Patent Abstract:
A two component polyurea coating composition that exhibits a dual cure phenomena. The coating composition comprises a polyaspartic ester that is combined together with a polyisocyanate in such a manner that the polyisocyanate is present is an amount that is greater than a normal stoichiometric amount for the polyaspartic ester. By over indexing the polyaspartic ester with the polyisocyanate advantages of moisture curing and or “fast curing” can be combined together in the final finish.

Full Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a continuation-in-part of U.S. patent application Ser. No. 09/934,936, filed Aug. 22, 2001 now U.S. Pat. No. 6,833,424, the disclosure of which is hereby incorporated by reference. 
    
    
     BACKGROUND OF THE INVENTION 
     The present invention relates to a polyurea coating composition that can be applied as a wet finish on any substrate. More particularly, the present invention relates to a two component polyurea coating composition that exhibits a dual cure phenomena. 
     Two component coating compositions containing a polyisocyanate component in combination with an isocyanate-reactive such as a polyhydroxyl component or a polyamine are known. These coating compositions are suitable for the formation of high quality coatings and can be adjusted to produce coatings which are hard, elastic, abrasion resistant, solvent resistant and weather resistant. 
     Generally, there are two mechanisms by which the curing of polyurea coating compositions takes place-moisture cure or plural component “fast cure” which involves cross-linking the polyisocyanate component with an amine. Aliphatic coating compositions which rely upon moisture cure demonstrate very slow curing times which can limit their use in some applications. Coating compositions which rely upon plural “fast cure” are susceptible to adhesion problems when the curing proceeds too quickly. 
     In accordance with the present invention, polyurea coating compositions based on a two component system of a polyisocyanate component and a polyaspartic ester isocyanate-reactive component are produced which demonstrate a dual cure phenomena which results in improved film properties and curing times. 
     SUMMARY OF THE INVENTION 
     According to other features, characteristics, embodiments and alternatives of the present invention which will become apparent as the description thereof proceeds below, the present invention provides a polyurea coating composition that exhibits a dual cure phenomena, the polyurea coating composition including:
         a polyaspartic ester; and   a polyisocyanate,   wherein the polyisocyanate is present in an amount that is greater than a normal stoichiometric amount for the polyaspartic ester.       

     The present invention further provides a method of preparing a polyurea coating composition which involves:
         providing a polyaspartic ester;   providing a polyisocyanate; and   mixing the polyaspartic ester and the polyisocyanate together so that the polyisocyanate is present in an amount that is greater than a normal stoichiometric amount for the polyaspartic ester.       

     The present invention also provides a surface finish which comprises a cured composition that includes a polyaspartic ester and a polyisocyanate, wherein the polyisocyanate is present in an amount that is greater than a normal stoichiometric amount for the polyaspartic ester prior to curing. 
     The present invention still further provides a method for a forming a surface finish which involves:
         providing a polyaspartic ester;   providing a polyisocyanate;   mixing the polyaspartic ester and the polyisocyanate together so that the polyisocyanate is present in an amount that is greater than a normal stoichiometric amount for the polyaspartic ester;   applying the mixed composition to a surface to form a surface coating; and   allowing the applied surface coating to cure.       

     The present invention further provides a coated object of:
         a substrate; and   a coating on the substrate of a polyurea coating composition including
           a polyaspartic ester, and   a polyisocyanate, wherein the polyisocyanate is present in an amount that is greater than a normal stoichiometric amount for the polyaspartic ester, and wherein the coating composition cures dry to handle after air drying at 72° F. and 40% relative humidity in less than 120 minutes.   
               

