Patent Publication Number: US-4923097-A

Title: Aerosol paint compositions

Description:
This application is a continuation of application Ser. No. 304,573 filed Jan. 31, 1989, now abandoned, which is a continuation of application Ser. No. 144,581 filed Dec. 30, 1987, now abandoned, which is a continuation of application Ser. No. 893,881 filed Aug. 6, 1986 now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     This invention relates to solvent-based (non-aqueous) aerosol paints containing dimethyl ether as solvent or solvent and propellant. 
     A solvent-based aerosol paint contains both a propellant and a film-forming paint resin formulation. Most commercial solvent-based aerosol paints contain mixtures of low molecular weight hydrocarbons as the propellant; most commonly, a blend of propane and isobutane is used. A paint resin formulation generally contains a paint resin(s), pigments, diluting and coalescing or film-forming solvents, and various additives, such as drying agents, thickeners, surfactants, antiskinning agents, plasticizers, mildewcides, mar-resistant agents, antiflooding agents, etc. 
     To form a uniform, smooth coating when a solvent-based aerosol paint is applied to a surface and allowed to dry, the paint resin(s) in the paint must be in a single phase with the solvents and propellant during application. The propellant can also function as a solvent in the paint. The other ingredients in the paint resin formulation, i.e., pigments and additives, may be dispersed or suspended in the paint; however, it is important that the paint resin(s) be in solution for satisfactory application of paints to substrates. 
     The low molecular weight hydrocarbon propellants are quite poor solvents for many paint resins and additional relatively powerful solvents are required in commercial aerosol paints as components of the diluting and coalescing or film-forming solvents in order to solubilize these resins. The solvents commonly used in solvent-based aerosol paints for solubilization of the paint resins are aromatic compounds such as toluene or xylene, various ethylene glycol ethers and methylene chloride. These compounds are good solvents and produce excellent solvent-based aerosol paints. 
     A problem with the use of these solvents, however, is their potential toxicity to humans when exposure results during normal use or when deliberate abuse occurs (inhalation). In many instances, the ethylene glycol ethers are being replaced in aerosol paints with the safer propylene glycol ether solvents. However, great difficulty has been experienced in finding good substitutes for the aromatic solvents and methylene chloride and special handling, storage and application procedures may be required in the near future when using aerosol paints which contain these solvents. 
     The introduction of dimethyl ether (DME) as an aerosol propellant has provided the opportunity to formulate attractive, low-toxicity solvent-based (non-aqueous) aerosol paints without requiring the use of toxic aromatic solvents or methylene chloride. 
     SUMMARY OF THE INVENTION 
     A solvent-based aerosol paint has been discovered comprising an effective amount of DME as a solvent or solvent and propellant and a non-aqueous paint resin formulation which contains a paint resin(s) which without dimethyl ether would require the use of a powerful solvent to solubilize the paint resin(s) when a blend of low-molecular weight hydrocarbons is the only propellant. 
     DETAILED DESCRIPTION 
     According to the present invention, DME has been found to be unexpectedly useful as the solvent or solvent and propellant in a non-aqueous aerosol paint by providing to the paint sufficient solubility characteristics to ensure that the resin/solvent/propellant system will be a single phase. DME provides the means for achieving this necessary aim without the need for the incorporation of aromatic solvents such as toluene and xylene or methylene chloride which are needed to solubilize many paint resins in hydrocarbon-propelled paints. Without the resin(s) being soluble in the solvent/propellant portion of the paint, satisfactory paint films on substrates are not possible. 
     By solvent-based aerosol paint is meant a non-aqueous paint capable of being applied to a surface from an aerosol container which contains both a propellant and a paint resin formulation. A paint resin formulation generally contains a paint resin(s), pigments, diluting and coalescing or film-forming solvents, and various additives, such as drying agents, thickeners, surfactants, antiskinning agents, plasticizers, mildewcides, mar-resistant agents, antiflooding agents, etc. 
     By paint resin is meant a polymeric material which is soluble in the paint resin/solvent/propellant system to produce a non-aqueous solution which can be sprayed satisfactorily from an aerosol can and which upon drying provides a flexible, durable, non-tacky film of the desired gloss. 
     By effective amount of DME is meant an amount of DME which causes the paint resin(s), any other solvents and propellants present, and the DME to form a single phase system in a non-aqueous solvent-based aerosol paint. 
     By powerful solvent is meant a liquid or mixture of liquids which has a Kauri-Butanol No. of about 90 or greater or which will cause a single phase system of the solvent(s), the paint resin(s), and the propellant to be formed when a mixture of low-molecular weight hydrocarbons is used as the only propellant in a solvent-based aerosol paint. Examples of these solvents are aromatic compounds such as toluene or xylene, various ethylene glycol ethers and methylene chloride. 
     By low-molecular weight hydrocarbons is meant aliphatic hydrocarbons containing one to six carbon atoms and mixtures thereof. Most commonly in the United States, the term hydrocarbon propellant is used to describe blends of propane and isobutane. Mixtures of hydrocarbons exert partial vapor pressures which, in accordance with the ideal gas laws, are dependent upon their mole fraction contents of a particular mixture. 
     Examples of paint resins for which DME has been found to be unexpectedly useful as a solvent or solvent and propellant are styrene-modified alkyd resins, vinyl toluene-modified alkyd resins, acrylic-modified alkyd resins, phenol-formaldehyde/rosin-modified alkyd resins, silicone-modified alkyd resins, short-oil and oil-free alkyd resins, chain-stopped alkyd resins, nitrocellulose resins, silicone resins, and acrylic resins. This list is not meant to be exhaustive or limiting and other resins which are soluble in DME and which without DME would require the use of powerful solvents to solubilize them in solvent-based aerosol paints when low-molecular weight hydrocarbons are the only propellants are intended to be included in this invention. 
     It is surprising and unexpected that DME should be such a good solvent for the paint resins of this invention. The Kauri-Butanol No. is an indication of the relative solvent power of a particular liquid; the higher the Kauri Butanol No. the better the solvency of the product. The Kauri Butanol No. for DME in 60; whereas the Kauri Butanol Nos. for toluene and methylene chloride are 105 and 136, respectively. With this large difference between solubility numbers, one would expect DME to be less effective as a solvent for these paint resins than aromatic solvents and methylene chloride when they are used with hydrocarbon propellants in solvent-based aerosol paints. 
     It is not a requirement of the invention that DME be the only propellant in the aerosol paint. DME performs satisfactorily in conjunction with fluorocarbons such as difluorochloromethane (FC-22) and hydrocarbons. Thus, the FC-22/DME azeotrope containing 40 wt. percent FC-22 and 60 wt. percent DME functions well as an aerosol paint propellant while allowing the DME to provide both propellancy and solvency benefits. Simularly, DME can be used with hydrocarbons such as A-70 (about 41.9 wt. percent propane and 58.1 wt. percent isobutane with a vapor pressure of 70 psig at 70 degrees Fahrenheit) in various ratios. For example, a blend of 60 wt. percent DME and 40 wt. percent A-70 provides excellent and economical paint resin solubility. 
     An additional important part of this invention is the property of DME to allow the incorporation of solvent components which reduce the flammability of aerosol paints. Thus, methyl chloroform can be used with DME to reduce the flammability hazard of non-aqueous aerosol paints in use and particularly during warehouse storage. As an additional example, the incorporation of FC-22 in aerosol paints reduces their flammability since FC-22 is a non-flammable propellant. 
     In the aerosol paint of this invention, the DME may be present in an amount of about 10-60 wt. percent, preferrably about 15-45 wt. percent, and more preferrably about 18-45 wt. percent. The paint resin(s) may be present in an amount of about 5-30 wt. percent, preferrably about 7.5-15 wt. percent. In addition to DME, other propellants such as FC-22 or A-70 may be present in the paint in an amount of about 5-30 wt. percent, preferrably about 10-20 wt. percent. Also, in addition to DME, methyl chloroform can be present in an amount of about 10-60 wt. percent, preferrably about 20 to 40 wt. percent. Other ingredients such as pigments, surfactants, thickeners, driers, antiskinning agents, plasticizers, mildewcides, solvents such as propylene glycol monomethyl ether, VM and P naphtha, esters, alcohols, ketones and mineral spirits, and solvents which are incidental to both the paint resin(s) and other paint constituents to facilitate their handling may be included to complete the aerosol paint. 
     If DME is the only propellant present in the solvent-based aerosol paint of this invention, the DME may be present in an amount of about 25-45 wt. percent based on the total weight of the aerosol paint. 
     A particularly preferred paint according to the present invention is: 
     
