WO2008070064A2

WO2008070064A2 - A composite article and method of making the same

Info

Publication number: WO2008070064A2
Application number: PCT/US2007/024816
Authority: WO
Inventors: David R. Phelps; Herbert L. Harmon
Original assignee: Basf Aktiengesellschaft
Priority date: 2006-12-05
Filing date: 2007-12-04
Publication date: 2008-06-12
Also published as: WO2008070064A3; CA2665314A1

Abstract

A composite article (10) for protecting a substrate comprises a first elastomeric layer (16) that is a show surface of the composite article (10). The first elastomeric layer (16) comprises the reaction product of first isocyanate and first isocyanate-reactive components. At least one of the first components is aliphatic. The composite article (10) further comprises a second elastomeric polyurea/urethane hybrid layer (18) adhered to the first elastomeric layer (16). The second elastomeric polyurea/urethane hybrid layer (18) comprises the reaction product of second isocyanate and second isocyanate-reactive components. At least one of the second components is aromatic. Each of the elastomeric layers (16,18) has a glass transition temperature less than 0-C. The composite article (10) can further include a substrate layer adhered to the second elastomeric polyurea/urethane hybrid layer (18) opposite the first elastomeric layer (16). The composite article (10) may be a bedliner for a vehicle, such as for a truck.

Description

A COMPOSITE ARTICLE AND METHOD OF MAKING THE SAME

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent

Application Serial No. 60/868,626, which was filed on December 5, 2006 and is incorporated herewith in its entirety.

FIELD OF THE INVENTION

[0002] The present invention generally relates to a composite article for protecting a substrate and, more specifically, to a composite article for protecting a vehicle substrate and to a method of forming the composite article.

DESCRIPTION OF THE RELATED ART

[0003] Articles such as bedliners and bed mats are well known to those skilled in the art of paints and coatings, and are also well known to the general public. Protection from cosmetic damage, as well as protection from corrosion, abrasion, impacts, chemicals, UV light, and other environmental conditions is often desired by vehicle owners. Bedliners and bed mats are useful for protecting a vehicle substrate, such as a truck bed, from these and other types of damage. The vehicle may be, for example, a truck, a railcar, a freight ship, a wagon, or other vehicle requiring protection. [0004] With trucks, a floor, a front and pair of side walls, a front and pair of side rails, and a tail gate generally define the truck bed. The truck bed is usually formed from a metal and may be coated with a primer layer, a basecoat layer, and/or a clearcoat layer; however, other materials may also be used to form the truck bed, such as composites and plastics, which may also be coated. Cargo carried in the truck bed often scratches, scuffs, dents, or damages the truck bed in other ways. In addition, moisture can corrode the truck bed, which often occurs when one or more coating layers have been compromised, e.g., scratched, and the metal is exposed to the environment. Bedliners are used to protect the floor, the walls, and optionally, the tail gate and the rails of the truck bed, while bed mats are used to protect the floor of the truck bed.

[0005] Bedliners generally comprise two main categories. The first category being traditional drop-in bedliners, and the second category being more recent spray- in (and/or brush-on/roll-on) bedliners. Drop-in bedliners are typically made by thermo forming a sheet of thermoplastic. The thermoplastic may be, for example, polyethylene, polypropylene, or polyvinylchloride. Drop-in bedliners are rigid, strong and durable, which offers protection for the truck bed. Drop-in bedliners are typically easy to install, remove, and clean. Drop-in bedliners are usually high in gloss, which may be aesthetically pleasing. [0006] However, drop-in bedliners have some disadvantages. Drop-in bedliners require fastening and can move and shift around, which scratches and scuffs the truck bed. In addition, water, dirt, sand and other materials get beneath the drop- in bedliner, i.e., between the drop-in bedliner and the truck bed, accelerating damage to the truck bed. Drop-in bedliners can also detach at high vehicular speeds if not held in place, and are also prone to vibrating and rattling, which creates undesirable noise. Drop-in bedliners can also be scuffed, scratched, gouged, warped, and cracked, which makes them aesthetically unappealing and diminishes protection for the truck bed. Some drop-in bedliners are very slick, i.e., have a low coefficient of friction, due to the type of thermoplastic used to form them. Cargo carried in the truck bed is prone to sliding, which can damage the truck bed, the drop-in bedliner, or the cargo itself. Drop-in bedliners are typically black or dark in color due to the materials used to form them, which makes color selection limited for consumers. In addition, drop- in bedliners also reduce cargo space in the truck bed due to their size and thickness, and are not easy to repair if damaged, if repairable at all. [0007] Spray-in bedliners are typically applied by spraying an elastomer onto the truck bed, but can also be applied by pouring, brushing, or roll coating the elastomer onto the truck bed. The elastomer cures to form the spray-in bedliner. Unlike drop-in bedliners, spray-in bedliners are directly adhered to the bed, which makes them generally a permanent part of the truck bed, i.e., the spray-in bedliner and the truck bed are integral. By being directly adhered to the truck bed, the spray-in bedliner resists movement or shifting, and prevents material from getting beneath the spray-in bedliner. Spray-in bedliners also have many color options, which allows consumers to match the spray-in bedliner with their vehicle. Like drop-in bedliners, spray-in bedliners are easy to clean. Spray-in bedliners are usually matte in appearance, due to a surface texture formed therein. The surface texture is useful for preventing cargo from sliding around the truck bed. Spray-in bedliners take up very little cargo space in the truck bed due to their thickness and are easy to repair if damaged. Some consumers have also applied the elastomer used to form spray-in bedliners to other parts of the vehicle besides the truck bed. For example, some consumers have applied the elastomer to other vehicle substrates, such as a frame, rocker panels, or an underbody of the vehicle, for additional protection of the vehicle substrate. The elastomer has also been used to protect other substrates altogether, such as walkways, docks, floors, etc. [0008] Some bedliners are composites having two or more layers. One type of composite bedliner is formed from a first and second composition. To form the composite bedliner, the first composition is poured onto a floor of a truck bed to form a first layer having a Shore D hardness of from 50 to 80. The second composition is sprayed over the first layer and over walls of the truck bed to form a second layer having a Shore D hardness of from 35 to 49. The layers are dissimilar, i.e., the second layer is softer than the first layer, which provides a higher coefficient of friction and makes the second layer less slippery. The second layer also acts as a sacrificial layer that sloughs off under impact. If the second layer sloughs off, the first layer generally remains intact to protect the floor of the bed. [0009] Another type of composite bedliner utilizes polyurea coating compositions. To form the composite bedliner, a first layer formed from a polyurea composition is applied to a truck bed. A second layer formed from a second polyurea composition is applied over the first layer. A dust coating of the second polyurea composition may be applied over the layers, which creates a surface texture on the composite bedliner. [0010] Bed mats are placed over the floor of the truck bed and are generally held in place by gravity, or optionally, by an adhesive. Bed mats are typically molded from rubber and have many of the advantages of the drop-in bedliners. However, bed mats are often more prone than drop-in bedliners to moving and shifting around or lifting off of the truck bed due to wind or vehicular movement. Bed mats are also prone to many of the other disadvantages of the drop-in bedliners.

[0011] The aforementioned bedliners are characterized by one or more inadequacies. Specifically, many of the aforementioned bedliners are prone to degradation and are difficult to install. The sacrificial layer of the first composite bedliner described above sloughs off under impact due to the sacrificial layers softness, which quickly leaves the composite bedliner aesthetically unappealing after a first impact occurrence. In addition, the truck bed must be thoroughly prepped before pouring the first layer. Drain holes and seams in the truck bed must be plugged and a dam must be erected to retain the first composition in place while curing to form the first layer. In addition, due to the viscosity of the first composition and time required to cure, it is believed that the first layer is only useful for pouring on the floor, and not on the side walls or, optionally, a front wall, rails, and/or a tailgate of the bed. Overall, preparation of the truck bed can take many hours, generally taking three or more hours. Inadequate preparation of the truck bed can lead to poor aesthetics, and can even result in adhesion failure between the truck bed and the composite bedliner, i.e., the composite bedliner will peel off of the truck bed over time.

[0012] Many bedliners, especially spray-in bedliners, are also prone to degradation from exposure to UV light, in addition to having the aforementioned adhesion problems. Specifically, consumers commonly complain of discoloring of the bedliners from black to gray in color, and in some instances, complain of the bedliners becoming chalky over time. These problems are generally due to UV degradation of the bedliners, which is aesthetically displeasing, and can lead to failure of the bedliner over time. The second composite bedliner described above attempts to address the UV light degradation problems by employing aliphatic amine and polyisocyanate components. Aliphatic components are more resistant to UV light degradation than aromatic components; however, aliphatic components are considerably more expensive.

[0013] In addition, isocyanates employed to form polyurethanes and polyureas, react with water, which causes foaming. Foaming reduces adhesion strength between the truck bed and the bedliner. Foaming also reduces tensile strength and tear resistance of the bedliner, and leaves the bedliner with an undesired appearance. To overcome these problems, the compositions used to form the bedliners described above need to be applied in a controlled environment. Alternatively, costly additives must be employed to prevent or slow the isocyanates reaction with water. Polyureas also tend to react very quickly, which requires fast and proper mixing and application techniques to properly apply polyureas to substrates. It is believed that the inherently fast reactions may reduce adhesion strength between the bedliners formed from polyureas and the truck bed.