     DETAILED DESCRIPTION OF THE INVENTION 
     The polyurea coating compositions of the present invention provide a hybrid curing system that combines the “fast cure” of a polyaspartic ester polyurea reaction with the enhanced adhesion and superior film properties of a slower curing moisture cure polyurea. The polyurea coating compositions of the present invention demonstrate enhanced adhesion, rapid cure rates and light stability, and can be used to produce bubble free, low to high film builds wit thicknesses that range from less that 1 mil to greater thank 20 mil. 
     The coating compositions of the present invention comprise two component polyureas that have exceptional direct-to-substrate adhesion and are based the use of a polyaspartic ester that is over indexed with a polyisocyanate. On component is a polyaspartic ester based component that can be pigmented or clear and incorporated with or without solvents. The other component is a polyisocyanate that can be incorporated with or without solvents. 
     Suitable polyisocyanates for use in accordance with the present invention include aliphatic polyisocyanates such as hexamethylenediisocyanate (HDI) and lysine diisocyanate; alicyclic polyisocyanates such as dicyclohexylene diisocyanate, isophorone diisocyanate (IPDI), cyclohexane diisocyanate (CHDI); aromatic polyisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate (NDI), xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI); and mixtures thereof. Higher functional Biruet polyisocyanates are usually preferred over trimers, dimmers, and hexamethylenediisocyanate (HDI) was found to be particularly useful for purposes of the present invention. 
     Suitable polyaspartic esters include single polyaspartic esters, or blends, such as those disclosed in U.S. Pat. Nos. 5,126,170; 5,243,012; 5,736,604 and 6,458,293, the disclosures of which are hereby incorporated by reference. 
     In formulating the coating compositions of the present invention, the polyaspartic ester is over indexed with an aliphatic polyisocyanate. That is, the polyisocyanate was used in an amount that is greater than the stoichiometric amount one would normally calculate for a specific amount of a polyaspartic ester. During the course of the invention, the applicant determined that measurable improvements in the film properties of a coating produced from the polyurea coating compositions of the present invention were obtained at an over indexing of the polyaspartic ester to a polyisocyanate at above about 1.5 NCO to NH. Optimum film properties were obtained without the use of a secondary catalyst at an over indexing of the polyaspartic ester to a polyisocyanate at above about 2.5±0.5 NCO to NH. When over indexing the polyaspartic ester with a polyisocyanate above about 3.0 NCO to NH, without the use of a secondary catalyst, the air dry cure times increase unfavorably. 
     Although not intending to be bound by an particular theory, and understanding that an applicant need not comprehend the scientific principles on which the practical effectiveness of his invention rests, applicant theorizes that by selectively over indexing the polyaspartic ester to the polyisocyanate, it is possible to reach an optimum balance between moisture curing and “fast curing” which involves cross-linking the polyisocyanate component with an aliphatic amine. When the mechanism of moisture curing predominates, surface adhesion is optimized; however, the curing times are very long and the film is susceptible to the formation of CO 2  bubbles when the applied dried film thickness exceeds 5 mil, or under high humidity conditions. When the cross-linking mechanism associated with fast curing predominates, surface adhesion is reduced in favor of quicker curing times. Applicant has determined that within an over indexing range of from about 1.5 up to about 3.0 of NCO to NH, the polyurea coating compositions of the present invention demonstrate a dual cure property in which the cross-linking mechanism associated with fast curing causes the surface of a coating to dry relatively fast, while the mechanism of moisture curing at the interface between the coating layer and substrate allows the coating composition to cure more slowly and thereby develop good adhesive properties. 
     The polyurea coating compositions of the present invention can be applied to virtually any surface as a wet coating which can be applied in any conventional manner such as spraying, dipping, brushing, etc. Once applied, if desired, the coatings can be air dried or forced dried according to conventional methods. The coating compositions can be suitably applied over a temperature range of about 40° F. to about 95° F. and relative humidity levels of about 40% to about 95%. 
     The polyurea coating compositions of the present invention have been found to produce finishes that have strong adhesion properties, high tensile strengths, chemical resistance to solvents and other chemical agents, resistance to ultraviolet light, and excellent color and gloss retention. The finishes are hard as well as impact and chip resistant, and can be recoated as desired. The coatings of the present invention can be applied to substrates such as cement, asphalt, metal, glass, and wood. The coatings may be used as an overcoat, on top of other coatings or treated surfaces such as zinc coated or zincated surfaces. 
     It is noted that the polyurea coating compositions can include single polyaspartic esters or blends of polyaspartic with or without additional catalytic agents. In addition, the compositions can include other conventional components such as pigments, dyes, fillers, carriers, solvents, surface texturing agents, etc. For convenience of field use, the two components of the compositions can be formulated to be mixed in a 1:1 ratio. Such a mixing ratio eliminates the need for measuring different amounts of the two components. The coating compositions have been determined to be particularly useful as an alternative to conventional coatings that require baking, when the parts or articles to be coated are too large or otherwise unsuitable for baking. 
     The following non-limiting examples were conducted to evaluate performance characteristics of the polyurea coating compositions of the present invention. The polyurea coating compositions tested in the following examples were non-pigmented clear coats that were applied at a dry film thickness (DFT) of 2 mil. The coating compositions were batch mixed and air spray applied. 
     Performance characteristics in the examples were evaluated using the following evaluation scale (ranging from 0 to 5):
         0=Total Failure   1=Near Total Failure   2=Partial Failure   3=Marginal   4=Acceptable   5=Excellent       

    
    
     EXAMPLE 1 
     Crosshatch Adhesion 
     In this Example, non-pigmented coatings were tested according to the procedure set forth in ASTM 1-3359-95, Test Method B. The test results are presented in Table 1 below: 
     
       
         
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                   
                   
                 Bonderite 1000 
                   
               
               
                 Stoichiometric 
                 Untreated Cold 
                 Pre-Treated Cold 
                 Grit Blasted 
               
               
                 Index 
                 Rolled Steel 
                 Rolled Steel 
                 Steel 
               
               
                   
               
             
             
               
                 1.00 
                 0 
                 4 
                 2 
               
               
                 1.25 
                 0 
                 4 
                 2 
               
               
                 1.50 
                 1 
                 5 
                 3 
               
               
                 1.75 
                 2 
                 5 
                 4 
               
               
                 2.00 
                 3 
                 5 
                 4 
               
               
                 2.25 
                 4 
                 5 
                 5 
               
               
                 2.50 
                 5 
                 5 
                 5 
               
               
                 2.75 
                 5 
                 5 
                 5 
               
               
                 3.00 
                 5 
                 5 
                 5 
               
               
                   
               
             
          
         
       
     
     EXAMPLE 2 
     Conical Mandrel 
     In this Example, non-pigmented coatings were tested according to the procedure set forth in ASTM D 522-93, Test Method A. The test results are presented in Table 2 below. 
     
       
         
               
               
               
               
             
           
               
                 TABLE 2 
               
               
                   
               
               
                   
                   
                 Bonderite 1000 
                   
               
               
                 Stoichiometric 
                 Untreated Cold 
                 Pre-Treated Cold 
                 Grit Blasted 
               
               
                 Index 
                 Rolled Steel 
                 Rolled Steel 
                 Steel 
               
               
                   
               
             
             
               
                 1.00 
                 0 
                 3 
                 N/A 
               
               
                 1.25 
                 0 
                 4 
                 N/A 
               
               
                 1.50 
                 0 
                 4 
                 N/A 
               
               
                 1.75 
                 1 
                 5 
                 N/A 
               
               
                 2.00 
                 2 
                 5 
                 N/A 
               
               
                 2.25 
                 4 
                 5 
                 N/A 
               
               
                 2.50 
                 5 
                 5 
                 N/A 
               
               
                 2.75 
                 5 
                 5 
                 N/A 
               
               
                 3.00 
                 5 
                 5 
                 N/A 
               
               
                   
               
             
          
         
       
     
     EXAMPLE 3 
     Recoat, Chemical Resistance and Drying 
     In this Example, non-pigmented coatings were tested according to the procedures set forth in ASTM D 3359-95, Test Method B (for recoat) and ASTM D 1308-87 (for Chemical resistance using n-methyl N-methylpyrrolidinone (NMP), 37% HCl, 20% HCl, 100% acetic acid and 50% acetic acid). In addition, drying characteristics were tested as indicated. The test results are presented in Table 3 below. 
     