         ______________________________________                                    
Ingredient             Wt. %                                              
______________________________________                                    
Organic Red Pigment.sup.1                                                 
                       10.0                                               
Vinyl Toluene-modified 15.0                                               
Alkyd Resin.sup.2                                                         
Methyl Chloroform      29.5                                               
PGME                   10.0                                               
Surfactant.sup.3        0.5                                               
DME                    35.0                                               
Vapor Pressure at 70° F., 37 PSIG                                  
______________________________________                                    
 .sup.1 &#34;Tint Ayd&#34; ST8673 (as purchased)                                  
 .sup.2 &#34;Styresol&#34; 13040 (as purchased)                                   
 .sup.3 &#34;Disperse Ayd&#34; #1 (as purchased)                                  
 
    
    
    
     The following examples will help to illustrate the practice of the present invention. 
     EXAMPLES 
     Solubility Tests 
     Solubility tests were conducted in 4 oz. plastic coated, glass pressure bottles. In these tests, the resin and solvents were combined in the pressure bottle and the aerosol valve was attached or crimped. Prior to attaching the valve, the bottle was purged of air with the propellant to be used in the solubility test. The propellant was introduced into the bottle as a liquid through the aerosol valve. Volume amounts corresponding to the weights of the propellants were calculated prior to loading, and a glass, calibrated pressure buret was used to measure and transfer the liquids from storage cylinders to the bottle. A nitrogen gas pressure of 100 psig was applied to the buret to aid in transferring the liquids from the buret to the bottle. After the propellant was loaded, the bottle was weighed and the weight of propellant recorded. 
     The solubility of the resin in the solvent/propellant system was visually determined by inspecting the pressure bottle for precipitated resin. If the contents of the pressure bottle were clear, the resin was determined to be soluble. Any sediment or precipitate resulted in a rating of insoluble. 
     Paint Tests 
     Paint samples were prepared in 3-piece lined 6 oz. aerosol can with Newman Green R-10-123 Valves (0.013 vapor tap and 120-20-18 actuator). The procedure for loading the samples into aerosol cans was the same as for the resin solubility tests, except glass agitating balls were placed in the cans to facilitate dispersion of pigments and other insolubles prior to spraying. The quality of the paints, as coatings, was determined by application to standard paint cards. 
     Chemicals Used in Tests 
     The following tables list the chemicals which were used in the above described tests. 
     