[0014] Accordingly, there remains an opportunity to provide a composite article that may be used as a bedliner or a bed mat that is lower in cost and has an improved UV light resistance as compared to existing composite articles used as bedliners or bed mats. There also remains an opportunity to provide a composite article that is easy to form and is aesthetically pleasing. There further remains an opportunity to provide a composite article having improved physical properties.

SUMMARY OF THE INVENTION AND ADVANTAGES

[0015] The present invention provides a composite article for protecting a substrate. The composite article comprises a first elastomeric layer that is a show surface of the composite article. The first elastomeric layer comprises the reaction product of a first isocyanate component comprising at least one of an aliphatic isocyanate and an aromatic isocyanate, and a first isocyanate-reactive component comprising at least one of an aliphatic amine, an aliphatic alcohol, an aromatic amine, and an aromatic alcohol. At least one of the first isocyanate component and the first isocyanate-reactive component is aliphatic. The composite article further comprises a second elastomeric polyurea/urethane hybrid layer adhered to the first elastomeric layer. The second elastomeric polyurea/urethane hybrid layer comprises the reaction product of a second isocyanate component comprising at least one of an aromatic isocyanate and an aliphatic isocyanate, and a second isocyanate-reactive hybrid component comprising at least one of an aromatic alcohol and an aliphatic alcohol and at least one of an aromatic amine and an aliphatic amine. At least one of the second isocyanate component and the second isocyanate-reactive hybrid component is aromatic. Each of the elastomeric layers has a glass transition temperature (Tg) less than O⁰C.

[0016] The present invention provides a unique combination of the first elastomeric layer and the second elastomeric polyurea/urethane hybrid layer. The composite article has improved physical properties including improved UV light resistance, improved adhesion strength, improved tensile strength, and improved tear resistance. The composite article is also lower in cost, is easy to form, and is aesthetically pleasing.

BRIEF DESCRIPTION OF THE DRAWINGS

[0017] 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 drawings wherein: [0018] Figure 1 is a perspective view of a truck having a truck bed and a composite article of the present invention as a bedliner for the truck bed, with the composite article made in accordance with the method of the present invention; [0019] Figure 2 is a cross-sectional side view of one embodiment of the composite article; [0020] Figure 2 A is an exploded side view of the composite article depicted in

Figure 2;

[0021] Figure 3 is a cross-sectional side view of another embodiment of the composite article disposed on the truck bed and taken along line 3-3 of Figure 1; [0022] Figure 4 is a simplified view of a test plate used for adhesion testing of the composite article;

[0023] Figure 5 is a graph depicting elastic modulus (E') curves based on dynamic mechanical thermal analysis (DMTA);

[0024] Figure 6 is a graph depicting viscous modulus (E") curves based on DMTA; and

[0025] Figure 7 is a graph depicting tan delta curves and glass transition temperatures (Tg) based on DMTA results of Figures 5 and 6.

DETAILED DESCRIPTION OF THE INVENTION [0026] Referring to the Figures, wherein like numerals indicate like parts throughout the several views, a composite article of the present invention is shown generally at 10. In one embodiment, as shown in Figure 1, the composite article 10 is a bedliner 10 for protecting a truck bed 12 of a truck 14. While the composite article 10 is shown as a bedliner 10 for protecting the truck bed 12, it is to be appreciated that in other embodiments, the composite article 10 may be used for numerous other applications such as for protecting other vehicles and other vehicle substrates, including, but not limited to, use as an underbody coating, a rocker panel coating, a frame coating, a running board coating, etc. It is to be appreciated that the composite article 10 may be used for other vehicles besides trucks, such as for airplanes, ships, trains, boats, ATVs, snowmobiles, agricultural vehicles, construction vehicles, etc. In addition, the composite article 10 may also be used for protecting substrates other than vehicle substrates. For example, the composite article 10 may be used for protecting pipes, freight ship surfaces, trailers, railcar surfaces, wagons, flooring, e.g. industrial flooring, boat decks, scoops and forks on construction and agricultural equipment, etc.

[0027] As shown in Figure 1, a floor 12a, a front and pair of side walls 12b, a front and pair of side rails 12c, and a tail gate 12d generally define the truck bed 12. While the composite article 10 is shown as the bedliner 10 for protecting the floor 12a, the walls 12b, the rails 12c, and the tail gate 12d, the composite article 10 may be used on any one of or a combination of the floor 12a, the walls 12b, the rails 12c, and/or the tailgate 12d. If employed for protecting just the floor 12a, the composite article 10 is generally classified as a bed mat 10 (not shown). The composite article 10 may be employed for protecting only a portion or portions of the truck bed 12. It is to be appreciated that the composite article 10 may also be used for protecting portions of other substrates, as described and exemplified above.

[0028] As best shown in Figures 2 and 2A, the composite article 10 includes a first elastomeric layer 16. The first elastomeric layer 16 provides a desired strength, moisture resistance, impact absorption, tear resistance, chemical resistance, abrasion resistance, and UV light resistance of the composite article 10. The first elastomeric layer 16 is generally a show surface of the composite article 10; however, it is to be appreciated that other layers may be placed on top of the first elastomeric layer 16. The first elastomeric layer 16 comprises the reaction product of a first isocyanate component and a first isocyanate-reactive component. At least one of the first isocyanate component and the first isocyanate-reactive component is aliphatic. In other words, the first elastomeric layer 16 can be formed from an aliphatic isocyanate component, an aliphatic isocyanate-reactive component, or a combination of the aliphatic isocyanate and aliphatic isocyanate-reactive components. For example, in one embodiment, both of the first components are aliphatic.

[0029] The first isocyanate component comprises at least one of an aliphatic isocyanate and an aromatic isocyanate. In other words, the first isocyanate component can include the aliphatic isocyanate, the aromatic isocyanate, or a combination of the aliphatic and aromatic isocyanates. Typically, the first isocyanate component comprises the aliphatic isocyanate, for imparting UV light resistance to the composite article 10. In one embodiment, the aliphatic isocyanate comprises isophorone diisocyanate (IPDI). Other suitable aliphatic isocyanates, for purposes of the present invention, include, but are not limited to, hexamethylene diisocyanates (HDI), dicyclohexylmethane diisocyanates (HMDI), cyclohexyl diisocyanates (CHDI), tetramethylxylene diisocyanates (TMXDI), and combinations thereof. Suitable aliphatic isocyanates are commercially available from BASF Corporation of Florham Park, NJ. Other suitable isocyanates, for use as the first isocyanate component, are described in U.S. Patent Nos. 6,617,032 (the '032 patent) and 6,841,1 11 (the ' 1 1 1 patent), both to Rickner et al., the disclosures of which are incorporated herewith in their entirety. [0030] In certain embodiments, the first isocyanate component is an isocyanate prepolymer, typically an isocyanate prepolymer, more typically an aliphatic isocyanate prepolymer. The aliphatic isocyanate prepolymer is generally the reaction product of a stoichiometric excess of the aliphatic isocyanate or aliphatic isocyanates, e.g. IPDI, an HDI trimer/polyisocyanate, etc., and at least one of a polyol and an amine, more typically the polyol. The polyol and/or amine may be of any type known to those skilled in the art, and can include those polyols and amines further described below. The aliphatic isocyanate or isocyanates is typically present in an amount of from about 50 to about 90, more typically from about 60 to about 80, most typically about 77, parts by weight, based on 100 parts by weight of the aliphatic isocyanate prepolymer. It is to be appreciated that the first isocyanate component may include a combination of two or more of the aforementioned isocyanates and/or isocyanate prepolymers.

[0031] Viscosity of the first isocyanate component may be changed by controlling specific components and ratios therein, as appreciated by those of ordinary skill in the art. For example, an excess of the aliphatic isocyanate typically decreases the viscosity of the aliphatic isocyanate prepolymer. The first isocyanate component typically has a viscosity of from about 20 to about 100, more typically from about 30 to about 50, most typically about 40, cps. Viscosity of the first isocyanate component can be determined according to ASTM D-1638/D-4878. A lower viscosity improves flow of the first isocyanate component, which can be useful for application purposes, which is described further below. It is to be appreciated that other viscosities may also be used.

[0032] The first isocyanate-reactive component comprises at least one of an aliphatic amine, an aliphatic alcohol, an aromatic amine, and an aromatic alcohol. In other words, the first isocyanate-reactive component can include the aliphatic amine, the aliphatic alcohol, the aromatic amine, the aromatic alcohol, or a combination of the aliphatic amine, the aliphatic alcohol, the aromatic amine, and/or the aromatic alcohol. Suitable alcohols include diols, i.e., alcohols having two hydroxyl functional groups, and polyols, i.e., alcohols having three or more hydroxyl functional groups. Suitable amines include diamines, i.e., amines having two amine functional groups, and polyamines, i.e., amines having three of more amine functional groups. Diols and diamines can be classified as chain extenders, as understood in the art. [0033] Typically, the first isocyanate-reactive component includes one or more aliphatic amines, for increasing UV light resistance of the composite article 10. If employed, the amine or amines can be selected from the group of ethylene diamine, toluene diamine, diaminodiphenylmethane and polymethylene polyphenylene polyamines, aminoalcohols, and combinations thereof. Examples of suitable aminoalcohols include ethanolamine, diethanolamine, triethanolamine, and combinations thereof. Other suitable amines, for purposes of the present invention, are described in the '032 and ' 11 1 patents.