       
         
               
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                   
                 Recoat After 
                 Chemical 
                 Dry to Handle 
               
               
                   
                 48 Hour Cure: 
                 Resistance 
                 Air Dry @ 72° F. 
               
               
                 Stoichiometric 
                 Intercoat 
                 After 30 
                 and 40% Relative 
               
               
                 Index 
                 Adhesion 
                 Day Cure 
                 Humidity @ 2 mils DFT 
               
               
                   
               
             
             
               
                 1.00 
                 0 
                 2 
                 &lt;30 Minutes 
               
               
                 1.25 
                 1 
                 3 
                 &lt;45 Minutes 
               
               
                 1.50 
                 2 
                 3 
                 &lt;45 Minutes 
               
               
                 1.75 
                 3 
                 3 
                 &lt;45 Minutes 
               
               
                 2.00 
                 4 
                 4 
                 &lt;45 Minutes 
               
               
                 2.25 
                 5 
                 4 
                 &lt;60 Minutes 
               
               
                 2.50 
                 5 
                 5 
                 &lt;60 Minutes 
               
               
                 2.75 
                 5 
                 5 
                 &lt;75 Minutes 
               
               
                 3.00 
                 5 
                 5 
                 &lt;120 Minutes  
               
               
                   
               
             
          
         
       
     
     EXAMPLE 4 
     Exposure to UV Light 
     In this Example, Gloss White coatings were tested according to the procedure set forth in ASTM D 4587-91, Procedure A (8 hour UV/70° C. followed by 4 hour CON/50° C.). The test results are presented in Table 4 below. 
     
       
         
               
               
               
               
             
           
               
                   
                 TABLE 4 
               
               
                   
                   
               
               
                   
                   
                 42 Day 
                 42 Day 
               
               
                   
                 Stoichiometric Index 
                 QUV-B 60 Gloss 
                 QUV-B Delta E 
               
               
                   
                   
               
             
             
               
                   
                 1.00–89.9 Gloss White 
                 52.1 
                 0.609 
               
               
                   
                 2.50–96.2 Gloss White 
                 78.7 
                 0.411 
               
               
                   
                   
               
             
          
         
       
     
     EXAMPLE 5 
     Black Semi Gloss 
     In this example Black Semi Gloss coatings were prepared as follows: 
     
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 5 
               
               
                   
                   
               
             
             
               
                   
                   
                   
                 Percent 
                 Suppl 
                 Solvent 
                 % 
               
               
                   
                 # Raw Material 
                 EqWt 
                 Solids 
                 lb/gal 
                 lb/gal 
                 H20 
               
               
                   
                   
               
             
          
           
               
                 1. 
                 ASPARTIC BLACK 
                 313.00 
                 100 
                 9.17 
                 0.00 
                 0 
               
               
                   
                 430 
               
               
                 2. 
                 WOLLASTOCOAT 
                 0.00 
                 100 
                 24.20 
                 0.00 
                 0 
               
               
                   
                 M-400 AS 
               
               
                 3. 
                 ACEMAT HK 188 
                 0.00 
                 100 
                 17.50 
                 7.51 
                 0 
               
               
                 4. 
                 BYK 307 10% IN 
                 0.00 
                 9 
                 7.61 
                 7.51 
                 0 
               
               
                   
                 EA 
               
               
                 5. 
                 ACETATE 
                 0.00 
                 0 
                 7.29 
                 7.29 
                 0 
               
               
                 6. 
                 DESMODUR N100 
                 382.00 
                 50 
                 8.40 
                 7.53 
                 0 
               
               
                   
                 50% CUT 
               
               
                 1. 
                 ASPARTIC BLACK 
                 207.92 
                 22.67 
                 207.92 
                 22.67 
                 0 
               
               
                   
                 430 
               
               
                 2. 
                 WOLLASTOCOAT 
                 158.06 
                 6.53 
                 158.06 
                 6.53 
                 0 
               
               
                   
                 M-400 AS 
               
               
                 3. 
                 ACEMAT HK 188 
                 29.64 
                 1.69 
                 29.64 
                 1.69 
                 0 
               
               
                 4. 
                 BYK 307 10% IN 
                 1.80 
                 0.24 
                 0.16 
                 0.02 
                 0 
               
               
                   
                 EA 
               
               
                 5. 
                 ACETATE 
                 137.23 
                 18.82 
                 0.00 
                 0.00 
                 0 
               
               
                 6. 
                 DESMODUR N100 
                 420.33 
                 50.04 
                 210.17 
                 22.13 
                 0 
               
               
                   
                 50% CUT 
                   
               
               
                 7. 
                 Total 
                 954.99 
                 100.00 
                 605.95 
                 53.05 
               
               
                   
               
             
          
           
               
                   
                 Weight Solids, ⅔ = 
                 63.45 
                 Weight/gallon = 
                 9.55 
               
               
                   
                 Volume Solids, ⅓ = 
                 53.05 
                 NCO: OH Ratio = 
                 1.66 
               
               
                   
                 P/3 Ratio = 
                 0.45 
                 Mix Ratio = 
                 1.00 
               
               
                   
                 PVC, % = 
                 15.51 
                 VOC, lbs/gal = 
                 3.49 
               
               
                   
                   
               
               
                   
                 # Raw Material 
               
               
                   
                 1. a polyaspartic ester from Bayer Material Science, Pittsburgh, PA. 
               
