includes the step of applying the first reaction mixture to the reinforcing surface of the first layer to form the second layer and applying the second reaction mixture to the second layer opposite the first layer to form the third layer. The second and third layers are cured to form the composite article.

[0010] The composite articles of this invention have excellent rigidity and strength therefore resisting deformation. Additionally, the composite articles are generally thinner, and therefore lighter, than conventional composite articles. The composite articles are useful for sanitary ware articles.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Other advantages of the present invention will be readily appreciated, as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawing wherein:

[0012] Figure 1 is a cross-sectional side view of a composite article including first, second, and third layers. Figure 1 is not drawn to scale.

DETAILED DESCRIPTION OF THE INVENTION

[0013] Referring to Figure 1, a composite article is shown generally at 10. Overall, the composite article 10 is thin yet still exhibits excellent rigidity and strength relative to conventional composite articles. Accordingly, the composite article 10 is suitable for use in a variety of sanitary ware applications including sinks, bathtubs, showers, etc. The composite article 10 is not limited to only these applications. The present invention also provides a method of forming the composite article 10, which is described further below.

[0014] The composite article 10 includes a first layer 12, a second layer 14, and a third layer 16. The first layer 12 comprises a polymeric material. The second layer 14 comprises a spray applied rigid polyurethane foam substantially free of reinforcing fillers. The second layer 14, i.e., polyurethane foam 14, is generally formed from a first reaction mixture also substantially free of reinforcing fillers. The third layer 16 comprises a spray applied rigid polyurethane elastomer substantially free of reinforcing fillers. The third layer 16, i.e., polyurethane elastomer 16, is generally formed from a second reaction mixture also substantially free of reinforcing fillers. Each of the layers 12, 14, 16 and reactions mixtures are described in greater detail below.

[0015] The terminology "substantially free", as used herein in reference to reinforcing fillers, refers to a sufficiently low amount of reinforcing fillers. Typically, the amount of reinforcing fillers that are present in each or the first and second reaction mixtures is less than 1, alternatively less than 0.5, alternatively less than 0.1, and alternatively approaching or equal to zero (0), percent by weight, each based on the total weight of the first and second reaction mixtures, respectively. Likewise, the amount of reinforcing fillers that are typically present in each of the second and third layers 14, 16 is less than 1, alternatively less than 0.5, alternatively less than 0.1, and alternatively approaching or equal to zero (0), percent by weight, each based on the total weight of each of the second and third layers 14, 16, respectively. In certain embodiments, each of the second and third layers 14, 16 is completely free of reinforcing filler.

[0016] Inclusion of reinforcing fillers in the first or second reaction mixtures would materially alter the first and second reaction mixtures, and therefore, the second or third layers 14, 16 of the composite article 10. Therefore, inclusion of reinforcing fillers would materially alter the composite article 10 overall. More specifically, fillers, including reinforcing fillers, typically increase the hygroscopic properties of composite articles which include the fillers. It is not suitable to have hygroscopic composite articles for use in a variety of sanitary ware applications including sinks, bathtubs, and showers, where moisture is often to always present. Reinforcing fillers are described further below.

[0017] The first layer 12 typically comprises a polymeric material and has a show surface 18 and a reinforcing surface 20 opposite from the show surface 18. Suitable examples of polymeric materials include, but are not limited to thermoplastic and thermosetting polymers. Particularly suitable polymeric materials for forming the first layer 12 are acrylonitrile butadiene styrene (ABS), acrylic resin/ ABS co-extrusions, and styrenated polyester resins. In certain embodiments, the first layer 12 is formed from a high impact polystyrene sheet (HIPS).

[0018] The first layer 12 may have any shape including (or mimicking) a shape of a sink, a bathtub, a shower, or any other type of sanitary ware article. Typically, the first layer 12 has an average thickness of from about 0.003 to about 0.006, alternatively from about 0.0035 to about 0.0055, and alternatively from about 0.004 to about 0.005, inches. Thickness of the first layer 12 may be uniform or may vary across the first layer 12. For example, different portions of the first layer 12 may have different thicknesses as compared to one another.

[0019] The second layer 14 typically abuts the reinforcing surface 20 of the first layer 12. In one embodiment, the second layer 14 abuts and is disposed over at least a portion of the reinforcing surface 20. Typically, the second layer 14 is coupled and/or bonded to a majority or an entirety of the reinforcing surface 20 of the first layer 12.