[0034] If employed, and as alluded to above, the first isocyanate-reactive component can include one or more alcohols such as diols, polyols, or combinations thereof. For example, the first isocyanate-reactive component can comprise a polyester polyol, a polyether polyol, and combinations thereof. Other suitable alcohols include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, glycerol, trimethylolpropane, amine-initiated polyols such as triethanolamine, pentaerythritol, sorbitol, biopolyols such as soybean oil, castor-oil, soy-protein, rapeseed oil, etc., and combinations thereof. Further suitable alcohols, for purposes of the present invention, are described in the '032 and ' 1 11 patents.

[0035] In certain embodiments, such as those employing aliphatic components and amines, the first elastomeric layer 16 is further defined as an elastomeric aliphatic polyurea layer 16. Suitable first isocyanate components and first isocyanate-reactive components for forming the first elastomeric layer 16 are commercially available under the trade name POLYEURO^® from Polycoat Products of Santa Fe Springs, CA. As alluded to above, if employed, the POLYEURO^® components are typically aliphatic, e.g. Part-A and Part-B of POLYEURO^® 7801. However, it is to be appreciated that the POLYEURO^® components, for purposes of the present invention, may be classified as aliphatic, aromatic, aliphatic/aromatic hybrids, and combinations thereof. The first elastomeric layer 16 may also be formed from a polyurea coating composition. Suitable polyurea coating compositions are disclosed in U.S. Patent Publication No. 2006/0046068 to Barancyk et al. (the '068 publication), the disclosure of which is incorporated herewith in its entirety. The first isocyanate component and the first isocyanate-reactive component are typically combined at a ratio of about 1 : 1 by volume to form the first elastomeric layer 16; however, other ratios may also be used, as understood in the art.

[0036] Viscosity of the first isocyanate-reactive component may be changed by controlling specific components and ratios therein, as appreciated by those of ordinary skill in the art. The first isocyanate-reactive component typically has a viscosity of from about 100 to about 900, more typically from about 120 to about 400, most typically about 200, cps. Viscosity of the first isocyanate-reactive component can be determined according to ASTM D-1638/D-4878. A lower viscosity improves flow of the first isocyanate-reactive component, which can be useful for application purposes. It is to be appreciated that other viscosities may also be used. [0037] As best shown in Figures 2 and 2A, the composite article 10 further includes a second elastomeric polyurea/urethane hybrid layer 18. The second elastomeric polyurea/urethane hybrid layer 18 provides a desired strength, moisture resistance, adhesion strength, impact absorption, and tear resistance of the composite article 10. As shown in Figures 2 and 3, the second elastomeric polyurea/urethane hybrid layer 18 is adhered to the first elastomeric layer 16. It should be appreciated that the composite article 10 may include more than one each of the elastomeric layers 16, 18, and may include any combination of the elastomeric layers 16, 18, if three or more of the elastomeric layers 16, 18 are present. As described above, the first elastomeric layer 16 is typically the show surface of the composite article 10 that covers the second elastomeric polyurea/urethane hybrid layer 18. However, at least a portion of the second elastomeric polyurea/urethane hybrid layer 18 may be uncovered, especially portions of the second elastomeric polyurea/urethane hybrid layer 18 that are not generally exposed to UV light for extended periods of time. As described above, the first elastomeric layer 16 is adhered to the second elastomeric polyurea/urethane hybrid layer 18. The composite article 10 typically has a cohesive strength of at least about 200, more typically at least about 300, most typically at least about 400, pounds per square inch (psi), according to ASTM D-4541. [0038] The second elastomeric polyurea/urethane hybrid layer 18 comprises the reaction product of a second isocyanate component and a second isocyanate- reactive component. At least one of the second isocyanate component and the second isocyanate-reactive component is aromatic. In other words, the second elastomeric polyurea/urethane hybrid layer 18 can be formed from an aromatic isocyanate component, an aromatic isocyanate-reactive component, or a combination of aromatic isocyanate and aromatic isocyanate-reactive components. For example, in one embodiment, both of the second components are aromatic.

[0039] The second isocyanate component comprises at least one of an aromatic isocyanate and an aliphatic isocyanate. In other words, the second isocyanate component can include the aliphatic isocyanate, the aromatic isocyanate, or a combination of the aliphatic and aromatic isocyanates. Typically, the second isocyanate component comprises an aromatic isocyanate to decrease cost of the composite article 10, relative to employing aliphatic isocyanates. In one embodiment, the aromatic isocyanate comprises diphenylmethane diisocyanate (MDI). Other suitable aromatic isocyanates, for purposes of the present invention, include, but are not limited to, polymeric diphenylmethane diisocyanates (pMDI), toluene diisocyanates (TDI), naphthalene diisocyanates (NDI), tolidine diisocyanates (TODI), and combinations thereof. Suitable aromatic isocyanates are commercially available from BASF Corporation of Florham Park, NJ. A specific example of a suitable aromatic isocyanate is Lupranate^® MM 103, commercially available from BASF Corporation. Other suitable isocyanates, for use as the second isocyanate component, are described in the '032 and ' 111 patents.

[0040] In certain embodiments, the second isocyanate component is an isocyanate prepolymer, typically an isocyanate prepolymer, more typically an aromatic isocyanate prepolymer. The aromatic isocyanate prepolymer is generally the reaction product of a stoichiometric excess of the aromatic isocyanate, e.g. MDI, and at least one of a polyol and an amine, such as those described and exemplified above. The aromatic isocyanate is typically present in an amount of from about 50 to about 90, more typically from about 60 to about 80, most typically about 70, parts by weight, based on 100 parts by weight of the aromatic isocyanate prepolymer. It is to be appreciated that the second isocyanate component may include a combination of two or more of the aforementioned isocyanates and/or isocyanate prepolymers.

[0041] Viscosity of the second isocyanate component may be changed by controlling specific components and ratios therein, as appreciated by those of ordinary skill in the art. For example, an excess of the aromatic isocyanate typically decreases the viscosity of the aromatic isocyanate prepolymer. The second isocyanate component typically has a viscosity of from about 300 to about 900, more typically from about 450 to about 750, most typically about 600, cps. Viscosity of the second isocyanate component can be determined according to ASTM D-1638/D-4878. A lower viscosity improves flow of the second isocyanate component, which can be useful for application purposes. It is to be appreciated that other viscosities may also be used.

[00421 The second isocyanate-reactive component comprises at least one of an aromatic alcohol and an aliphatic alcohol and at least one of an aromatic amine and an aliphatic amine. In other words, the second isocyanate-reactive component includes the aromatic amine and/or the aliphatic amine, and further includes the aromatic alcohol and/or the aliphatic alcohol. Specifically, the second isocyanate-reactive component is a blend of at least one amine-functional component, e.g. amines, and at least one hydroxyl-functional component, e.g. alcohols. In the aforementioned embodiments, the second isocyanate-reactive component typically has a ratio of hydroxyl-functional components to amine-functional components, in parts by weight, of from about 1 : 1 to about 5: 1, more typically from about 2: 1 to about 4:1, most typically from about 2.5: 1 to about 3.5: 1. Changing the ratio of the functional components imparts the second isocyanate-reactive component with different ratios of hydroxyl and amine functionality, and therefore, imparts the second elastomeric polyurea/urethane hybrid layer 18 with different ratios of urethane and urea linkages formed therefrom. In addition, different ratios of the functional components may be useful for changing a reaction time between the second isocyanate component and the second isocyanate-reactive component. The hydroxyl-functional component or components is typically present in an amount of from about 50 to about 85, more typically from about 60 to about 75, most typically from about 65 to about 70, parts by weight, based on 100 parts by weight of the second isocyanate-reactive component. The amine-functional component or components is typically present in an amount of from about 15 to about 50, more typically from about 20 to about 35, most typically from about 25 to about 30, parts by weight based on 100 parts by weight of the second isocyanate-reactive component. In certain embodiments, such as those employing aromatic components, polyols, and amines, the second elastomeric polyurea/urethane hybrid layer 18 is further defined as an elastomeric aromatic polyurea/urethane hybrid layer 18.

[0043] The amine-functional component includes at least one amine, such as one or more of the amines as described and exemplified above. The amine-functional component can comprise primary amines, secondary amines, tertiary amines, and combinations thereof. A specific example of a suitable amine is Polyetheramine D 2000, commercially available from BASF Corporation of Florham Park, NJ. Other specific examples of suitable amines are Ethacure^® 100-LC diethyltoluenediamine (DETDA), commercially available from Albemarle Corporation of Baton Rouge, LA; and Unilink™ 4200 Diamine, commercially available from UOP of Des Plaines, IL. [0044] The hydroxyl-functional component includes at least one polyol, such as one or more of the polyols as described and exemplified above. The polyol typically has a nominal functionality of from 2 to 8, more typically from 2 to 6, most typically from 2 to 4. By "nominal functionality", it is meant that the functionality is based upon the functionality of an initiator molecule, rather than the actual functionality of the polyol after manufacture. A lower nominal functionality, i.e., 3 or less, is useful for decreasing a crosslink density of the second elastomeric polyurea/urethane hybrid layer 18. The polyol typically has an OH value of from about 100 to about 800, more typically from about 200 to about 600, most typically from about 300 to about 400, mg KOH/g. Suitable grades of polyols, for purposes of the present invention, such as those under the trade name Pluracol^®, e.g. Pluracol P- 945, Pluracol^® 1421, etc., are commercially available from BASF Corporation of Florham Park, NJ. The second isocyanate component and the second isocyanate- reactive component are typically combined at a ratio of about 1 : 1 by volume to form the second elastomeric polyurea/urethane hybrid layer 18; however, other ratios may also be used.