               
                   
                 2. a surface modified wollastonite from NYCO, Calgary, Alberta, Canada 
               
               
                   
                 3. a filler/glass flattening agent from Degausa Corp., Düsseldorf, Germany 
               
               
                   
                 4. a silicon surface additive from Byk Chemie, Wessel, Germany 
               
               
                   
                 5. Acetate 
               
               
                   
                 6. An aliphatic polyisocyanate from Bayer Material Science, Pittsburgh, PA. 
               
             
          
         
       
     
     EXAMPLE 6 
     High Gloss White 
     In this example High Gloss White coatings were prepared as follows: 
     
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 6 
               
               
                   
                   
               
             
             
               
                   
                   
                   
                 Percent 
                 Suppl 
                 Solvent 
                 % 
               
               
                   
                 # Raw Material 
                 EqWt 
                 Solids 
                 lb/gal 
                 lb/gal 
                 H20 
               
               
                   
                   
               
             
          
           
               
                 1. 
                 DESMOPHEN 7053 
                 277.00 
                 100 
                 8.83 
                 0.00 
                 0 
               
               
                 2. 
                 Ti-Pure R-900 
                 0.00 
                 100 
                 33.30 
                 0.00 
                 0 
               
               
                 3. 
                 Aerosil 200 
                 0.00 
                 100 
                 18.40 
                 0.00 
                 0 
               
               
                 4. 
                 Aerosil R-972 
                 0.00 
                 100 
                 18.40 
                 0.00 
                 0 
               
               
                 5. 
                 Disperbyk-160 
                 0.00 
                 29 
                 7.93 
                 7.27 
                 0 
               
               
                 6. 
                 BYK 307 10% IN 
                 0.00 
                 9 
                 7.61 
                 7.51 
                 0 
               
               
                   
                 EA 
               
               
                 7. 
                 ACETATE 
                 0.00 
                 0 
                 7.29 
                 7.29 
                 0 
               
               
                 8. 
                 DESMODUR 
                 272.00 
                 70 
                 8.90 
                 7.51 
                 0 
               
               
                   
                 N-100/ea 30% 
               
               
                 1. 
                 DESMOPHEN 7053 
                 181.67 
                 20.57 
                 181.67 
                 20.57 
                 0 
               
               
                 2. 
                 Ti-Pure R-900 
                 442.67 
                 13.29 
                 442.67 
                 13.29 
                 0 
               
               
                 3. 
                 Aerosil 200 
                 1.89 
                 0.10 
                 1.89 
                 0.10 
                 0 
               
               
                 4. 
                 Aerosil R-972 
                 2.83 
                 0.15 
                 2.83 
                 0.15 
                 0 
               
               
                 5. 
                 Disperbyk-160 
                 4.72 
                 0.59 
                 1.37 
                 0.13 
                 0 
               
               
                 6. 
                 BYK 307 10% IN 
                 1.89 
                 0.25 
                 0.17 
                 0.02 
                 0 
               
               
                   
                 EA 
               
               
                 7. 
                 ACETATE 
                 109.19 
                 14.98 
                 0.00 
                 0.00 
                 0 
               
               
                 8. 
                 DESMODUR 
                 445.49 
                 50.05 
                 311.84 
                 32.26 
                 0 
               
               
                   
                 N-100/ea 30% 
                   
               
               
                 9. 
                 Total 
                 1190.35 
                 100.00 
                 942.44 
                 66.54 
               
               
                   
               
             
          
           
               
                   
                 Weight Solids, ⅔ = 
                 79.17 
                 Weight/gallon = 
                 11.90 
               
               
                   
                 Volume Solids, ⅓ = 
                 66.54 
                 NCO:OH Ratio = 
                 2.50 
               
               
                   
                 P/B Ratio = 
                 0.91 
                 Mix Ratio = 
                 1.00 
               
               
                   
                 PVC, % = 
                 20.41 
                 VOC, lbs/gal = 
                 2.48 
               
               
                   
                   
               
               
                   
                 # Raw Material 
               
               
                   
                 1. a polyaspartic ester from Bayer Material Science, Pittsburgh, PA. 
               
               
                   
                 2. titanium dioxide from DuPont de Nemours, Willmington, Delaware. 
               
               
                   
                 3. a silicon from Degausa Corp., Düsseldorf, Germany 
               
               
                   
                 4. a silicon from Degausa Corp., Düsseldorf, Germany 
               
               
                   
                 5. a wetting agent from BYK Chemie, Wessel, Germany 
               
               
                   
                 6. a silicon surface additive from BYK Chemie, Wessel, Germany 
               
               
                   
                 7. Acetate 
               
               
                   
                 8. An aliphatic polyisocyanate from Bayer Material Science, Pittsburgh, PA. 
               
             
          
         
       
     
     EXAMPLE 7 
     Blended Aspartic 
     In this example a blend of polyaspartic esters was used to prepare coating as follows: 
     
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 7 
               
               
                   
                   
               
             
             
               
                   
                   
                   
                 Percent 
                 Suppl 
                 Solvent 
                 % 
               
               
                   
                 # Raw Material 
                 EqWt 
                 Solids 
                 lb/gal 
                 lb/gal 
                 H20 
               