         ______________________________________                                    
Solvents                                                                  
Designation Structure/Properties                                          
                             Source                                       
______________________________________                                    
UCAR PM Solvent                                                           
            Propylene glycol Union Carbide                                
            monomethyl ether Corp.                                        
            (PGME)                                                        
UCAR PM Acetate                                                           
            Propylene glycol Union Carbide                                
            monomethyl ether Corp.                                        
            acetate (PGMEA)                                               
VM and P Naphtha                                                          
            52° F. flash point                                     
                             --                                           
            (TCC)                                                         
Mineral Spirits                                                           
            10°  F. flash point                                    
                             --                                           
            (TCC)                                                         
&#34;Aerothene&#34; TT                                                            
            Methyl chloroform                                             
                             Dow Chemical                                 
                             Co.                                          
DBE         Mixture of dimethyl                                           
                             Du Pont Co.                                  
            adipate, glutarate                                            
            and succinate                                                 
______________________________________                                    
Pigments                                                                  
Designation*         Color                                                
______________________________________                                    
&#34;Tint Ayd&#34; ST-8673   Deep Organic                                         
                     Red                                                  
&#34;Tint Ayd&#34; ST-8317   Tinting Black                                        
&#34;Tint Ayd&#34; ST-8451   Light Lemon                                          
                     (Yellow)                                             
&#34;Tint Ayd&#34; ST-8703   Phthalo Green                                        
&#34;Tint Ayd&#34; ST-8003   Titanium                                             
                     Dioxide                                              
                     (White)                                              
&#34;Tint Ayd&#34; ST-8298   Phthalo Blue                                         
&#34;Tint Ayd&#34; ST-8610   Red Oxide                                            
______________________________________                                    
 *Daniel Products Company                                                 
 
    
     
         Resins                                                                    
Designation Composition      Source                                       
______________________________________                                    
&#34;Beckosol&#34; 10-001                                                         
            Phenol-formaldehyde/                                          
                             Reichhold                                    
            rosin-modified alkyd                                          
                             Chemicals,                                   
            (50% AI in mineral                                            
                             Inc.                                         
            spirits)                                                      
&#34;Beckosol&#34; 10-638                                                         
            Silicone-modified alkyd                                       
                             Reichhold                                    
            (60% AI in mineral                                            
                             Chemicals,                                   
            spirits)         Inc.                                         
&#34;Beckosol&#34; 12-005                                                         
            Short-oil alkyd  Reichhold                                    
            (50% AI in Xylene)                                            
                             Chemicals,                                   
                             Inc.                                         
&#34;Beckosol&#34; 12-101                                                         
            Chain-stopped alkyd                                           
                             Reichhold                                    
            (50% AI in Xylene)                                            
                             Chemicals,                                   
                             Inc.                                         
&#34;Styresol&#34; 13-031                                                         
            Styrene-modified alkyd                                        
                             Reichhold                                    
            (50% AI in Xylene)                                            
                             Chemicals,                                   
                             Inc.                                         
&#34;Styresol&#34; 13-040                                                         
            Vinyl toluene-modified                                        
                             Reichhold                                    
            alkyd (50% AI in VM and                                       
                             Chemicals,                                   
            P Naphtha)       Inc.                                         
&#34;Lustrasol&#34; 13-046                                                        
            Acrylic-modified alkyd                                        
                             Reichhold                                    
            (50% AI in Xylene)                                            
                             Chemicals,                                   
                             Inc.                                         
&#34;Elvacite&#34; 2016                                                           
            Acrylic (100% AI)                                             
                             DuPont Co.                                   
&#34;Kepolac&#34; SSL-A                                                           
            Nitrocellulose   Henkel                                       
            (about 15% AI in mixed                                        
                             Corp.                                        
            solvent)                                                      
Dow Corning #804                                                          
            Silicone (60% AI in                                           
                             Dow                                          
            toluene)         Corning                                      
                             Corp.                                        
Dow Corning #840                                                          
            Silicone (60% AI in                                           
                             Dow                                          
            toluene)         Corning                                      
                             Corp.                                        
______________________________________                                    
 Note:                                                                    
 &#34;AI&#34; means &#34;active ingredient&#34;.                                          
 
    
     
         Surfactants                                                               
Designation Composition      Source                                       
______________________________________                                    
&#34;Triton&#34; X-15                                                             
            Octylphenoxy     Rohm &amp; Haas                                  
            polyethoxy       Co.                                          
            ethanol                                                       
FC-430      Fluorosurfactant 3M Company                                   
&#34;Disperse-Ayd&#34; 1                                                          
            Proprietary      Daniel                                       
                             Products Co.                                 
&#34;Disperse-Ayd&#34; 6                                                          
            Proprietary      Daniel                                       
                             Products Co.                                 
&#34;Disperse-Ayd&#34; 8                                                          
            Proprietary      Daniel                                       
                             Products Co.                                 
&#34; Disperse-Ayd&#34; XL                                                        
            Proprietary      Daniel                                       
1/80                         Products Co.                                 
______________________________________                                    
 