[0045] Viscosity of the second isocyanate-reactive component may be changed by controlling specific components and ratios therein, as appreciated by those of ordinary skill in the art. The second isocyanate-reactive component typically has a viscosity of from about 600 to about 1700, more typically from about 1000 to about 1200, most typically about 1000, cps. Viscosity of the second isocyanate- reactive component can be determined according to ASTM D-1638/D-4878. A lower viscosity improves flow of the second isocyanate-reactive component, which can be useful for application purposes. It is to be appreciated that other viscosities may also be used.

[0046] Each of the elastomeric layers 16, 18 has a glass transition temperature

(Tg) less than 0°C, more typically less than about -20°C, most typically less than about -40°C. In certain embodiments, both of the elastomeric layers 16, 18 have a Tg of about -43⁰C. As understood in the art, materials such as the elastomeric layers 16, 18, which are elastomers, according to DIN 7724, have glass transition temperatures. Conversely, thermoset materials do not have glass transition temperatures, i.e., thermosets do not soften or melt, but only permanently degrade, at elevated temperatures. Thermosets are also highly cross-linked, which often makes thermosets hard, but brittle. Elastomers are cross-linked, but to a degree less than that of thermosets, which often makes elastomers rubber-like or rubberelastic. As such, elastomers soften with increase in temperature. Cross-linking in elastomers is generally reduced due to the components used to form them, namely, predominantly difunctional components, such as the diisocyanates, diols, and diamines, as described and exemplified above, or high molecular weight functional components, such as long linear cross-linkers. Physical properties of elastomers also depend on a degree of physical entanglement of such components, rather than relying just on chemical cross- linking of such components. Cross-linking in thermosets is generally increased due to the components used to form them, namely, predominantly tri- and higher functional components or low molecular weight functional components, such as short highly branched cross-linkers. Unlike elastomers, physical properties of thermosets depend heavily on chemical cross-linking of such components. An example of a thermoset, for example, is an OEM basecoat/clearcoat system.

[0047] In certain embodiments, the first elastomeric layer 16 has a cross link density of from about 500 to about 2000, more typically from about 750 to about 1500, most typically from about 900 to about 1000, mol/m³. In other embodiments, the first elastomeric layer 16 has a cross-link density of from about 20000 to about 35000, more typically from about 22000 to about 32000, most typically from about 24000 to about 30000, mol/m³. In certain embodiments, the second elastomeric polyurea/urethane hybrid layer 18 has a cross-link density of from about 20000 to about 35000, more typically from about 22000 to about 32000, most typically from about 24000 to about 30000, mol/m³. As understood by those skilled in the art, crosslink density (XLD) can be determined by the following formula: XLD=E73RT, wherein E' (elastic modulus) is a point on the rubbery plateau of a curve generated by results from dynamic mechanical thermal analysis (DMA or DMTA) of the respective layer, for example, as shown in Figure 5 and as further described below. Further, R is the universal gas constant, i.e., 8.3145 J*K^"'*mor^l and T is the temperature in degrees Kelvin at the point of E'. The cross link densities described above are generally determined by E' at 25⁰C (298.15°K). The XLD formula and explanation thereof is described by ZENO W. WICKS JR. ET AL., ORGANIC COATINGS SCIENCE AND TECHNOLOGY 71 (2nd ed. 1999).

[0048] Optionally, at least one of the elastomeric layers 16, 18 may be formed in the presence of an additive component. The additive component may be selected from the group of, but is not limited to, colorants including metallic, organic, and inorganic pigments; inorganic and organic fillers including particulate and fibrous fillers; adhesion promoters; moisture scavengers and molecular sieves; UV light absorbers and hindered amine light stabilizers; catalysts; acid stabilizers; plasticizers; inorganic and organic surfactants; cross-linking agents and curatives; chain extenders; anti-foaming agents, surfactants, surface modifiers, and gas releasing agents; chain terminators; flame retardants; thixotropic agents; silicas including fumed silicas; clays; aluminum oxide; wetting agents; processing additives; oxidative and thermal stabilizers; reinforcing agents and fibers including glass fibers, carbon fibers, metallic fibers, Kevlar^® fibers, thermoplastic fibers, thermoset fibers, cellulosic fibers, polymeric fibers, and fiberglass fibers; rubber crumb; waxes; impact modifiers; and combinations thereof. It is to be appreciated that the additive component may be reactive, and therefore may react with other components within the elastomeric layers 16, 18 while forming; alternatively, the additive component may be inert. Some of these additives and other suitable additives, for purposes of the present invention, are described in the '032 and ' 11 1 patents. It is to be appreciated that the additive component may include a combination of two or more of the aforementioned additives. [0049] If employed, the additive component may be included in one or both of the elastomeric layers 16, 18. The additive component may be present in an amount of from about 0.1 to about 35, more typically from about 5 to about 25, most typically from about 10 to about 15, parts by weight, based on 100 parts by weight of the respective elastomeric layer 16, 18. For example, if the additive is a pigment, the pigment may be useful for matching a color of the composite article 10 with a color of the truck 14. It is to be appreciated that the composite article 10 may be of any color or combination of colors, such as black, gray, blue, red, etc. In addition, each of the elastomeric layers 16, 18 may be of the same color or may be different. [0050] The first elastomeric layer 16, e.g. the elastomeric aliphatic polyurea layer 16, and the second elastomeric polyurea/urethane hybrid layer 18, e.g. the elastomeric aromatic polyurea/urethane hybrid layer 18, typically have an overall thickness T of from about 25 to about 250, more typically from about 50 to about 150, most typically from about 60 to about 100, mils. The second elastomeric polyurea/urethane hybrid layer 18 typically has a thickness T2 of from about 10% to about 90%, more typically from about 30% to about 80%, most typically from about 50% to about 70%, of the overall thickness T. In certain embodiments, the second elastomeric polyurea/urethane hybrid layer 18 has a thickness T₂ of from about 55% to about 65%, more typically from about 57% to about 63%, and most typically about 60%, of the overall thickness T. It is to be appreciated that generally, the first elastomeric layer 16 has a thickness Ti making up the remainder of the overall thickness T. Increasing the thickness T₂ of the second elastomeric polyurea/urethane hybrid layer 18, while decreasing the thickness Ti of the first elastomeric layer 16, generally decreases cost of the composite article 10, due to the components used to form the elastomeric layers 16, 18. The first elastomeric layer 16 is typically thick enough to prevent UV light from penetrating and degrading the second elastomeric polyurea/urethane hybrid layer 18. It is to be appreciated that thicknesses Ti, T₂ of the elastomeric layers 16, 18 may be uniform or may vary. In addition, the overall thickness T of the composite article 10 may be uniform or may vary. For example, the overall thickness T of the composite article 10 on the walls 12b may be from about 60 to about 80 mils, and the overall thickness T on the floor 12a may be from about 80 to about 100 mils. In certain embodiments, the overall thickness T of the composite article 10 on the walls 12b may be from about 30 to about 50 mils, and the overall thickness T on the floor 12a may be from about 50 to about 70 mils. It is to be appreciated that the overall thickness T of the composite article 10 may be adjusted to change protection and cost of the composite article 10. In certain embodiments, the overall thickness T is kept at a minimum of about 80 mils or less to reduce cost of the composite article 10 while still offering protection for the truck bed 12. [0051] In certain embodiments, at least one of the first elastomeric layer 16, e.g. the elastomeric aliphatic polyurea layer 16, and the second elastomeric polyurea/urethane hybrid layer 18, e.g. the elastomeric aromatic polyurea/urethane hybrid layer 18, has a Shore D hardness less than 65. In other words, the first elastomeric layer 16, the second elastomeric polyurea/urethane hybrid layer 18, or both of the first and second elastomeric layers 16, 18 can have a Shore D hardness less than 65. The first elastomeric layer 16 typically has a Shore A hardness of at least about 70, more typically from about 70 to about 95, most typically from about 75 to about 85. The second elastomeric polyurea/urethane hybrid layer 18 typically has a Shore A hardness of at least about 60, more typically from about 60 to about 85, most typically from about 65 to about 75. In certain embodiments, the first elastomeric layer 16 has a Shore A hardness of from about 70 to about 95 and the second elastomeric polyurea/urethane hybrid layer 18 has a Shore A hardness of from about 60 to about 85. Shore hardness of the elastomeric layers 16, 18 can be determined in accordance with ASTM D-2240.

[0052] As shown in Figures 2 through 3, the first elastomeric layer 16 has a textured surface 26. In other embodiments (not shown), the first elastomeric layer 16 has a smooth surface. It is to be appreciated that at least a portion of the first elastomeric layer 16 may have the textured surface 26 and at least a portion of the first elastomeric layer 16 may have the smooth surface. The textured surface 26 increases the coefficient of friction of the composite article 10. It is to be appreciated that the textured surface 26 may be a discrete layer, or may be integral with the first elastomeric layer 16. The textured surface 26 is generally considered to be elastomeric. The textured surface 26 may also be referred to as a texturizing layer 26. [0053] The textured surface 26 may be made by any method known in the art.