               
                   
                   
               
             
          
           
               
                 1. 
                 DESMOPHEN 7053 
                 277.00 
                 100 
                 8.83 
                 0.00 
                 0 
               
               
                 2. 
                 DESMOPHEN 7052 
                 325.00 
                 90 
                 8.66 
                 7.35 
                 0 
               
               
                 3. 
                 Ti-Pure R-900 
                 0.00 
                 100 
                 33.30 
                 0.00 
               
               
                 4. 
                 BAROTE 1075 
                 0.00 
                 100 
                 33.00 
                 0.00 
                 0 
               
               
                 3. 
                 Aerosil 200 
                 0.00 
                 100 
                 18.40 
                 0.00 
                 0 
               
               
                 6. 
                 Methyl Ethyl 
                 0.00 
                 9 
                 6.71 
                 6.71 
                 0 
               
               
                   
                 Ketone 
               
               
                 7. 
                 DESMODUR 
                 224.00 
                 85 
                 9.19 
                 7.51 
                 0 
               
               
                   
                 N-100/ea 15% 
               
               
                 1. 
                 DESMOPHEN 7053 
                 122.83 
                 13.91 
                 122.83 
                 13.91 
                 0 
               
               
                 2. 
                 DESMOPHEN 7052 
                 18.70 
                 2.16 
                 16.83 
                 1.91 
                 0 
               
               
                 3. 
                 Ti-Pure R-900 
                 436.44 
                 13.11 
                 436.44 
                 13.11 
                 0 
               
               
                 4. 
                 BAROTE 1075 
                 87.29 
                 2.65 
                 87.29 
                 2.65 
                 0 
               
               
                 3. 
                 Aerosil 200 
                 4.36 
                 0.24 
                 4.36 
                 0.24 
                 0 
               
               
                 6. 
                 Methyl Ethyl 
                 288.07 
                 25.01 
                 0.00 
                 0.00 
                 0 
               
               
                   
                 Ketone 
               
               
                 7. 
                 DESMODUR 
                 229.84 
                 25.01 
                 195.37 
                 20.42 
                 0 
               
               
                   
                 N-100/ea 15% 
                   
               
               
                 8. 
                 Total 
                 1187.53 
                 100.00 
                 863.12 
                 52.22 
               
               
                   
               
             
          
           
               
                   
                 Weight Solids, ⅔ = 
                 72.68 
                 Weight/gallon = 
                 11.88 
               
               
                   
                 Volume Solids, ⅓ = 
                 52.22 
                 NCO:OH Ratio = 
                 2.05 
               
               
                   
                 P/B Ratio = 
                 1.58 
                 Mix Ratio = 
                 3.00 
               
               
                   
                 PVC, % = 
                 30.62 
                 VOC, lbs/gal = 
                 3.24 
               
               
                   
                   
               
               
                   
                 # Raw Material 
               
               
                   
                 1. a polyaspartic ester from Bayer Material Science, Pittsburgh, PA. 
               
               
                   
                 2. a polyaspartic ester from Bayer Material Science, Pittsburgh, PA. 
               
               
                   
                 3. titanium dioxide from Degausa Corp., Düsseldorf, Germany 
               
               
                   
                 4. barium sulfate 
               
               
                   
                 5. a silicon from Degausa Corp., Düsseldorf, Germany 
               
               
                   
                 6. Methyl Ethyl Ketone 
               
               
                   
                 7. an aliphatic polyisocyanate from Bayer Material Science, Pittsburgh, PA. 
               
             
          
         
       
     
     EXAMPLE 8 
     Metallic Over Indexed 
     In this example coatings having a metallic finish were prepared as follows: 
     
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 8 
               
               
                   
                   
               
             
             
               
                   
                   
                   
                 Percent 
                 Suppl 
                 Solvent 
                 % 
               
               
                   
                 # Raw Material 
                 EqWt 
                 Solids 
                 lb/gal 
                 lb/gal 
                 H20 
               
               
                   
                   
               
             
          
           
               
                 1. 
                 DESMOPHEN 7053 
                 277.00 
                 100 
                 8.83 
                 0.00 
                 0 
               
               
                 2. 
                 Aerosil 200 
                 0.00 
                 100 
                 18.40 
                 0.00 
                 0 
               
               
                 3. 
                 Sparkle Silver 
                 0.00 
                 62 
                 12.08 
                 6.55 
                 0 
               
               
                   
                 5251-AR 
               
               
                 4. 
                 BYK 307 10% IN 
                 0.00 
                 9 
                 7.61 
                 7.51 
                 0 
               
               
                   
                 EA 
               
               
                 5. 
                 Acetate 
                 0.00 
                 9 
                 7.53 
                 7.53 
                 0 
               
               
                 6. 
                 DESMODUR 
                 318.00 
                 60 
                 8.74 
                 7.51 
                 0 
               
               
                   
                 N-100/ea 40% 
               
               
                 1. 
                 DESMOPHEN 7053 
                 241.97 
                 27.40 
                 241.97 
                 27.40 
                 0 
               
               
                 2. 
                 Aerosil 200 
                 2.83 
                 0.15 
                 2.83 
                 0.15 
                 0 
               
               
                 3. 
                 Sparkle Silver 
                 54.67 
                 4.53 
                 33.90 
                 1.35 
                 0 
               
               
                   
                 5251-AR 
               
               
                 4. 
                 BYK 307 10% IN 
                 1.62 
                 0.21 
                 0.15 
                 0.02 
                 0 
               
               
                   
                 EA 
               
               
                 5. 
                 Acetate 
                 134.10 
                 17.81 
                 0.00 
                 0.00 
                 0 
               