[0020] The second layer 14 comprises a spray applied rigid polyurethane foam substantially free of reinforcing fillers. More specifically, the spray applied rigid polyurethane foam is substantially free of reinforcing fillers including carbon, fibers, and metals. More specific examples of conventional reinforcing fillers include carbon fibers, glass fibers, nylon fibers, microspheres, and mineral fillers, such as calcium carbonate, barium sulfate, etc. Even more specifically, the spray applied rigid polyurethane foam is substantially free of transition metals of the periodic table including iron, e.g. cast iron reinforcing filler. In one embodiment, the second layer 14 consists essentially of the spray applied rigid polyurethane foam. In another embodiment, the second layer 14 consists of the spray applied rigid polyurethane foam.

[0021] Typically, the rigid polyurethane foam is formed from the first reaction mixture including a first isocyanate and a first isocyanate-reactive component. The first isocyanate may include any isocyanate known in the art including isocyanates, polyisocyanates, biurets of isocyanates and polyisocyanates, isocyanurates of isocyanates and polyisocyanates, and combinations thereof. The first isocyanate may also include an isocyanate selected from the group of aromatic isocyanates.

[0022] The first isocyanate may have any % NCO content and any viscosity. In certain embodiments, the first isocyanate has an NCO content of from 25% to 35%. In various embodiments, the first isocyanate has a viscosity of 200 cps, measured at 25°C, in accordance with ASTM D 4889.

[0023] If the first isocyanate includes an aromatic isocyanate, the aromatic isocyanate may correspond to the formula R'(NCO)_z wherein R' is a polyvalent organic radical which is aromatic and z is an integer that corresponds to the valence of R'. Typically, z is at least two. If the first isocyanate includes the aromatic isocyanate, the first isocyanate may include, but is not limited to, the tetramethylxylylene diisocyanate (TMXDI), 1,4-diisocyanatobenzene, 1,3-diisocyanato-oxylene, l,3-diisocyanato-/?-xylene, 1,3-diisocyanato-m-xylene, 2,4- diisocyanato-l-chlorobenzene, 2,4-diisocyanato-l-nitro-benzene, 2,5-diisocyanato-l- nitrobenzene, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, l-methoxy-2,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'- diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, triisocyanates such as 4,4',4"-triphenylmethane triisocyanate polymethylene polyphenylene polyisocyanate and 2,4,6-toluene triisocyanate, tetraisocyanates such as 4,4'-dimethyl-2,2'- 5,5'-diphenylmethane tetraisocyanate, toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, corresponding isomeric mixtures thereof, and combinations thereof. Alternatively, the aromatic isocyanate may include a triisocyanate product of m-TMXDI and 1,1,1-trimethylolpropane, a reaction product of toluene diisocyanate and 1,1,1-trimethyolpropane, and combinations thereof.

[0024] Examples of commercially available products suitable as the first isocyanate include Elastopor® products and Lupranate® products, which are commercially available from BASF Corporation of Florham Park, NJ. In specific embodiments, the first isocyanate is selected from Elastopor® P1001U, Lupranate® M20, and combinations thereof.

[0025] The first isocyanate, or rigid polyurethane foam in general, may also include an additive selected from the group of chain extenders, anti-foaming agents, processing additives, plasticizers, chain terminators, surface-active agents, adhesion promoters, flame retardants, anti- oxidants, water scavengers, fumed silicas, dyes, ultraviolet light stabilizers, non-reinforcing fillers, thixotropic agents, silicones, amines, catalysts, blowing agents, surfactants, cross-linking agents, inert diluents, water, and combinations thereof. The additive may be included in the first isocyanate in any amount.

[0026] Typically, the first isocyanate-reactive component includes a first polyol. The first polyol may include one or more polyols. The first polyol includes one or more OH functional groups, typically at least two OH functional groups. Typically, the first polyol is selected from the group of polyether polyols, polyester polyols, polyether/ester polyols, and combinations thereof; however, it is to be appreciated that other polyols may also be included. In certain embodiments, the first polyol has a number average molecular weight of from about 300 to about 400, alternatively from about 300 to about 350, and alternatively from about 310 to about 330, g/mol. In various embodiments, the first polyol has a hydroxyl number of from about 400 to about 500, alternatively from about 425 to about 475, and alternatively from about 435 to about 455, mg KOH/g. In certain embodiments, the first polyol has a functionality of form about 2 to about 4, alternatively from about 2.5 to about 3.5, and alternatively of from about 2.9 to about 3.2.

[0027] Examples of commercially available products suitable as the first polyol include Elastopor® products, which are commercially available from BASF Corporation. In specific embodiments, the first polyol is Elastopor® H 11711R RESIN.