For example, a dust coating method may be used to form the textured surface 26. Dust coating may be accomplished by, for example, increasing a distance between an applicator and the first elastomeric layer 16 to form discrete droplets of the first elastomeric layer 16 prior to curing and contacting the first elastomeric layer 16. The droplets adhere to, but do not generally coalesce with the first elastomeric layer 16 to form the textured surface 26. Dust coating may also be referred to as fog coating. It is to be appreciated that the textured surface 26 may be made by other methods known in the art. For example, the additive component, e.g. fiberglass fibers, could be used to form the textured surface 26 of the first elastomeric layer 16. [0054] Optionally, the composite article 10 may have at least one decal (not shown). The decal may be a discrete element attached to or formed integral with the composite article 10. For example, the decal can be a sticker or a badge attached to the composite article 10. The decal provides a desired aesthetic, identifying or informative feature of the composite article 10. For example, the decal may present a company name, a product name, a team name, a school name, a logo, a picture, text, a warning, an instruction, indicia, a symbol, etc. The composite article 10 can include a plurality of decals. For example, one decal may present each letter in a company name. The decal may be of any size, shape, pattern, and/or color. In one embodiment, the decal is planar with the first elastomeric layer 16. It is to be appreciated that the decal may also be recessed or raised relative to the first elastomeric layer 16. [0055] If included, the decal may be formed integral with the composite article 10 by utilizing a stenciling method. Stenciling may be accomplished by, for example, placing a stencil over the first elastomeric layer 16 and applying an additional layer (not shown) over the stencil to form the decal. The additional layer may be the dust coating, i.e., droplets, or a complete layer, e.g. an elastomeric layer, similar to the first elastomeric layer 16. If employed, the additional layer typically has a different color than the first elastomeric layer 16. However, the additional layer may be different from the first elastomeric layer 16 in other ways, such as by having a different gloss, texture, etc. Two or more stencils may be used to form the decal. Therefore, two or more of the additional layers may be on the composite article 10. Multiple stencils may be useful for making a decal having two or more colors.

[0056] In certain embodiments, as best shown in Figure 3, the composite article 10 further includes a substrate layer 20. As alluded to above, and as shown in Figure 1, the substrate layer 20 can be the truck bed 12. However, as also described above, the substrate layer 20 may comprise other vehicle substrates, or non-vehicle substrates (not shown). The substrate layer 20 is adhered to the second elastomeric polyurea/urethane hybrid layer 18 opposite the first elastomeric layer 16. [0057] In certain embodiments, such as shown in Figure 3, the substrate layer 20 is further defined as a coating layer 22 selected from the group of a clearcoat layer 22a, a basecoat layer 22b, a primer layer 22c, and combinations thereof. In other embodiments (not shown), the coating layer 22 comprises an electrocoating layer, which is also known in the coating art as an e-coating layer. It is to be appreciated that the e-coating layer may be used alone or in combination with one or more of the aforementioned layers 22a, 22b, 22c. The coating layer 22 is typically formed from a coating composition selected from the group of acrylic paint compositions, urethane paint compositions, urethane/acrylic paint compositions, carbamate paint compositions, polyester paint compositions, and combinations thereof. It is to be appreciated that the coating composition may comprise other coating compositions known in the coating art, and can include cross-linking agents, such as melamine. The coating composition may be a one component (IK) or a two component (2K) system. Suitable coating compositions for forming the coating layer 22 are incorporated herewith and are disclosed in U.S. Patent Nos. 5,137,972 to Cook; 4,720,528 to Etzell et al; 5,216,078 to Cook et al. ; 5,238,999 to Cook et al. ; 5,276,096 to Serdiuk et al. ; 5,356,669 to Rehfuss et al. ; 5,379,947 to Williams et al.; 5,494,970 to Serdiuk; 5,498,783 to Foukes et al.; 5,559,195 to McGee et al. ; 5,596,043 to Harris et al.; 5,635,302 to Budde et al., 6,995,208 to Mehta et al., 6,071,568 to Harmon et al. ; 5,605,965 to Rehfuss et al. ; 5,474,811 to Rehfuss et al.; and 5,726,246 to Rehfuss et al. Thickness of the coating layer 22 may be uniform or may vary. In addition, thickness of the coating layer 22 can be of any thickness, such as those thicknesses commonly used in the coating art. Accordingly, each of the layers 22a, 22b, 22c may also be of any thickness. In addition, the thickness of each of the layers 22a, 22b, 22c may be uniform or may vary. Generally, the coating layer 22 is a thermoset, due to the components used to form the coating layer 22, as understood in the coating art. Unlike elastomers, thermosets lack a glass transition temperature (Tg), as described above. Other suitable coating compositions, for purposes of the present invention, are described in the '068 publication. [0058] In other embodiments, the substrate layer 20 is further defined as a vehicle substrate 24 selected from the group of metal substrates 24a, composite substrates (not shown), plastic substrates (not shown), and combinations thereof. It is to be appreciated that the substrate layer 20 may comprise a combination of the coating layer 22 and the vehicle substrate 24, e.g. as illustrated in Figure 3. Thickness of the vehicle substrate layer 24 may be uniform or may vary. In addition, thickness of the vehicle substrate 24 can be of any thickness, such as those thicknesses commonly used in the automotive art. [0059] As described above, the second elastomeric polyurea/urethane hybrid layer 18 is typically adhered to the substrate layer 20. Typically, the second elastomeric polyurea/urethane hybrid layer 18 has an adhesion strength of at least about 200, more typically at least about 300, most typically at least about 400, psi, relative to the substrate layer 20 according to ASTM D-4541. In certain embodiments, without being bound or limited by any particular theory, it is believed that the excess isocyanate groups in the aromatic isocyanate prepolymer, if employed, improve adhesion strength between the second elastomeric polyurea/urethane hybrid layer 18 and the truck bed 12. For example, the coating layer 22 may have functional groups, e.g., hydroxyl groups, which are reactive with the isocyanate groups. It is believed that a reaction between the functional groups on a surface of the coating layer 22 and the isocyanate groups improves the adhesion strength between the second elastomeric polyurea/urethane hybrid layer 18 and the truck bed 12. There may also be a degree of hydrogen bonding between the second elastomeric polyurea/urethane hybrid layer 18 and the truck bed 12. It is also believed that the reaction speed of the second elastomeric polyurea/urethane hybrid layer 18 increases adhesion strength between the truck bed 12 and the second elastomeric polyurea/urethane hybrid layer 18. Due to the hybrid nature of the second elastomeric polyurea/urethane hybrid layer 18, it is believed that a slower reaction of the urethane linkages forming, e.g. when diols and/or polyols are employed, compared to the urea linkages forming, e.g. when diamines and/or polyamines are employed, increases adhesion strength between the truck bed 12 and the second elastomeric polyurea/urethane hybrid layer 18. Formation of urethane and urea linkages based upon reaction of the isocyanate and isocyanate-reactive components is understood by those of ordinary skill in the art. [0060] To form the composite article 10, a second composition is applied onto a substrate, e.g. the coating layer 22, to form the second elastomeric polyurea/urethane hybrid layer 18. The second composition comprises the second isocyanate component and the second isocyanate-reactive component, and, optionally, the additive component. In one embodiment, the second composition is an aromatic polyurea/urethane hybrid composition. In one embodiment, the second composition is applied to the truck bed 12 while the coating layer 22 has not fully cured to a final cure state. In another embodiment, the second composition is applied to the truck bed 12 once the coating layer 22 has fully cured or otherwise set to a generally hardened condition to prevent mixing or cross-contamination with the second composition. Typically, the second elastomeric polyurea/urethane hybrid layer 18 substantially cures in less than about 10 seconds, more substantially cures after about 1 to about 2 minutes, and fully cures after about 12 to about 24 hours, at room temperature. By "substantially cures", it is meant that the second elastomeric polyurea/urethane hybrid layer 18 has achieved at least about 90% of its final cure state. [0061] A first composition is applied on the second elastomeric polyurea/urethane hybrid layer 18 to form the first elastomeric layer 16. The first composition comprises the first isocyanate component and the first isocyanate- reactive composition, and, optionally, the additive component. In one embodiment, the first composition is an aliphatic polyurea composition. In one embodiment, the first composition is applied while the second elastomeric polyurea/urethane hybrid layer 18 has not fully cured to a final cure state. In another embodiment, the second elastomeric polyurea/urethane hybrid layer 18 has fully cured or otherwise set to a generally hardened condition prior to applying the first composition to prevent mixing or cross-contamination with the first composition. It is believed that adhesion strength between the elastomeric layers 16, 18 may be increased when the second elastomeric polyurea/urethane hybrid layer 18 has not fully cured to a final cure state prior to applying the first composition. Typically, the first elastomeric layer 16 substantially cures in less than about 10 seconds, more substantially cures after about 2 to about 5 minutes, and fully cures after about 18 to about 30, more typically about 24 hours, at room temperature. By "substantially cures", it is meant that the first elastomeric layer 16 has achieved at least about 90% of its final cure state. [0062] The first and second compositions may be applied by any method known to those of ordinary skill in the art. Typically, the first and second compositions are applied by spraying, such as by impingement mixing and spraying; and/or by atomizing such as static mix tube atomizing and rotary bell atomizing. Spray mixing blends the respective isocyanate and isocyanate-reactive components together, to form the respective first and second compositions while application takes place. Alternatively, one or both of the first and second compositions may be individually premixed and then applied. The respective isocyanate and isocyanate- reactive components are typically mixed at a ratio of about 1 : 1 by volume to form the respective first and second compositions, as described above; however, other ratios are also possible. Other methods for applying the first and second compositions include, but are not limited to, brushing, rolling, pouring, sheeting, dipping, and combinations thereof. It is to be appreciated that one or both of the first and second compositions may also be applied to the composite article 10 after being made, which may be useful for repair purposes.