    
     The following tables are separated into two groups. The Paint Tables 1-15 show successful application to substrates of solvent-based aerosol paints which contain DME as solvent or solvent and propellant. The Solubility Tables 1-26 show the solubility of various paint resins when DME is present in the mixture. Both groups of tables use identified ingredients from the above listing of &#34;Chemicals Used in Tests&#34; with preparation and testing procedures as described in &#34;Solubility Tests&#34; and &#34;Paint Tests.&#34; All weight percentages for the indicated ingredients are on an &#34;as is&#34; or &#34;as purchased&#34; basis as listed in &#34;Chemicals Used in Tests&#34; above. 
     
                       PAINT TABLE 1                                               
______________________________________                                    
RED PAINT FORMULATIONS                                                    
           Wt. %                                                          
Formulation  1        2        3      4                                   
______________________________________                                    
Organic Red Pigment                                                       
             5.0      10.0     5.0    10.0                                
Styrene-modified                                                          
             15.0     15.0     --     --                                  
Alkyd Resin                                                               
Vinyl Toluene-                                                            
             --       --       15.0   --                                  
modified Alkyd Resin                                                      
Acrylic-modified                                                          
             --       --       --     15.0                                
Alkyd Resin                                                               
VM and P Naphtha                                                          
             24.5     19.5     24.5   19.5                                
PGME         10.0     10.0     10.0   10.0                                
&#34;Triton&#34; X-15                                                             
             0.5      0.5      0.5    0.5                                 
DME          45.0     45.0     45.0   45.0                                
Vapor Pressure at                                                         
             47       48       45     47                                  
70° F. PSIG                                                        
Appearance   Glossy,  Glossy,  Glossy,                                    
                                      Glossy,                             
             quick    quick    quick  quick                               
             drying   drying,  drying drying,                             
                      excellent       excellent                           
                      hiding          coverage                            
                      power                                               
______________________________________                                    
 
    
     
                       PAINT TABLE 2                                               
______________________________________                                    
BLACK PAINT FORMULATIONS                                                  
              Wt. %                                                       
Formulation     1          2                                              
______________________________________                                    
Black Pigment   10.0       10.0                                           
Styrene-modified                                                          
                15.0       --                                             
Alkyd Resin                                                               
Vinyl Toluene-  --         15.0                                           
modified Alkyd                                                            
Resin                                                                     
VM and P Naphtha                                                          
                19.5       19.5                                           
PGME            10.0       10.0                                           
&#34;Triton&#34; X-15    0.5        0.5                                           
DME/A-70 (60/40)                                                          
                45.0       45.0                                           
Vapor Pressure at                                                         
                53         52                                             
70° F. PSIG                                                        
Appearance      Glossy,    Glossy,                                        
                quick drying                                              
                           quick drying                                   
______________________________________                                    
 
    
     
                       PAINT TABLE 3                                               
______________________________________                                    
YELLOW PAINT FORMULATION                                                  
                Wt. %                                                     
Formulation     1                                                         
______________________________________                                    
Light Lemon Pigment                                                       
                10.0                                                      
Styrene-modified                                                          
                15.0                                                      
Alkyd Resin                                                               
VM and P Naphtha                                                          
                24.5                                                      
PGME            5.0                                                       
&#34;Triton&#34; X-15   0.5                                                       
DME             45.0                                                      
Vapor Pressure at                                                         
                50                                                        
70° F. PSIG                                                        
Appearance      Glossy, quick drying,                                     
                excellent                                                 
                hiding power                                              
______________________________________                                    
 
    
     
                       PAINT TABLE 4                                               
______________________________________                                    
YELLOW PAINT FORMULATIONS                                                 
           Wt. %                                                          
Formulation  1          2         3                                       
______________________________________                                    
Light Lemon Pigment                                                       
             10.0       10.0      10.0                                    
Vinyl Toluene-                                                            
             15.0       15.0      15.0                                    
modified Alkyd Resin                                                      
VM and P Naphtha                                                          
             34.5       34.5      34.5                                    
PGME         10.0       10.0      10.0                                    
&#34;Triton&#34; X-15                                                             
              0.5        0.5       0.5                                    
DME          30.0       --        --                                      
FC-22/DME (40/60)                                                         
             --         30.0      --                                      
DME/A-70 (60/40)                                                          
             --         --        30.0                                    
Vapor Pressure at                                                         
             36         30        40                                      
70° F. PSIG                                                        
Appearance   Glossy, quick drying, good hiding power                      
______________________________________                                    
 
    
     