[0028] Typically, the second layer 14 has a density of from about 2 to about 10, alternatively from about 5 to 8, and alternatively from about 6 to 7, lbs/ft . Additionally, the second layer 14 typically has an adhesion to the first layer 12 of from about 80 to about 120 and alternatively from about 90 to about 110, psi, as measured in accordance with ASTM D1623.

[0029] The second layer 14 typically has an average thickness of from about 0.1 to about 0.5, alternatively from about 0.2 to about 0.4, and alternatively from about 0.25 to about 0.375, inches. Thickness of the second layer 14 may be uniform or may vary across the second layer 14. For example, different portions of the second layer 14 may have different thicknesses as compared to one another.

[0030] The third layer 16 typically abuts the second layer 14 opposite the first layer 12. In one embodiment, the third layer 16 abuts and is disposed over at least a portion of the second layer 14. Typically, the third layer 16 is coupled and/or bonded to a majority or an entirety of the second layer 14.

[0031] The third layer 16 comprises a spray applied rigid polyurethane elastomer substantially free of reinforcing fillers. More specifically, the spray applied rigid polyurethane elastomer is substantially free of reinforcing fillers including carbon, fibers, and metals. Even more specifically, the spray applied rigid polyurethane elastomer is substantially free of transition metals of the periodic table including iron, e.g. cast iron reinforcing filler. In one embodiment, the third layer 16 consists essentially of the spray applied rigid polyurethane elastomer. In another embodiment, the third layer 16 consists of the spray applied rigid polyurethane elastomer.

[0032] Typically, the rigid polyurethane elastomer is the reaction product of a second isocyanate and a second isocyanate-reactive component. In one embodiment, the second isocyanate is selected from one or more of the suitable examples of the first isocyanate exemplified above. Like the first isocyanate exemplified above, the second isocyanate may have any % NCO content and any viscosity. Typically, the second isocyanate has a viscosity of from 300 to 500 and alternatively from 350 to 450, cps measured at 25°C, in accordance with ASTM D 2196.

[0033] Examples of commercially available products suitable as the second isocyanate include Elastofoam® products, which are commercially available from BASF Corporation. In specific embodiments, the second isocyanate is Elastofoam® I3070T.

[0034] The second isocyanate, or rigid polyurethane elastomer in general, may also include an additive selected from the group of suitable examples of additives exemplified above. The additive may be included in the second isocyanate in any amount.

[0035] Typically, the second isocyanate -reactive component includes a second polyol. In one embodiment, the second polyol is selected from one or more of the suitable examples of the first polyol exemplified above. In certain embodiments, the second polyol has a number average molecular weight of from about 410 to about 510, alternatively from about 440 to about 490, and alternatively from about 455 to about 475, g/mol. In various embodiment, the second polyol has a hydroxyl number of from about 365 to about 465, alternatively from about 390 to about 440, and alternatively from about 405 to about 425, mg KOH/g. In various embodiments, the polyol has a functionality of form about 2.5 to about 4.5, alternatively from about 3 to about 4, and alternatively of from about 3.3 to about 3.6.

[0036] Examples of commercially available products suitable as the second polyol include Elastocast® products, which are commercially available from BASF Corporation. In specific embodiments, the second polyol is Elastocast® S 72181R RESIN.

[0037] Typically, the third layer 16 has a density of from about 30 to about 75, alternatively from about 40 to about 65, and alternatively from about 45 to about 60, lbs/ft . Typically, the third layer has a tensile strength of from about 4,000 to about 6,000, alternatively from about 4,500 to about 5,000, and alternatively from about 4,600 to about 4,800, psi, as measured in accordance with ASTM D412. The third layer typically has an elongation of from about 1 to about 25, alternatively from about 5 to about 20, and alternatively from about 5 to about 15, percent, as measured in accordance with ASTM D412. Typically, the third layer 16 has a flexural strength of from about 5,000 to about 8,000, alternatively from about 6,000 to about 7,250, and alternatively 6,600 to 6,900, psi, as measured in accordance with ASTM D790. The third layer 16 typically has a flexural modulus of from about 200,000 to about 250,000, alternatively from about 220,000 to about 240,000, and alternatively from about 230,000 to about 235,000, psi, as measured in accordance with ASTM D790. Typically, the third layer 16 has a Shore D hardness, instant and after five seconds, of from about 50 to about 80, alternatively from about 55 to about 75, and alternatively from about 60 to about 70. Shore D hardness can be determined via ASTM D2240. The third layer 16 typically has a notched izod of from about 0.1 to about 0.9, alternatively from about 0.2 to about 0.7, and alternatively from about 0.4 to about 0.5, ft-lb/in, as measured in accordance with ASTM D256. Typically, the third layer 16 typically has an adhesion to the second layer 14 of from about 80 to about 120 and alternatively from about 90 to about 110, psi, as measured in accordance with ASTM D4541.