[0063] The first and second compositions may be at any temperature prior to and during application. For example, the first and second compositions may be at ambient temperature or may be preheated to a temperature of from about 12O⁰F to about 170°F prior to application. The first and second compositions may also be applied at any pressure, such as when applied with a spray gun. For example, the compositions may be applied at a pressure of from about 1500 psi to about 2500 psi. It is to be appreciated that the first and second compositions may also be applied to the substrate at other temperatures and pressures than those described above. [0064] The elastomeric layers 16, 18 may be formed at ambient temperatures, such as from about 65°F to about 85⁰F. However, the elastomeric layers 16, 18 may be formed at lower or higher temperatures. The truck bed 12 may be preheated to a temperature higher than ambient temperature to decrease cure time of the elastomeric layers 16, 18. The elastomeric layers 16, 18 and the truck bed 12 may also be heated to a temperature higher than ambient temperature to cure the elastomeric layers 16, 18, for example, by heating in an oven. It is to be appreciated that the elastomeric layers 16, 18 may be formed and cured at other temperatures. In addition, the elastomeric layers 16, 18 may also be cured utilizing other methods known to those skilled in the art. [0065] Application of the first and second compositions may be achieved manually and/or robotically. The first and second compositions may be applied at different locations of the truck bed 12, at different thicknesses, and may be applied in multiple layers. For example, the dust coating may be applied to the first elastomeric layer 16 to form the textured surface 26 of the composite article 10. The truck bed 12 may be taped or partitioned off from the rest of the truck 14 prior to applying the first and second compositions. However, application of the first and second compositions may be controlled in such a way as to minimize or prevent drift of particulates of the first and second compositions from leaving the truck bed 12 during application. [0066] The first and second compositions of the present invention have little to no reactivity with water, which makes application of the first and second compositions and formation of the elastomeric layers 16, 18 generally easier relative to conventional systems. Specifically, prior art compositions include components that quickly react with water, which causes foaming. It is believed that polyurea compositions have less foaming issues relative to polyurea/urethane hybrid compositions, and polyurea/urethane hybrid compositions have less foaming issues relative to polyurethane compositions. Foaming decreases strength, adhesion, and other properties of layers formed from the prior art compositions, which is undesirable. [0067] Optionally, the truck bed 12 may be pretreated before applying the first and second compositions. For example, the truck bed 12 may be physically and/or chemically abraded and roughened, which can increase adhesion strength between the truck bed 12 and the second elastomeric polyurea/urethane hybrid layer 18. However, the truck bed 12 may be left untreated, which may be desirable for aesthetic and protective purposes. [0068] Optionally, the decal may be applied to the composite article 10. In one embodiment, the stencil is placed over a portion of the first elastomeric layer 16. A third composition is applied over the stencil and onto the first elastomeric layer 16 not covered by the stencil to form the additional layer. The third composition may be substantially the same as the first composition but, for example, with a different pigment as the additive component. In this embodiment, the different pigment provides the additional layer with a different color than the first elastomeric layer 16. In one embodiment, the decal is applied to the first elastomeric layer 16 while the first elastomeric layer 16 has not fully cured to a final cure state. In another embodiment, the first elastomeric layer 16 has fully cured or otherwise set to a generally hardened condition prior to applying the decal. It is believed that adhesion strength between the decal and the composite article 10 may be increased while the first elastomeric layer 16 has not fully cured to a final cure state.

[0069] The following examples, illustrating the first and second compositions, the composite articles, and the method of the present invention, are intended to illustrate and not to limit the present invention.

EXAMPLES

[0070] A first composition is made by combining a first isocyanate component and a first isocyanate-reactive component. The first isocyanate and isocyanate- reactive components of the first composition are mixed at a 1 : 1 ratio by volume. The first composition is POLYEURO^® 7801, which is a two component, i.e., Part-A and Part-B, aliphatic polyurea composition, commercially available from Polycoat Products of Santa Fe Springs, CA. A second composition is made by combining a second isocyanate component and a second isocyanate-reactive component. The second isocyanate and isocyanate-reactive components of the second composition are mixed at a 1 : 1 ratio by volume. The second composition is applied to a substrate to form a second elastomeric polyurea/urethane hybrid layer. The substrate is a test plate formed from metal, the test plate having a rectangular configuration as depicted in Figure 4. The test plate is further described below. The first composition is applied to the second elastomeric polyurea/urethane hybrid layer, which is already on the substrate, to form the first elastomeric layer. The amount and type of each component used to form the second composition is indicated in Table 1 below with all values in parts by weight based on 100 parts by weight of the second composition unless otherwise indicated. TABLE 1

[0071] Polyol A is a high molecular weight polyol having an average hydroxyl number of from about 34.0 to about 36.0 mg KOH/g and a nominal functionality of 3, commercially available from BASF Corporation of Florham Park, NJ.

[0072] Polyol B is a polyether polyol having an average hydroxyl number of about 800.0 mg KOH/g and a nominal functionality of 4, commercially available from Arch Chemicals of Norwalk, CT. [0073] Polyol C is a polypropylene glycol having an average hydroxyl number of from about 34.0 to about 36.0 mg KOH/g and a nominal functionality of 3, commercially available from BASF Corporation of Florham Park, NJ. [0074] Polyamine A is a polyetheramine having a molecular weight of 2000 and an amine number of from about 53.3 to about 58.9 mg KOH/g, commercially available from BASF Corporation of Florham Park, NJ. [0075] Chain Extender A is ethylene glycol. [0076] Chain Extender B is diethylene glycol.

[0077] Chain Extender C is an aromatic diamine having a molecular weight of

310, commercially available from UOP of Des Plaines, IL.

[0078] Chain Extender D is diethyltoluenediamine (DETDA), commercially available from Albemarle Corporation of Baton Rouge, LA.

[0079] Catalyst A is triethylenediamine (33% by weight in DPG).

[0080] Catalyst B is dibutyltindilaurate, commercially available from Air

Products and Chemicals, Incorporated of Allentown, PA.

[0081] Molecular Sieve A is potassium sodium alumosilicate, commercially available from Sigma- Aldrich Corporation of St. Louis, MO.

[0082] Pigment is carbon black pigment.

[0083] Isocyanate A is a modified 4,4'-diphenylmethane diisocyanate having a NCO content of about 29.5%, commercially available from BASF Corporation of

Florham Park, NJ. [0084] The viscosity of the first and second compositions is determined in accordance with ASTM D-1638/D-4878. In addition, density of the resulting first and second elastomeric layers is measured in accordance with ASTM D- 1622, hardness of the resulting first and second elastomeric layers is measured in accordance with

ASTM D-2240 (Shore), tensile strength and elongation of the resulting first and second elastomeric layers is measured in accordance with ASTM D-2370, tear resistance of the resulting first and second elastomeric layers is measured in accordance with ASTM D- 1004, and abrasion resistance of the resulting first and second elastomeric layers is measured in accordance with ASTM D-4060.

TABLE 2

[0085] Comparative examples and inventive examples of the present invention are prepared. Twenty test plates are prepared for comparative testing. The test plates are first prepared by spraying a basecoat paint composition onto the metal substrate to form a basecoat layer. The thickness of the basecoat paint composition applied to the test plate is increased from bottom to top of the test plate by a robotic applicator, as illustrated in Figure 4. The test plates are then baked in an oven for a set time at a set temperature to cure the basecoat layer. A clearcoat composition is then applied to the basecoat layer by a robotic applicator. The thickness of the clearcoat paint composition is increased from left to right of the test plate, as illustrated in Figure 4. The test plates are then baked in the oven for the set time at the set temperature to cure the clearcoat layer. The twenty test plates are made utilizing different temperatures for baking and/or are made utilizing different clearcoat paint compositions, which is described further below. All of these variables are constant between the examples with regard to adhesion strength measurements, which is described further below.