                       PAINT TABLE 5                                               
______________________________________                                    
GREEN PAINT FORMULATIONS                                                  
               Wt. %                                                      
Formulation      1           2                                            
______________________________________                                    
Phthalo Green Pigment                                                     
                 10.0        10.0                                         
Styrene-modified 15.0        --                                           
Alkyd Resin                                                               
Vinyl Toluene-modified                                                    
                 --          15.0                                         
Alkyd Resin                                                               
VM and P Naphtha 19.5        19.5                                         
PGME             10.0        10.0                                         
&#34;Triton&#34; X-15     0.5         0.5                                         
FC-22/DME (40/60)                                                         
                 45.0        45.0                                         
Vapor Pressure at                                                         
                 41          41                                           
70° F. PSIG                                                        
Appearance       Glossy,     Glossy,                                      
                 quick drying                                             
                             quick drying                                 
______________________________________                                    
 
    
     
                       PAINT TABLE 6                                               
______________________________________                                    
PAINT FORMULATIONS                                                        
          Wt. %                                                           
Formulation 1      2       3    4     5    6                              
______________________________________                                    
White Pigment                                                             
            10.0   --      --   10.0  --   --                             
Phthalo Green                                                             
            --     10.0    --   --    10.0 --                             
Pigment                                                                   
Phthalo Blue                                                              
            --     --      10.0 --    --   10.0                           
Pigment                                                                   
Styrene-mod.                                                              
            15.0   15.0    15.0 --    --   --                             
Alkyd Resin                                                               
Vinyl Toluene-                                                            
            --     --      --   15.0  15.0 15.0                           
modified                                                                  
Alkyd Resin                                                               
VM and P    19.5   19.5    19.5 19.5  19.5 19.5                           
Naphtha                                                                   
PGME        10.0   10.0    10.0 10.0  10.0 10.0                           
&#34;Triton&#34; X-15                                                             
             0.5    0.5     0.5  0.5   0.5  0.5                           
DME         45.0   45.0    45.0 45.0  45.0 45.0                           
Vapor Pressure at                                                         
            48     48      48   49    47   48                             
70° F. PSIG                                                        
Appearance  All glossy, quick drying                                      
______________________________________                                    
 
    
     
                       PAINT TABLE 7                                               
______________________________________                                    
BLUE PAINT FORMULATION                                                    
                 Wt. %                                                    
Formulation      1                                                        
______________________________________                                    
Phthalo Blue Pigment                                                      
                 10.00                                                    
Vinyl Toluene-modified                                                    
                 15.00                                                    
Alkyd Resin                                                               
Methyl Chloroform                                                         
                 34.95                                                    
FC-430            0.05                                                    
DME              40.00                                                    
Vapor Pressure at                                                         
                 40                                                       
70° F. PSIG                                                        
Appearance       Glossy, quick drying                                     
______________________________________                                    
 
    
     
                       PAINT TABLE 8                                               
______________________________________                                    
RED PAINT FORMULATIONS                                                    
           Wt. %                                                          
Formulation  1       2       3     4     5                                
______________________________________                                    
Organic Red  10.00   10.00   10.00 10.00 10.00                            
Pigment                                                                   
Styrene-mod. 15.00   --      --    --    --                               
Alkyd Resin                                                               
Vinyl Toluene-                                                            
             --      5.00    --    15.00 15.00                            
mod. alkyd                                                                
resin                                                                     
Acrylic-mod. --      --      15.00 --    --                               
Alkyd Resin                                                               
PGME          5.00    5.00    5.00 --    --                               
Methyl       34.95   34.95   34.95 44.95 39.95                            
Chloroform                                                                
FC-430        0.05    0.05    0.05  0.05  0.05                            
DME          35.00   35.00   35.00 30.00 35.00                            
Vapor Pressure at                                                         
             36      35      35    32    36                               
70° F. PSIG                                                        
Appearance   High gloss, quick drying                                     
______________________________________                                    
 
    
     
                       PAINT TABLE 9                                               
______________________________________                                    
BLUE PAINT FORMULATIONS                                                   
           Wt. %                                                          
Formulation  1       2       3     4     5                                
______________________________________                                    
Phthalo Blue 10.00   10.00   10.00 10.00 10.00                            
Pigment                                                                   
Styrene-mod. 15.00   --      --    --    --                               
Alkyd Resin                                                               
Vinyl Toluene-                                                            
             --      15.00   --    15.00 15.00                            
mod. Alkyd                                                                
Resin                                                                     
Acrylic-mod. --      --      15.00 --    --                               
Alkyd Resin                                                               
PGME          5.00    5.00    5.00 ----                                   
Methyl       34.95   34.95   34.95 44.95 39.95                            
Chloroform                                                                
FC-430        0.05    0.05    0.05  0.05  0.05                            
DME          35.00   35.00   35.00 30.00 35.00                            
Vapor Pressure at                                                         
             35      35      34    31    35                               
70° F. PSIG                                                        
Appearance   High gloss, quick drying                                     
______________________________________                                    
 
    
     
                       PAINT TABLE 10                                              
______________________________________                                    
BLUE PAINT FORMULATIONS                                                   
              Wt. %                                                       
Formulation     1      2        3    4                                    
______________________________________                                    
Phthalo Blue    10.0   10.0     10.0 10.0                                 
Pigment                                                                   
Vinyl Toluene-  15.0   15.0     15.0 15.0                                 
mod. Alkyd Resin                                                          
VM and P naphtha                                                          
                19.5   19.5     19.5 19.5                                 
PGME            10.0   10.0     10.0 10.0                                 
&#34;Disperse Ayd&#34; #1                                                         
                 0.5   --       --   --                                   
&#34;Disperse Ayd&#34; #6                                                         
                --      0.5     --   --                                   
&#34;Disperse Ayd&#34; #8                                                         
                --     --        0.5 --                                   
&#34;Disperse Ayd&#34;  --     --       --    0.5                                 
XL-1/80                                                                   
DME             45.0   45.0     45.0 45.0                                 
Vapor Pressure at                                                         
                42     41       41   41                                   
70° F. PSIG                                                        
Appearance      Glossy, quick drying                                      
______________________________________                                    
 