[0038] The third layer 16 typically has an average thickness of from about 0.01 to about 0.1, alternatively from about 0.02 to about 0.08, and alternatively from about 0.04 to about 0.06, inches. Thickness of the third layer 16 may be uniform or may vary across the third layer 16. For example, different portions of the third layer 16 may have different thicknesses as compared to one another.

[0039] As introduced above, the composite article 10 has excellent rigidity and strength. Accordingly, the composite article 10 is resistant to damage, e.g. cracking, has reduced weight, and is both easy to transport and install. Further, sanitary ware articles comprising the composite article 10, e.g. a bathtub, may define an increased interior volume yet occupy an overall volume comparable or equal to conventional composite articles.

[0040] Without being bound to or limited by any particular theory, it is believed that layering the composite article 10 such that the second layer 14 abuts the first layer 12 with the third layer 16 abutting the second layer 14 results in a composite article 10 that efficiently distributes applied force, even more so than conventional composite articles. Because the layering of the composite article 10 distributes applied force so efficiently, less material is required in the second and third layers 14, 16, to provide the composite article 10 with excellent physical properties. This contrasts with conventional composite articles which typically rely on increasing the thickness of layers, increasing the number of layers, and/or compounding the layers with reinforcing fillers to improve physical properties. Stated differently, the layering of the composite article 10 achieves excellent physical properties without requiring thicker and/or additional reinforcing layers or reinforcing/insulating layers compounded with reinforcing fillers, typical of conventional composite articles.

Method of Forming the Composite Article

[0041] As first introduced above, the present invention also provides the method of forming the composite article 10. The method includes the steps of applying the first reaction mixture to the reinforcing surface 20 of the first layer 12 to form the second layer 14, and applying the second reaction mixture to the second layer 14 opposite the first layer 12 to form the third layer 16.

[0042] In certain embodiments, the method of forming the composite article 10 includes the step of forming the first layer 12. In these embodiments, the first layer 12 is typically formed via melt processing. Suitable examples of melt processing include injection molding, extrusion, compression molding, and vacuum forming.

[0043] In further embodiments, the method of forming the composite article 10 includes preparing the reinforcing surface 20 of the first layer 12 via a mechanical or chemical process to receive the first reaction mixture. The step of preparing the reinforcing surface 20 may include cleaning, applying an abrasive, and/or applying an adhesive to the reinforcing surface 20.

[0044] The first and second reaction mixtures may be prepared and applied in any manner known in the art. In various embodiments, the steps of applying the first and second reaction mixtures are each further defined as spraying the first and second reaction mixtures. In certain embodiments, the step of applying the second reaction mixture to the second layer 14 is further defined as applying the second reaction mixture wet-on-wet onto the second layer 14. Said another way, the second reaction mixture can be applied to the second layer 14 to form the third layer 16 before the second layer 14 has reached a final cure state.

[0045] The method may further include the step (or steps) of curing the second and third layers 14, 16 to form the composite article 10. In one embodiment, the first layer 12 is cured before the step of applying the second reaction mixture. In another embodiment, the step of curing the second and third layers 14, 16 is further defined as curing the second and third layers 14, 16 simultaneously. Typically, the second and third layers 14, 16 are cured at ambient temperatures. In one embodiment, the second and third layers 14, 16 are cured at a temperature of from about 20° to about 25° C for an amount of time of from about 1 to about 120, alternatively from about 5 to about 90, and alternatively from about 5 to about 65, minutes.

[0046] It is to be understood that the appended claims are not limited to express and particular compounds, compositions, or methods described in the detailed description, which may vary between particular embodiments which fall within the scope of the appended claims. With respect to any Markush groups relied upon herein for describing particular features or aspects of various embodiments, it is to be appreciated that different, special, and/or unexpected results may be obtained from each member of the respective Markush group independent from all other Markush members. Each member of a Markush group may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims.