               
                 6. 
                 DESMODUR 
                 436.09 
                 79.90 
                 261.65 
                 25.67 
                 0 
               
               
                   
                 N-100/ea 40% 
                   
               
               
                 7. 
                 Total 
                 871.28 
                 100.00 
                 540.50 
                 55.60 
               
               
                   
               
             
          
           
               
                   
                 Weight Solids, ⅔ = 
                 62.04 
                 Weight/gallon = 
                 8.71 
               
               
                   
                 Volume Solids, ⅓ = 
                 53.60 
                 NCO:OH Ratio = 
                 1.37 
               
               
                   
                 P/B Ratio = 
                 0.07 
                 Mix Ratio = 
                 1.00 
               
               
                   
                 PVC, % = 
                 2.71 
                 VOC, lbs/gal = 
                 3.31 
               
               
                   
                   
               
               
                   
                 # Raw Material 
               
               
                   
                 1. a polyaspartic ester from Bayer Material Science, Pittsburgh, PA. 
               
               
                   
                 2. a silicon from Degausa Corp., Düsseldorf, Germany 
               
               
                   
                 3. a metallic silver pigment 
               
               
                   
                 4. a silicon surface additive from BYK Chemie, Wessel, Germany 
               
               
                   
                 5. Acetate 
               
               
                   
                 6. an aliphatic polyisocyanate from Bayer Material Science, Pittsburgh, PA. 
               
             
          
         
       
     
     EXAMPLE 9 
     Blend with Aldimine 
     In this example a blend of polyaspartic esters was used to prepare coatings as follows: 
     
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 9 
               
               
                   
                   
               
             
             
               
                   
                   
                   
                 Percent 
                 Suppl 
                 Solvent 
                 % 
               
               
                   
                 # Raw Material 
                 EqWt 
                 Solids 
                 lb/gal 
                 lb/gal 
                 H20 
               
               
                   
                   
               
             
          
           
               
                 1. 
                 DESMOPHEN 7053 
                 277.00 
                 100 
                 8.83 
                 0.00 
                 0 
               
               
                 2. 
                 DESMOPHEN 7052 
                 325.00 
                 90 
                 8.66 
                 7.35 
                 0 
               
               
                 3. 
                 Desmophen XP-7076 
                 139.00 
                 100 
                 7.30 
                 0.00 
                 0 
               
               
                 4. 
                 BYK 307 10% IN EA 
                 0.00 
                 9 
                 7.61 
                 7.51 
                 0 
               
               
                 5. 
                 Byk-321 
                 0.00 
                 52 
                 7.51 
                 7.52 
                 0 
               
               
                 6. 
                 Acetate 
                 0.00 
                 0 
                 7.29 
                 7.29 
                 0 
               
               
                 7. 
                 Desmodur XP-7100 
                 205.00 
                 100 
                 9.50 
                 0.00 
                 0 
               
               
                 1. 
                 DESMOPHEN 7053 
                 214.31 
                 24.27 
                 214.31 
                 24.27 
                 0 
               
               
                 2. 
                 DESMOPHEN 7052 
                 71.12 
                 8.21 
                 64.01 
                 7.24 
                 0 
               
               
                 3. 
                 Desmophen XP-7076 
                 31.50 
                 4.32 
                 31.50 
                 4.32 
                 0 
               
               
                 4. 
                 BYK 307 10% IN EA 
                 0.95 
                 0.13 
                 0.09 
                 0.01 
                 0 
               
               
                 5. 
                 Byk-321 
                 0.00 
                 52 
                 7.51 
                 7.52 
                 0 
               
               
                 6. 
                 Acetate 
                 94.30 
                 12.94 
                 0.00 
                 0.00 
                 0 
               
               
                 7. 
                 Desmodur XP-7100 
                 475.73 
                 50.08 
                 475.73 
                 50.08 
                 0 
               
               
                 8. 
                 Total 
                 888.39 
                 100.00 
                 785.88 
                 85.95 
               
               
                   
               
             
          
           
               
                   
                 Weight Solids, ⅔ = 
                 88.46 
                 Weight/gallon = 
                 8.88 
               
               
                   
                 Volume Solids, ⅓ = 
                 85.95 
                 NCO:OH Ratio = 
                 1.90 
               
               
                   
                 P/B Ratio = 
                 0.00 
                 Mix Ratio = 
                 1.00 
               
               
                   
                 PVC, % = 
                 0.00 
                 VOC, lbs/gal = 
                 3.03 
               
               
                   
                   
               
               
                   
                 # Raw Material 
               
               
                   
                 1. a polyaspartic ester from Bayer Material Science, Pittsburgh, PA. 
               
               
                   
                 2. a polyaspartic ester from Bayer Material Science, Pittsburgh, PA. 
               
               
                   
                 3. a polyaspartic ester from Bayer Material Science, Pittsburgh, PA. 
               
               
                   
                 4. a silicon surface additive from BYK Chemie, Wessel, Germany 
               
               
                   
                 5. a silicon surface additive from BYK Chemie, Wessel, Germany 
               
               
                   
                 6. Acetate 
               
               
                   
                 7. an aliphatic polyisocyanate from Bayer Material Science, Pittsburgh, PA. 
               