    
     
                       PAINT TABLE 11                                              
______________________________________                                    
PAINT FORMULATIONS                                                        
             Wt. %                                                        
Formulation    1           2      3                                       
______________________________________                                    
Red Oxide Pigment                                                         
               10.0        10.0   10.0                                    
Silicone Resin*                                                           
               12.5        --     12.5                                    
Silicone Resin**                                                          
               --          12.5   --                                      
Methyl Chloroform                                                         
               32.0        32.0   32.0                                    
PGME           10.0        10.0   10.0                                    
&#34;Disperse Ayd&#34; #1                                                         
               0.5         0.5    0.5                                     
DME            45.0        45.0   --                                      
FC-22/DME (40/60)                                                         
               --          --     35.0                                    
Vapor Pressure at                                                         
               37          38     32                                      
70° F. PSIG                                                        
Appearance     Glossy, quick drying                                       
______________________________________                                    
 *Dow Corning #804                                                        
 **Dow Corning #840                                                       
 
    
     
                       PAINT TABLE 12                                              
______________________________________                                    
BLUE PAINT FORMULATIONS                                                   
       Wt. %                                                              
Formulation                                                               
         1      2      3    4    5    6    7    8                         
______________________________________                                    
Phthalo Blue                                                              
         10.0   10.0   10.0 10.0 10.0 10.0 10.0 10.0                      
Pigment                                                                   
Vinyl    15.0   15.0   15.0 15.0 15.0 15.0 15.0 15.0                      
Toluene-                                                                  
modified                                                                  
Alkyd Resin                                                               
Methyl   29.5   29.5   29.5 29.5 29.5 29.5 29.5 29.5                      
Chloroform                                                                
PGME     10.0   10.0   10.0 10.0 --   --   --   --                        
DBE      --     --     --   --   10.0 10.0 10.0 10.0                      
&#34;Disperse                                                                 
         0.5    --     --   --   0.5  --   --   --                        
Ayd&#34; #1                                                                   
&#34;Disperse                                                                 
         --     0.5    --   --   --   0.5  --   --                        
Ayd&#34; #6                                                                   
&#34;Disperse                                                                 
         --     --     0.5  --   --   --   0.5  --                        
Ayd&#34; #8                                                                   
&#34;Disperse                                                                 
         --     --     --   0.5  --   --   --   0.5                       
Ayd&#34; XL-1/80                                                              
DME      35.0   35.0   35.0 35.0 35.0 35.0 35.0 35.0                      
Vapor Press-                                                              
         36     37     36   36   36   37   37   36                        
ure at 70° F.                                                      
PSIG                                                                      
Appearance                                                                
         High gloss, quick drying #1 to 4; slow                           
         drying #5 to 8.                                                  
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                       PAINT TABLE 13                                              
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RED PAINT FORMULATIONS                                                    
             Wt. %                                                        
Formulation    1           2      3                                       
______________________________________                                    
Organic Red Pigment                                                       
               10.0        10.0   10.0                                    
Acrylic Resin  15.0        15.0   15.0                                    
VM and P Naphtha                                                          
               29.5        --     --                                      
PGME           10.0        10.0   --                                      
Methyl Chloroform                                                         
               --          29.5   39.5                                    
&#34;Disperse Ayd&#34; #1                                                         
               0.5         0.5    0.5                                     
DME            35.0        35.0   35.0                                    
Vapor Pressure at                                                         
               36          37     36                                      
70° F. PSIG                                                        
Appearance     High gloss, quick drying                                   
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                       PAINT TABLE 14                                              
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PAINT FORMULATIONS                                                        
              Wt. %                                                       
Formulation     1           2                                             
______________________________________                                    
White Pigment   15.0        --                                            
Phthalo Green   --          5.0                                           
Pigment                                                                   
Acrylic Resin   7.5         7.5                                           
Methyl Chloroform                                                         
                32.0        42.0                                          
PGME            10.0        10.0                                          
&#34;Disperse Ayd&#34; #1                                                         
                0.5         0.5                                           
DME             35.0        35.0                                          
Vapor Pressure at                                                         
                36          36                                            
70° F., PSIG                                                       
Appearance      Medium gloss,                                             
                            High gloss,                                   
                quick drying                                              
                            quick drying                                  
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                       PAINT TABLE 15                                              
______________________________________                                    
WHITE PAINT FORMULATIONS                                                  
           Wt. %                                                          
Formulation  1       2         3     4                                    
______________________________________                                    
White Pigment                                                             
             15.0    15.0      15.0  15.0                                 
Styrene-mod. 15.0    15.0      --    --                                   
Alkyd Resin                                                               
Vinyl Toluene-                                                            
             --      --        15.0  15.0                                 
mod. Alkyd Resin                                                          
VM &amp; P Naphtha                                                            
             --      24.5      --    24.5                                 
Methyl Chloro-                                                            
             24.5    --        24.5  --                                   
form                                                                      
PGME         10.0    10.0      10.0  10.0                                 
&#34;Disperse Ayd&#34;                                                            
             0.5     0.5       0.5   0.5                                  
#1                                                                        
DME          35.0    35.0      35.0  35.0                                 
Vapor Pressure at                                                         
             36      37        36    38                                   
70° F., PSIG                                                       
Appearance   Glossy, Very      Glossy,                                    
                                     Very                                 
             quick   glossy,   quick glossy,                              
             drying  quick     drying                                     
                                     quick                                
                     drying          drying                               
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                                           TABLE 1                                 
__________________________________________________________________________
SOLUBILITY                                                                
          Wt. %                                                           
Formulation                                                               
          1  2  3  4  5  6  7  8  9  10 11 12                             
__________________________________________________________________________
Styrene-modified                                                          
          15.0                                                            
             10.0                                                         
                10.0                                                      
                   10.0                                                   
                      10.0                                                
                         10.0                                             
                            10.0                                          
                               10.0                                       
                                  15.0                                    
                                     15.0                                 
                                        30.0                              
                                           60.0                           
Alkyd resin                                                               
VM and P naphtha                                                          
          40.0                                                            
             40.0                                                         
                20.0                                                      
                   55.0                                                   
                      30.0                                                
                         55.0                                             
                            30.0                                          
                               40.0                                       
                                  30.0                                    
                                     70.0                                 
                                        25.0                              
                                           40.0                           
Mineral spirits                                                           
          -- -- 20.0                                                      
                   -- 25.0                                                
                         -- 25.0                                          
                               -- -- -- -- --                             
PGME      --  5.0                                                         
                 5.0                                                      
                    5.0                                                   
                       5.0                                                
                         -- -- -- 10.0                                    
                                     -- -- --                             
PGMEA     -- -- -- -- --  5.0                                             
                             5.0                                          
                                5.0                                       
                                  -- -- -- --                             
DME       45.0                                                            
             45.0                                                         
                45.0                                                      
                   30.0                                                   
                      30.0                                                
                         30.0                                             
                            30.0                                          
                               45.0                                       
                                  45.0                                    
                                     15.0                                 
                                        45.0                              
                                           40.0                           
Solubility                                                                
          Sol.                                                            
             Sol.                                                         
                Sol.                                                      
                   Sol.                                                   
                      Sol.                                                
                         Sol.                                             
                            Sol.                                          
                               Sol.                                       
                                  Sol.                                    
                                     Sol.                                 
                                        Sol.                              
                                           Sol.                           
__________________________________________________________________________
 
