Abstract:
A substrate, such as a roofing substrate, is protected by coating it with a low density polyurethane foam which is then coated with an essentially non-porous, dense, elastomeric polyurethane layer. The layer is formed by spraying a volatile-free spray of polyurethane precursor reactants onto the surface of the foam and rapidly reacting the precursors.

Description:
BACKGROUND OF THE INVENTION 
     This invention relates to the use of polymeric compositions for roofing and the like. More specifically, it relates to the use of such compositions containing polyurethane foams. 
     It is known to use polyurethane foam layers on roofs, walls, and the like, to protect against weather and provide insulation, among other things. One method of applying such foams involves spraying precursor reactants for polyurethanes directly onto wooden, metallic, or other roof substrates, and allowing the precursors to react in place to form a rigid foam layer. The layer is then painted, or otherwise coated, with a thin protective layer of paint to protect the polyurethane foam against damage, for example, from the weather. 
     Difficulties have been encountered using prior compositions and techniques, in that the resulting painted polyurethanes are soft and are easily damaged, for example, by workers walking on the roofs, by hail storms, or by the eventual wearing away or cracking of the protective paint layer. 
     To overcome some of these problems, attempts have been made to make sturdy polyurethane foams having densities sufficiently high to give structural rigidity to the foam sufficient to resist the expected abuse typically encountered. However, these attempts have been largely unsuccessful, because the polyurethane foam roofs with paint coatings have still been insufficiently sturdy for many uses, lack durability, require large amounts of reactants to form the high density foams, and are expensive not only in raw materials, but also in the amount of labor required to apply the materials to a roofing substrate. Also, the applications are often unduly time-consuming. 
     These and other problems of the prior art compositions and techniques can be overcome, or greatly alleviated, in accordance with the present invention. 
     SUMMARY OF THE INVENTION 
     This invention contemplates methods and techniques for applying composite structures of polyurethane foams sandwiched between a substrate, such as a roofing substrate, and a tough elastomeric coating which is applied as a covering for the urethane foam. 
     In accordance with the invention, a two-component polyurethane system comprising an isocyanate component and a polyol component is pumped and sprayed through a conventional urethane foam spray gun or mixing head directly upon a roof, wall, or other substrate. The components react immediately to expand and polymerize to form a low density polyurethane foam insulating layer, which may range typically from a fraction of an inch to about four inches in thickness. An elastomeric layer is then sprayed directly over the foam layer to coat and protect the same. The elastomeric layer is an essentially non-porous polyurethane, which is dense, tough, and does not expand significantly. It is formed by spraying a volatile-free spray of polyurethane precursor reactants onto the surface of the foam and rapidly reacting the precursors. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The invention may be better understood by reference to the following examples in which a tough elastomeric layer is formed and test sprayed onto a specimen of very low density polyurethane foam insulation to achieve the results indicated: 
     EXAMPLE 1 
     The following ingredients, designated component &#34;B&#34; were mixed: 
     
         ______________________________________Polypropylene glycol, ethylene oxide capped tiol 4800                       73.0 partsmolecular weight1.4 butanediol              22.0 partsdi butyltin dilaurate        1.0______________________________________ 
    
     The following were mixed and designated component &#34;A&#34;: 
     
         ______________________________________Modified liquid 4,4&#39;diphenylmethane diisocyanate                       88.0Chlorinated paraffin 38.5% chlorine                       22.0______________________________________ 
    
     The components &#34;A&#34; and &#34;B&#34; were processed through a standard Gusmer FF spray foam machine onto a one inch thick piece of 1.5 lb. density urethane foam. The material was maintained at 115°-120° F. The reaction rate of the sprayed liquid was three seconds. The adhesion to the foam was excellent and the surface was usable within five minutes. The coating thickness approximated 50 mils and the density was 45 pounds per cubic foot and the shore hardness 75 A. 
     EXAMPLE 2 
     Component &#34;B&#34; 
     
         ______________________________________Propylene oxide based, 2000 molecular weight diol                      65.0 partsDiethylene glycol          24.0 parts24% lead napthenate         1.0______________________________________ 
    