[0086] Ten of the test plates are prepared with inventive examples of the composite article of the present invention. To form the composite article, the components of the first and second compositions, respectively, are spray mixed while applying to the test plates. Spray mixing blends the first isocyanate and isocyanate- reactive components together, while application takes place. The same process is followed for the second isocyanate and isocyanate-reactive components. The second composition is first applied to the test plate, i.e., over the clearcoat layer, to form the second elastomeric polyurea/urethane hybrid layer. The first composition is then applied over the second elastomeric polyurea/urethane hybrid layer to form the first elastomeric layer. The first and second compositions are both applied by spray guns. The spray guns apply the first and second compositions at a pressure of from about 1500 to about 2500 psi. The first and second compositions are preheated to a temperature of from about 12O⁰F to about 17O⁰F, prior to application. The composite article is allowed to cure. The thickness of each of the first and second elastomeric layers, and therefore, the composite article, is uniform across the test plate. [0087] The remaining ten test plates are prepared with comparative examples of a comparative article. To form the comparative article, a first comparative composition and a second comparative composition are applied to the test plate, i.e., over the clearcoat layer. The comparative article is a 100% aliphatic layer. The comparative article is allowed to cure. The thickness of the comparative article is uniform across the test plate, and is the same as the composite article. [0088] Adhesion strengths of the examples are measured in accordance with ASTM D-4541. Pull off adhesion testing is carried out using dollies adhered to the test plates with glue. A simplified test plate is illustrated by Figure 4, as described above. As depicted, the thickness of the basecoat layer increases from bottom to top, and the thickness of the clearcoat layer increases from left to right. A dolly is adhered to each location of the test plate for adhesion strength measurements. Referring to Figure 4, locations 1 through 16 represent test plate locations with the comparative articles and locations 17 through 32 represent test plate locations with the composite articles of the present invention. In other words, location 1 of the comparative article can be compared to location 17 of the composite article, on two different plates having the same parameters, but for the articles disposed thereon. To better elaborate on thicknesses of the coating layers, the thickness of the basecoat and clearcoat layers are at a minimum at location 1/17 and are at a maximum at location 16/32. In addition, thickness of the basecoat layer is at a maximum and thickness of the clearcoat layer is at a minimum at location 13/29. Further, thickness of the basecoat layer is at a minimum and thickness of the clearcoat layer is at a maximum at location 4/20. The articles are uniform in thickness across all of the numbers, as described above. Adhesion strengths of the articles, relative to the locations and therefore thicknesses of the basecoat and clearcoat layers, can be readily appreciated by reference to the tables illustrated and described below.

TABLE 3 TABLE 4

[0089] Referring to Table 3 above, each of the test plates are baked at about

285°F for 20 minutes to cure each of the coating layers. Dollies 1 and 5 released prior to obtaining an adhesion value. A first clearcoat paint composition is used to form the clearcoat layer. Referring to Dollies 2, 3, 4, 6, 7, 9, 10, and 13, the composite article has higher adhesion strength than the comparative article. It is to be appreciated that the Dolly # represents the location of a specific dolly used for the adhesion testing. [0090] Referring to Table 4 above, each of the test plates is baked at about

285⁰F for 20 minutes to cure each of the coating layers. Dollies 1 and 13 released prior to obtaining an adhesion value. A second clearcoat paint composition is used to form the clearcoat layer. Referring to Dollies 2, 3, 4, 5, 6, 7, 8, 9, 10, and 14, the composite article has higher adhesion strength than the comparative article. TABLE 5 TABLE 6

[0091] Referring to Table 5 above, each of the test plates is baked at about

320⁰F for 20 minutes to cure each of the coat layers. The second clearcoat paint composition is used to form the clearcoat layer. Referring to Dollies 1, 2, 5, 6, 9, 10, and 13, the composite article has higher adhesion strength than the comparative article.

[0092] Referring to Table 6 above, each of the test plates is baked at about

320⁰F for 20 minutes to cure each of the coating layers. Dolly 28 had glue failure at 400 PSI prior to obtaining adhesion strength. The first clearcoat paint composition is used to form the clearcoat layer. Referring to Dollies 1 and 4, the composite article has higher adhesion strength than the comparative article.

TABLE 7 TABLE 8

[0093] Referring to Table 7 above, each of the test plates is baked at about

32O⁰F for 20 minutes to cure each of the coating layers. The second clearcoat paint composition is used to form the clearcoat layer. Referring to Dollies 2, 3, 4, 6, 7, 9, 10, and 13, the composite article has higher adhesion strength than the comparative article. [0094] Referring to Table 8 above, each of the test plates is baked at about

285°F for 20 minutes to cure each of the coating layers. The first clearcoat paint composition is used to form the clearcoat layer. Referring to Dolly 13, the composite article has higher adhesion strength than the comparative article.

TABLE 9 TABLE 10

[0095] Referring to Table 9 above, each of the test plates is baked at about

285⁰F for 20 minutes to cure each of the coating layers. The second clearcoat paint composition is used to form the clearcoat layer. Referring to Dollies 1, 2, 4, 5, 6, 9, and 13, the composite article has higher adhesion strength than the comparative article.

[0096] Referring to Table 10 above, each of the test plates is baked at about

320⁰F for 20 minutes to cure each of the coating layers. The first clearcoat paint composition is used to form the clearcoat layer. [0097] While some of the comparative articles may have adhesion strengths greater than or equal to the composite articles of the present invention, the composite articles of the present invention are much lower in cost due to the components used to form them, e.g. by using aromatic components. Optimum basecoat and clearcoat layer thicknesses for the composite articles can be appreciated by reference to the tables above, and can be readily determined by routine experimentation. No adhesion failure was observed in any of the composite articles between the first and second elastomeric layers, i.e., the composite articles do not have cohesive failures. In addition, no bubbling or separation was observed between any of the composite articles, i.e., between the second elastomeric polyurea/urethane hybrid layers and the test plates. Abrasion resistance of each of the composite articles is deemed to be higher than abrasion resistance of each of the respective comparative articles. [0098] Two additional inventive examples of the first elastomeric layer are prepared. Dynamic mechanical thermal analysis (DMA or DMTA) of the first elastomeric layers, the second elastomeric polyurea/urethane hybrid layer, and the comparative article is determined according to ASTM D-4065-01. Figure 5 illustrates elastic modulus (E') curves based on DMA of the examples. Here, First Layer A is the same as the first elastomeric layer as described above. First Layer B is similar to First Layer A, but employs a different chain extender, specifically, 3,3'-dimethyl- 4,4'-diamino-dicyclohexylmethane (DMDC). First Layer C is similar to First Layer B, but employs a polyetheramine having a functionality of 3.0 and having a molecular weight of 5000, commercially available from BASF Corporation of Florham Park, NJ. Figure 6 illustrates viscous modulus (E") curves based on DMA. Figure 7 illustrates tan delta (E"/E') curves based on DMA. [0099] First Layer A and Second Layer have been described above in Table 2.

First Layer B has a hardness of 42 D, a tensile strength of 2893 lb/in², a % elongation of 345, a tear resistance of 425 ppi, and a Tg of about -44. First Layer C has a hardness of 45 D, a tensile strength of 2371 lb/in², a % elongation of 482, a tear resistance of 382 ppi, and a Tg of about -46. Referring to Figure 7, it can be appreciated that the Comparative Article has a considerable higher Tg relative to the inventive examples. Cross-link density (XLD) of the layers can be determined by the following formula: XLD=E73RT, wherein E' is a point on a rubbery plateau of the curve of the respective layer, as shown in Figure 5. Further, R is the universal gas constant, i.e., 8.3145 J*K^"'*mor' and T is the temperature in degrees Kelvin at the point of E'. The rubbery plateau is considered that area of the curve that is relatively flat, or slightly downwardly sloping, such as from about -20⁰C (253.15°K) to about 25°C (298.15°K). By using the formula above for E' at 25°C, First Layer A has a XLD of about 961 mol/m3, and Comparative Article has a XLD similar to First Layer A. First Layer B has a XLD of about 27848 mol/m3, and First Layer C has a XLD similar to First Layer B. Second Layer has a XLD of about 24216 mol/m3. As described above, the XLD formula and explanation thereof is described by ZENO W. WICKS JR. ET AL., ORGANIC COATINGS SCIENCE AND TECHNOLOGY 71 (2nd ed. 1999). [00100] 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. Obviously, many modifications and variations of the present invention are possible in light of the above teachings. The invention may be practiced otherwise than as specifically described within the scope of the appended claims.

Claims

CLAIMS What is claimed is:

1. A composite article comprising:

(I) a first elastomeric layer that is a show surface of said composite article, said first elastomeric layer comprising the reaction product of

(i) a first isocyanate component comprising at least one of an aliphatic isocyanate and an aromatic isocyanate, and

(ii) a first isocyanate-reactive component comprising at least one of an aliphatic amine, an aliphatic alcohol, an aromatic amine, and an aromatic alcohol, wherein at least one of said first isocyanate component (i) and said first isocyanate-reactive component (ii) is aliphatic;

(II) a second elastomeric polyurea/urethane hybrid layer adhered to said first elastomeric layer and comprising the reaction product of (i) a second isocyanate component comprising at least one of an aromatic isocyanate and an aliphatic isocyanate, and

(ii) a second isocyanate-reactive component comprising at least one of an aromatic alcohol and an aliphatic alcohol and at least one of an aromatic amine and an aliphatic amine, wherein at least one of said second isocyanate component (i) and said second isocyanate-reactive component (ii) is aromatic; and

(III) a substrate layer adhered to said second elastomeric polyurea/urethane hybrid layer opposite said first elastomeric layer; wherein each of said elastomeric layers has a glass transition temperature (Tg) less than O⁰C.

2. A composite article as set forth in claim 1 wherein said second elastomeric polyurea/urethane hybrid layer is adhered to said substrate layer and said second elastomeric polyurea/urethane hybrid layer has an adhesion strength of at least about 200 psi relative to said substrate layer according to ASTM D-4541.

3. A composite article as set forth in claim 2 wherein said first elastomeric layer is adhered to said second elastomeric polyurea/urethane hybrid layer and said composite article has a cohesive strength of at least about 200 psi according to ASTM D-4541.