    
     
                       SOLUBILITY TABLE 2                                          
______________________________________                                    
              Wt. %                                                       
Formulation     1      2        3    4                                    
______________________________________                                    
Styrene-modified                                                          
                5.0    10.0     10.0 15.0                                 
alkyd resin                                                               
VM and P naphtha                                                          
                40.0   40.0     40.0 30.0                                 
PGME            --     5.0      --   10.0                                 
PGMEA           --     --       5.0  --                                   
FC-22/DME       45.0   45.0     45.0 45.0                                 
(40/60)                                                                   
Solubility      Sol.   Sol.     Sol. Sol.                                 
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                       SOLUBILITY TABLE 3                                          
______________________________________                                    
                 Wt. %                                                    
Formulation        1       2                                              
______________________________________                                    
Styrene-modified   15.0    15.0                                           
alkyd resin                                                               
VM and P naphtha   40.0    30.0                                           
PGME               --      10.0                                           
DME/A-70           45.0    45.0                                           
(60/40)                                                                   
Solubility         Insol.  Sol.                                           
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                                           TABLE 4                                 
__________________________________________________________________________
SOLUBILITY                                                                
          Wt. %                                                           
Formulation                                                               
          1  2  3  4  5  6  7  8  9  10 11 12                             
__________________________________________________________________________
Vinyl toluene-                                                            
          15.0                                                            
             10.0                                                         
                10.0                                                      
                   10.0                                                   
                      10.0                                                
                         10.0                                             
                            10.0                                          
                               10.0                                       
                                  15.0                                    
                                     15.0                                 
                                        30.0                              
                                           60.0                           
modified alkyd                                                            
resin                                                                     
VM and P naphtha                                                          
          40.0                                                            
             40.0                                                         
                20.0                                                      
                   55.0                                                   
                      30.0                                                
                         55.0                                             
                            30.0                                          
                               40.0                                       
                                  30.0                                    
                                     70.0                                 
                                        25.0                              
                                           --                             
Mineral spirits                                                           
          -- -- 20.0                                                      
                   -- 25.0                                                
                         -- 25.0                                          
                               -- -- -- -- --                             
PGME      --  5.0                                                         
                 5.0                                                      
                    5.0                                                   
                       5.0                                                
                         -- -- -- 10.0                                    
                                     -- -- --                             
PGMEA     -- -- -- -- --  5.0                                             
                             5.0                                          
                                5.0                                       
                                  -- -- -- --                             
DME       45.0                                                            
             45.0                                                         
                45.0                                                      
                   30.0                                                   
                      30.0                                                
                         30.0                                             
                            30.0                                          
                               45.0                                       
                                  45.0                                    
                                     15.0                                 
                                        45.0                              
                                           45.0                           
Solubility                                                                
          Sol.                                                            
             Sol.                                                         
                Sol.                                                      
                   Sol.                                                   
                      Sol.                                                
                         Sol.                                             
                            Sol.                                          
                               Sol.                                       
                                  Sol.                                    
                                     Sol.                                 
                                        Sol.                              
                                           Sol.                           
__________________________________________________________________________
 