             
          
         
       
     
     EXAMPLE 10 
     Childlife Green 
     In this example coatings having a childlike green finish were prepared as follows: 
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                   
               
               
                 CHILDLIFE GREEN POLYOL 
               
             
          
           
               
                 # Raw Material 
                 QUANTITY 
                 UNITS 
               
               
                   
               
             
          
           
               
                 DESMOPHEN NH1420 (XP-7053) DA- 
                 82.86 
                 Lb 
               
               
                 ASPARTIC YELLOW OXIDE SHADE PA 
                 51.79 
                 Lb 
               
               
                 GREEN ASPARTIC SHADE PASTE 
                 60.00 
                 Lb 
               
               
                 ASPARTIC BLACK SHADE PASTE 
                 30.00 
                 Lb 
               
               
                 WOLLASTACOAT M-400 (10012) 
                 273.59 
                 Lb 
               
               
                 DESMPHEN 1220 
                 54.45 
                 Lb 
               
               
                 BYK 307 10% IN ACETATE 
                 0.77 
                 Lb 
               
               
                 T-12 (10% IN PMA) 
                 1.27 
                 Lb 
               
               
                 ACETATE 99% 
                 16.04 
                 Lb 
               
               
                   
               
             
          
         
       
         
         
           
             1. a polyaspartic ester from Bayer Material Science, Pittsburgh, Pa. 
             2. color shade 
             3. color shade 
             4. color shade 
             5. color shade 
             6. a surface modified wollastonite from NYCO, Calgany, Alberta, Canada 
             7. a polyaspartic ester from Bayer Material Science, Pittsburgh, Pa. 
             8. a silicone surface additive from Byk Chemie, Wessel, Germany 
             9. a tin catalyst 
             10. Acetate 
           
         
       
    
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                   
               
               
                 PHYSICAL PROPERTIES 
               
             
          
           
               
                   
                 DESCRIPTION 
                 VALUE 
               
               
                   
                   
               
             
          
           
               
                   
                 TOTAL WEIGHT 
                 880.864 
               
               
                   
                 TOTAL VEH WT % 
                 100.000 
               
               
                   
                 PIGMENT WT % 
                 0.000 
               
               
                   
                 VOLATILE WT % 
                 30.000 
               
               
                   
                 ORG. SOLV. WT % 
                 30.000 
               
               
                   
                 SOLIDS WT % 
                 70.000 
               
               
                   
                 VEH SOLIDS WT % 
                 70.000 
               
               
                   
                 DENSITY 
                 8.809 
               
               
                   
                 BULKING FACTOR 
                 0.114 
               
               
                   
                 P/B RATIO 
                 0.000 
               
               
                   
                 CPSFA @ 1 MIL 
                 0.0265 
               
               
                   
                 MATERIAL VOC 
                 316.662 
               
               
                   
                 TOTAL VOLUME 
                 100.000 
               
               
                   
                 TOTAL VEH VOL % 
                 100.000 
               
               
                   
                 PIGMENT VOL % 
                 0.000 
               
               
                   
                 VOLATILE VOL % 
                 35.094 
               
               
                   
                 ORG. SOLV. VOL % 
                 35.094 
               
               
                   
                 SOLIDS VOL % 
                 64.906 
               
               
                   
                 VEH SOLIDS VOL % 
                 64.906 
               
               
                   
                 SPEC. GRAVITY 
                 1.058 
               
               
                   
                 P.V.C. % 
                 0.000 
               
               
                   
                 SPREAD @ 1 MIL 
                 1041.089 
               
               
                   
                 COATING VOC 
                 316.662 
               
               
                   
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
             
           
               
                   
               
               
                 CHILDLIFE GREEN ACTIVATOR 
               
             
          
           
               
                 # RAW MATERIAL 
                 QUANTITY 
                 UNITS 
               
               
                   
               
               
                 DESMODUR N-100 (TOLONATE HDB) 
                 616.61 
                 Lb 
               
               
                 ACETATE 99% 
                 264.26 
                 Lb 
               
               
                   
               
             
          
         
       
         
         
           
             1. an aliphatic polyisocyanate from Bayer Material Science, Pittsburgh, Pa. 
             2. ethyl acetate 
           
         
       
    
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                   
               
               
                 PHYSICAL PROPERTIES 
               
             
          
           
               
                   
                 DESCRIPTION 
                 VALUE 
               
               
                   
                   
               
             
          
           
               
                   
                 TOTAL WEIGHT 
                 629.948 
               
               
                   
                 TOTAL VEH WT % 
                 44.389 
               
               
                   
                 PIGMENT WT % 
                 55.611 
               
               
                   
                 VOLATILE WT % 
                 3.331 
               
               
                   
                 ORG. SOLV. WT % 
                 2.728 
               
               
                   
                 SOLIDS WT % 
                 96.669 
               
               
                   
                 VEH SOLIDS WT % 
                 41.057 
               
               
                   
                 DENSITY 
                 13.295 
               
               
                   
                 BULKING FACTOR 
                 0.075 
               
               
                   
                 P/B RATIO 
                 0.354 
               
               
                   
                 CPSFA @ 1 MIL 
                 0.0180 
               
               
                   
                 MATERIAL VOC 
                 43.455 
               
               
                   
                 TOTAL VOLUME 
                 47.384 
               
               
                   
                 TOTAL VEH VOL % 
                 70.363 
               
               
                   
                 PIGMENT VOL % 
                 29.637 
               
               
                   
                 VOLATILE VOL % 
                 5.988 
               
               
                   
                 ORG. SOLV. VOL % 
                 4.793 
               
               
                   
                 SOLIDS VOL % 
                 94.012 
               
               
                   
                 VEH SOLIDS VOL % 
                 64.375 
               
               
                   
                 SPEC. GRAVITY 
                 1.597 
               
               
                   
                 P.V.C. % 
                 31.524 
               
               
                   
                 SPREAD @ 1 MIL 
                 1507.950 
               
               
                   
                 COATING VOC 
                 43.980 
               
               
                   
                   
               
             
          
         
       
     
     EXAMPLE 11 
     Gloss White Over Zinc Rich Primer 
     In this example Gloss White coatings of the present invention were topcoated over a zinc rich moisture cure urethane (i.e. zinc rich urethane-ZRU) primer. 
     