     Component &#34;A&#34; 
     A 2.3 functionality polymethylene polyphenyl isocyanate was reacted with a 660 molecular weight diol containing 46% bromine to form a prepolymer. Reaction time at 75° F. was completed within 16 hours. 
     The mix ratio was: 
     
         ______________________________________  Isocyanate          90.0  Diol    10.0______________________________________ 
    
     When the reaction was completed the prepolymer was blended with Tris (B-chloopropyl phosphate), a fire retardant, in the following ratio: 
     
         ______________________________________  Prepolymer            96.0  Fire retardant            14.5______________________________________ 
    
     The material was processed at a ratio of 1:1 through standard spray foam to a thickness of 100 mils. The resultant product had an 85 Shore A hardness, a density of 50 lbs. per cubic ft. and was extremely fire retardant. Reaction time was four seconds. 
     EXAMPLE 3 
     Component &#34;B&#34; Blended 
     
         ______________________________________A trifunctional poly (oxyalkylene) polyol containing                       17.7 parts20% by weight polyurea in dispersionA mixed phosphonate ester containing 19% by weight                        7.0phosphorous with a hydroxyl number of 255A tetrafunctional amine based crosslinker with a 290                       18.0molecular weight1-4 butanediol               2.0Non hydrolyzable silicone surfactant                        .3______________________________________ 
    
     Component &#34;A&#34; 
     
         ______________________________________A 2.7 functionality polymethylene polyphenyl                     46.0isocyanateIsodecyl diphenyl phosphate                     7.0______________________________________ 
    
     The material was processed through standard spray equipment to a thickness of 60 mils. The density was 62 pounds per cubic foot and the durometer was 750. Reaction time was 10 seconds. This was by far the hardest product applied to the foam. 
     To achieve optimum chemical bonding of the elastomeric layer with the underlying low-density foam layer, it is preferred that the foam layer be clean and essentially free of dirt, moisture, or excessively oxidized surface constituents. Thus, it is preferred that the elastomeric layer be applied within from about one minute to about 24 hours, preferably within about two hours of the completion of the curing of the foam layer. Alternatively, the foam can be protected by other means, if it is necessary to delay application of the elastomeric coating for long periods of time. 
     The foam substrate should be maintained at temperatures within the range of about 40° F. to about 120° F. and preferably in the range from about 70° F. to about 100° F. when the elastomeric coating is applied. 
     The elastomeric coating should be applied as a layer ranging above about 20 mils in thickness and preferably from about 40 to 100 mils. In particularly preferred embodiments, it is desired to use coatings in the range from about 50 to 70 mils in thickness to provide optimum economy while maintaining adequate coverage, sealing of the foam, high impact strength, and good penetration resistance. 
     The elastomeric coating itself is applied preferably at temperatures in the range from about 120° F. to about 140° F. 
     The elastomeric coatings of the present invention are essentially non-porous and are prepared from 100% reactive constituents so that there is no waste material, no volatiles to dispose of or which require drying or evaporation to finish the reaction and coating process. 
     The hardness of the elastomeric layer is much higher than that of the foam and may vary from about 20 Shore A to about 80 Shore D by varying the chemical composition of the reactants. To provide softer, more durable and flexible layers, isocyanates having a functionality of approximately 2, such as 4,4&#39; diphenylmethane, diisocyanate, or similar reactants. The polyol choice would be a high molecular weight diol or triol, either propylene oxide or ethylene oxide cross-linked using an agent, such as a low molecular weight diol. Metallic or amine catalysts can be used to obtain desired reaction times. 
     To produce elastomeric layers in the higher hardness range, higher functionality isocyanates, such as polymethylene, polyphenyl isocyanate, together with high molecular weight diols and triols, can be used together with crosslinking agents having a functionality of up to four. 
     It is also contemplated to use various modifiers, such as fire retardants, extenders, pigments, and flow control agents, to enhance the characteristics of the raw materials, as well as those of the finished product. 
     Many other uses and variations of the invention will be apparent to those skilled in the art, and while specific embodiments of this invention have been described, these are intended for illustrative purposes only. It is intended that the scope of the invention be limited only to the attached claims.