4. A composite article as set forth in claim 1 wherein said Tg of said first elastomeric layer is less than -20°C and said Tg of said second elastomeric polyurea/urethane hybrid layer is less than -2O⁰C.

5. A composite article as set forth in claim 1 wherein said substrate layer is further defined as a coating layer selected from the group of an electrocoat layer, a clearcoat layer, a basecoat layer, a primer layer, and combinations thereof.

6. A composite article as set forth in claim 5 wherein said coating layer is formed from a coating composition selected from the group of acrylic paint compositions, urethane paint compositions, urethane/acrylic paint compositions, carbamate paint compositions, polyester paint compositions, and combinations thereof.

7. A composite article as set forth in claim 5 wherein the coating layer is a thermoset lacking a glass transition temperature (Tg).

8. A composite article as set forth in claim 1 wherein said substrate layer is further defined as a vehicle substrate selected from the group of metal substrates, composite substrates, plastic substrates, and combinations thereof.

9. A composite article as set forth in claim 1 wherein said substrate layer is further defined as a truck bed.

10. A composite article as set forth in claim 1 wherein both of said first isocyanate component (i) and said first isocyanate-reactive component (ii) are aliphatic.

1 1. A composite article as set forth in claim 10 wherein both of said second isocyanate component (i) and said second isocyanate-reactive component (ii) are aromatic.

12. A composite article as set forth in claim 1 wherein both of said second isocyanate component (i) and said second isocyanate-reactive component (ii) are aromatic.

13. A composite article as set forth in claim 1 wherein said first elastomeric layer and said second elastomeric polyurea/urethane hybrid layer have an overall thickness of from about 25 to about 250 mils.

14. A composite article as set forth in claim 13 wherein said second elastomeric polyurea/urethane hybrid layer has a thickness of from about 10% to about 90% of said overall thickness.

15. A composite article as set forth in claim 1 wherein said first elastomeric layer has a Shore A hardness of from about 70 to about 95 and said second elastomeric polyurea/urethane hybrid layer has a Shore A hardness of from about 60 to about 85.

16. A composite article as set forth in claim 1 wherein said first elastomeric layer is further defined as an elastomeric aliphatic polyurea layer and said second elastomeric polyurea/urethane hybrid layer is further defined as an elastomeric aromatic polyurea/urethane hybrid layer.

17. A composite article as set forth in claim 1 wherein both said first and second isocyanate components are further defined as isocyanate prepolymers.

18. A composite article as set forth in claim 17 wherein said alcohols of said second isocyanate-reactive component (ii) comprise diols and said amines of said second isocyanate-reactive component (ii) comprise diamines.

19. A composite article for protecting a substrate, said composite article comprising:

(I) a first elastomeric layer that is a show surface of said composite article, said first elastomeric layer comprising the reaction product of (i) a first isocyanate component comprising at least one of an aliphatic isocyanate and an aromatic isocyanate, and

(ii) a first isocyanate-reactive component comprising at least one of an aliphatic amine, an aliphatic alcohol, an aromatic amine, and an aromatic alcohol, wherein at least one of said first isocyanate component (i) and said first isocyanate-reactive component (ii) is aliphatic; and

(II) a second elastomeric polyurea/urethane hybrid layer adhered to said first elastomeric layer and comprising the reaction product of

(i) a second isocyanate component comprising at least one of an aromatic isocyanate and an aliphatic isocyanate, and

(ii) a second isocyanate-reactive component comprising at least one of an aromatic alcohol and an aliphatic alcohol and at least one of an aromatic amine and an aliphatic amine, wherein at least one of said second isocyanate component (i) and said second isocyanate-reactive component (ii) is aromatic; with the proviso that at least one of said first elastomeric layer and said second elastomeric polyurea/urethane hybrid layer has a Shore D hardness less than 65.

20. A composite article as set forth in claim 19 wherein said first elastomeric layer has a Shore A hardness of at least about 70.

21. A composite article as set forth in claim 20 wherein said second elastomeric polyurea/urethane hybrid layer has a Shore A hardness of at least about 60.

22. A composite article as set forth in claim 19 wherein said first elastomeric layer has a Shore A hardness of from about 70 to about 95 and said second elastomeric polyurea/urethane hybrid layer has a Shore A hardness of from about 60 to about 85.

23. A composite article as set forth in claim 19 wherein both of said first isocyanate component (i) and said first isocyanate-reactive component (ii) are aliphatic.

24. A composite article as set forth in claim 23 wherein both of said second isocyanate component (i) and said second isocyanate-reactive component (ii) are aromatic.

25. A composite article as set forth in claim 19 wherein both of said second isocyanate component (i) and said second isocyanate-reactive component (ii) are aromatic.

26. A composite article as set forth in claim 19 wherein said first elastomeric layer is adhered to said second elastomeric polyurea/urethane hybrid layer and said composite article has a cohesive strength of at least about 200 psi according to ASTM D-4541.

27. A composite article as set forth in claim 19 wherein said first elastomeric layer and said second elastomeric polyurea/urethane hybrid layer have an overall thickness of from about 25 to about 250 mils.

28. A composite article as set forth in claim 27 wherein said second elastomeric polyurea/urethane hybrid layer has a thickness of from about 10% to about 90% of said overall thickness.

29. A composite article as set forth in claim 19 wherein said first elastomeric layer is further defined as an elastomeric aliphatic polyurea layer and said second elastomeric polyurea/urethane hybrid layer is further defined as an elastomeric aromatic polyurea/urethane hybrid layer.

30. A composite article as set forth in claim 19 wherein each of said elastomeric layers has a glass transition temperature (Tg) less than 0°C.

31. A composite article as set forth in claim 19 wherein both said first and second isocyanate components are isocyanate prepolymers.

32. A composite article as set forth in claim 31 wherein said alcohols of said second isocyanate-reactive component (ii) comprise diols and said amines of said second isocyanate-reactive component (ii) comprise diamines.

33. A composite article comprising:

(I) an elastomeric aliphatic polyurea layer that is a show surface of said composite article, said elastomeric aliphatic polyurea layer comprising the reaction product of a first isocyanate component comprising an aliphatic isocyanate, and a first isocyanate-reactive component comprising an amine;

(II) an elastomeric aromatic polyurea/urethane hybrid layer adhered to said elastomeric aliphatic polyurea layer and comprising the reaction product of a second isocyanate component comprising an aromatic isocyanate, and a second isocyanate-reactive component comprising an alcohol and an amine; and

(III) a truck bed adhered to said elastomeric aromatic polyurea/urethane hybrid layer opposite said elastomeric aliphatic polyurea layer; with the proviso that said elastomeric aromatic polyurea/urethane hybrid layer has an adhesion strength of at least about 200 psi relative to said truck bed according to ASTM D-4541.

34. A composite article as set forth in claim 33 wherein said aliphatic isocyanate comprises isophorone diisocyanate (IPDI).

35. A composite article as set forth in claim 34 wherein said aromatic isocyanate comprises diphenylmethane diisocyanate (MDI).

36. A composite article as set forth in claim 33 wherein said aliphatic polyurea layer has a Shore A hardness of from about 70 to about 95 and said aromatic polyurea/urethane layer has a Shore A hardness of from about 60 to about 85.

37. A composite article as set forth in claim 33 wherein said aliphatic polyurea layer and said aromatic polyurea/urethane layer have an overall thickness of from about 25 to about 250 mils.

38. A composite article as set forth in claim 37 wherein said aromatic polyurea/urethane layer has a thickness of from about 10% to about 90% of said overall thickness.

39. A composite article as set forth in claim 33 wherein each of said elastomeric layers has a glass transition temperature (Tg) less than O⁰C.

40. A composite article as set forth in claim 33 wherein both said first and second isocyanate components are isocyanate prepolymers.

41. A composite article as set forth in claim 40 wherein said alcohols of said second isocyanate-reactive component (ii) comprise diols and said amines of said second isocyanate-reactive component (ii) comprise diamines.

42. A method of forming a composite article on a substrate, the method comprising the steps of: applying a second elastomeric polyurea/urethane hybrid layer composition on the substrate to form a second elastomeric polyurea/urethane hybrid layer, the second elastomeric polyurea/urethane hybrid layer composition comprising

(ii) a second isocyanate-reactive component comprising at least one of an aromatic alcohol and an aliphatic alcohol and at least one of an aromatic amine and an aliphatic amine, wherein at least one of the second isocyanate component (i) and the second isocyanate-reactive component (ii) is aromatic; and applying a first elastomeric layer composition on the second elastomeric polyurea/urethane hybrid layer to form a first elastomeric layer that is a show surface of the composite article, the first elastomeric layer composition comprising

(ii) a first isocyanate-reactive component comprising at least one of an aliphatic amine, an aliphatic alcohol, an aromatic amine, and an aromatic alcohol, wherein at least one of the first isocyanate component (i) and the first isocyanate-reactive component (ii) is aliphatic.

43. A method as set forth in claim 42 wherein the steps of applying are further defined as spraying.

44. A method as set forth in claim 42 wherein the substrate is further defined as a vehicle substrate.

45. A method as set forth in claim 44 wherein the vehicle substrate is further defined as a truck bed.

46. A method as set forth in claim 42 wherein the first elastomeric layer is further defined as an elastomeric aliphatic polyurea layer and the second elastomeric polyurea/urethane hybrid layer is further defined as an elastomeric aromatic polyurea/urethane hybrid layer.