       
         
               
             
               
               
             
               
             
               
               
             
               
             
               
               
               
             
               
             
               
               
             
           
               
                   
               
               
                 ZRU PRIMER 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Finish: 
                 Flat 
               
               
                 Color: 
                 Gray 
               
               
                 Volume Solids: 
                 63% ± 2% 
               
               
                 Weight Solids: 
                 87.9% ± 2% 
               
               
                 Theoretical VOC: 
                 &lt;340 g/l: 2.8 lbs/gal 
               
               
                 Zinc Content in Dry Film: 
                 86% ± 2% 
               
             
          
           
               
                 Theoretical Coverage 
               
             
          
           
               
                 Wet mils: 
                 3.0 to 8.0 
               
               
                 Dry mils: 
                 2.0 to 5.0 above profile 
               
               
                 Coverage: 
                 202 to 336 sq ft theoretical 
               
             
          
           
               
                 Drying Schedule @ 5.0 mils wft 77° F. 5% RH: 
               
             
          
           
               
                   
                 Unaccelerated 
                 Accelerated 
               
               
                 To Touch: 
                 20 minutes 
                 5 minutes 
               
               
                 To recoat: atomospheric 
                 4–6 hours 
                 5 minutes 
               
               
                 To cure: atomospheric 
                 3 days 
                 6–8 hours 
               
             
          
           
               
                 Drying time is temperature, humidity and film thickness dependent. 
               
             
          
           
               
                 Shelf Life: 
                 6 months unopened 
               
               
                   
                 Store indoor at 40° F.–100° F. 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
             
               
             
               
               
               
               
             
               
               
               
               
             
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                   
               
               
                 GLOSS WHITE TOPCOAT 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Finish: 
                 Gloss White 
               
               
                 Volume Solids: 
                 53.5%–85.5% ± 2% 
               
               
                 Weight Solids: 
                 60%–88% ± 2% 
               
               
                 Theoretical VOC: 
                 &lt;384 g/l: 3.2 lbs/gal* 
               
               
                 Typical Exampel - can vary based on 
               
               
                 customer requirements with higher 
               
               
                 solids lower VOC capability. 
               
               
                 Mix Ratio: 
                 1:1 to 2:1 
               
               
                 Induction Time: 
                 None 
               
               
                 Theoretical Coverage: 
               
               
                 @ 57% Volume Solids equals 914 sq ft 
               
               
                 @1 mil DFT 
               
               
                 Shelf Life: 
                 12 months unopened 
               
               
                   
                 Store indoor at 40° F.–100° F. 
               
               
                 Hardness: 
                 H–2H 
               
               
                 Direct Impact: 
                 &gt;320 inch/lbs 
               
               
                 Reverse Impact: 
                 &gt;160 inch/lbs 
               
               
                 Conical Mandrel: 
                 ⅛″ pass 
               
               
                 Gravel-O-Meter: 
                 5+ 
               
               
                 Graffiti and Chemical Resistance: 
                 Good 
               
               
                 Salt Spray Direct: 
               
               
                 B-1000 @ 2.5 mils DFT 
                 &gt;500 hours 
               
               
                 Gloss White @ 2.5 mils DFT 
               
               
                 Over 3.5 mils DFT ZRU 
                 &gt;10,000 hours 
               
               
                 Drying Schedule @ 2.0 mils WFT 
               
               
                   
                 77° F. 50% RH 
               
               
                 To Touch: 
                 20 minutes 
               
               
                 To Handle: 
                 40 minutes 
               
               
                 Drying time is temperature, humidity 
               
               
                 and film thickness dependent. 
               
               
                 Weathering: 
               
               
                   
               
             
          
           
               
                 QUV-A 
               
               
                 Gloss White 
               
             
          
           
               
                   
                 60 Gloss 
                   
                 D E* 
               
             
          
           
               
                   
                 Initial 
                 2400 hours 
                 2400 hours 
               
               
                   
                   
               
               
                   
                 92 
                 88 
                 &lt;2.0 
               
               
                   
                   
               
             
          
           
               
                 Florida 
               
               
                 Gloss White 
               
             
          
           
               
                   
                 60 Gloss 
                   
                 D E* 
               
             
          
           
               
                   
                 Initial 
                 24 months 
                 24 months 
               
               
                   
                   
               
               
                   
                 92 
                 87 
                 &lt;2.5 
               
               
                   
                   
               
             
          
         
       
     
     RECOMMENDED USES 
     
         
         On steel, aluminum and galvanized where resistance to rust and corrosion undercutting is required 
         As a primer for urethane coatings system 
         Low temperature cure application 
         As a spot primer on hand and power tool cleaned surfaces 
         Product Finish 
         Structural Steel 
         General Maintenance 
         Industrial and Transportation 
       
    
     From the above examples, it can be seen that the properties of the polyurea coating compositions of the present invention begin improving as the polyaspartic ester is over indexed with polyisocyanate at above a 1.00 and continues to improve up to a stoichiometric index of about 2.25, after which the properties maintain the level of improvement. 
     Although the present invention has been described with reference to particular means, materials and embodiments, from the foregoing description, one skilled in the art can easily ascertain the essential characteristics of the present invention and various changes and modifications can be made to adapt the various uses and characteristics without departing from the spirit and scope of the present invention as described above and set forth in the following claims.

Technology Classification (CPC): 2