[0047] It is also to be understood that any ranges and subranges relied upon in describing various embodiments of the present invention independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein. One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on. As just one example, a range "of from 0.1 to 0.9" may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims. In addition, with respect to the language which defines or modifies a range, such as "at least," "greater than," "less than," "no more than," and the like, it is to be understood that such language includes subranges and/or an upper or lower limit. As another example, a range of "at least 10" inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims. Finally, an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims. For example, a range "of from 1 to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1, which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

[0048] The present invention has been described herein in an illustrative manner, and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. Many modifications and variations of the present invention are possible in light of the above teachings. The present invention may be practiced otherwise than as specifically described within the scope of the appended claims. The subject matter of all combinations of independent and dependent claims, both singly and multiply dependent, is herein expressly contemplated.

Claims

CLAIMS What is claimed is:

1. A composite article comprising:

a first layer comprising a polymeric material and having a show surface and a reinforcing surface opposite from said show surface;

a second layer abutting said reinforcing surface and comprising a spray applied rigid polyurethane foam substantially free of reinforcing fillers; and

a third layer abutting said second layer opposite said first layer and comprising a spray applied rigid polyurethane elastomer substantially free of reinforcing fillers.

2. A composite article as set forth in claim 1 wherein said polymeric material is further defined as acrylonitrile butadiene styrene (ABS).

3. A composite article as set forth in claim 1 or 2, wherein said first layer has an average thickness of from about 30 to about 60 thousands of an inch (or about 0.7 to about 1.5 millimeters).

4. A composite article as set forth in any one of claims 1 through 3, wherein said rigid polyurethane foam of said second layer is the reaction product of an aromatic isocyanate and a first isocyanate-reactive component.

5. A composite article as set forth in any one of claims 1 through 4, wherein said second layer has a density of from about 5 to about 8 lbs/ft 3 (or about 80 to about 128 kg/m 3 ).

6. A composite article as set forth in any one of claims 1 through 5, wherein said second layer has an adhesion to said first layer of from about 90 to about 110 psi (or about 620 to about 760 kPa) as measured according to ASTM D1623.

7. A composite article as set forth in any one of claims 1 through 6, wherein said rigid polyurethane elastomer of said third layer is the reaction product of an aromatic isocyanate and a second isocyanate-reactive component.

8. A composite article as set forth in any one of claims 1 through 7, wherein said third layer has a density of from about 45 to about 60 lbs/ft 3 (or about 720 to about 960 kg/m 3 ).

9. A composite article as set forth in any one of claims 1 through 8, wherein said third layer has a tensile strength of from about 4,500 to about 5,000 psi (or about 30,000 to about 35,000 kPa) as measured according to ASTM D412.

10. A composite article as set forth in any one of claims 1 through 9, wherein said third layer has an elongation of from about 5 to about 15 percent as measured according to ASTM D412.

11. A composite article as set forth in any one of claims 1 through 10, wherein said third layer has a flexural modulus of from about 230,000 to about 235,000 psi (or about 1,500 to about 1,600 MPa) as measured according to ASTM D790.

12. A composite article as set forth in any one of claims 1 through 11, wherein said third layer has a Shore D hardness after five seconds of about 60 to about 70.

13. A composite article as set forth in any one of claims 1 through 12, wherein each of said second and third layers is completely free of reinforcing filler.

14. A method of forming a composite article including a first layer comprising a polymeric material and having a show surface and a reinforcing surface opposite from the show surface; a second layer abutting the reinforcing surface and formed from a first reaction mixture which is substantially free of reinforcing fillers and comprises a first isocyanate and a first isocyanate-reactive component; and a third layer abutting the second layer opposite the first layer formed from a second reaction mixture which is substantially free of reinforcing fillers and comprises a second isocyanate and a second isocyanate-reactive component; said method comprising the steps of:

applying the first reaction mixture to the reinforcing surface of the first layer to form a second layer;

applying the second reaction mixture to the second layer opposite the first layer to form a third layer; and

curing the second and third layers to form the composite article.

15. A method as set forth in claim 14 wherein the steps of applying are further defined as spraying.

16. A method as set forth in claim 14 or 15, wherein the step of applying the second reaction mixture to the second layer is further defined as applying the second reaction mixture wet-on- wet onto the second layer.

17. A method as set forth in any one of claims 14 through 16, wherein the step of curing the second and third layers is further defined as curing the second and third layers simultaneously.

18. A method as set forth in any one of claims 14 through 17, wherein the second layer is a rigid polyurethane foam substantially free of reinforcing fillers.

19. A method as set forth in any one of claims 14 through 18, wherein the third layer is a rigid polyurethane elastomer substantially free of reinforcing fillers.

20. A method as set forth in any one of claims 14 through 19, wherein each of the second and third layers is completely free of reinforcing filler.