    
     
                       SOLUBILITY TABLE 5                                          
______________________________________                                    
             Wt. %                                                        
Formulation    1           2      3                                       
______________________________________                                    
Vinyl toluene- 15.0        10.0   10.0                                    
modified alkyd resin                                                      
VM and P naphtha                                                          
               40.0        40.0   40.0                                    
PGME           --          5.0    --                                      
PGMEA          --          --     5.0                                     
FC-22/DME      45.0        45.0   45.0                                    
(40/60)                                                                   
Solubility     Sol.        Sol.   Sol.                                    
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                       SOLUBILITY TABLE 6                                          
______________________________________                                    
                  Wt. %                                                   
Formulation         1      2                                              
______________________________________                                    
Vinyl toluene-      15.0   15.0                                           
modified alkyd                                                            
resin                                                                     
VM and P naphtha    40.0   30.0                                           
PGME                --     10.0                                           
DME/A-70            45.0   45.0                                           
(60/40)                                                                   
Solubility          Sol.   Sol.                                           
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                       SOLUBILITY TABLE 7                                          
______________________________________                                    
           Wt. %                                                          
Formulation  1      2      3     4     5    6                             
______________________________________                                    
Acrylic-modified                                                          
             15.0   10.0   15.0  15.0  30.0 60.0                          
alkyd resin                                                               
VM and P naphtha                                                          
             40.0   40.0   70.0  60.0  25.0 --                            
PGME         --     5.0    --    --    --   --                            
DME          45.0   45.0   15.0  25.0  45.0 40.0                          
Solubility   Sol.   Sol.   Insol.                                         
                                 Insol.                                   
                                       Sol. Sol.                          
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                       SOLUBILITY TABLE 8                                          
______________________________________                                    
                  Wt. %                                                   
Formulation         1      2                                              
______________________________________                                    
Acrylic-modified    10.0   10.0                                           
alkyd resin                                                               
VM and P naphtha    40.0   40.0                                           
PGME                --     5.0                                            
FC-22/DME           45.0   45.0                                           
(40/60)                                                                   
Solubility          Sol.   Sol.                                           
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                       SOLUBILITY TABLE 9                                          
______________________________________                                    
                 Wt. %                                                    
Formulation        1       2                                              
______________________________________                                    
Acrylic-modified   15.0    15.0                                           
alkyd resin                                                               
VM and P naphtha   40.0    30.0                                           
PGME               --      10.0                                           
DME/A-70           45.0    45.0                                           
(60/40)                                                                   
Solubility         Insol.  Insol.                                         
 
    
     
                       SOLUBILITY TABLE 10                                         
______________________________________                                    
           Wt. %                                                          
Formulation  1      2      3     4    5    6                              
______________________________________                                    
Phenol-      15.0   10.0   15.0  15.0 30.0 60.0                           
formaldehyde/                                                             
rosin-modified                                                            
alkyd resin                                                               
VM and P naphtha                                                          
             40.0   40.0   30.0  70.0 25.0 --                             
PGME         --     5.0    10.0  --   --   --                             
DME          45.0   45.0   45.0  15.0 45.0 40.0                           
Solubility   Sol.   Sol.   Sol.  Sol. Sol. Sol.                           
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                       SOLUBILITY TABLE 11                                         
______________________________________                                    
                  Wt. %                                                   
Formulation         1      2                                              
______________________________________                                    
Phenol-             15.0   10.0                                           
formaldehyde/                                                             
rosin-modified                                                            
alkyd resin                                                               
VM and P naphtha    40.0   40.0                                           
PGME                --      5.0                                           
FC-22/DME           45.0   45.0                                           
(40/60)                                                                   
Solubility          Sol.   Sol.                                           
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                       SOLUBILITY TABLE 12                                         
______________________________________                                    
                 Wt. %                                                    
Formulation        1       2                                              
______________________________________                                    
Phenol-            15.0    15.0                                           
formaldehyde/                                                             
rosin-modified                                                            
alkyd resin                                                               
VM and P naphtha   40.0    30.0                                           
PGME               --      10.0                                           
DME/A-70           45.0    45.0                                           
(60/40)                                                                   
Solubility         Insol.  Sol.                                           
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                       SOLUBILITY TABLE 13                                         
______________________________________                                    
             Wt. %                                                        
Formulation    1      2         3    4                                    
______________________________________                                    
Chain-stopped  15.0   30.0      60.0 15.0                                 
alkyd resin                                                               
VM and P naphtha                                                          
               30.0   --        --   --                                   
PGME           10.0   --        --   10.0                                 
Methyl chloroform                                                         
               --     --        --   40.0                                 
DME            45.0   70.0      40.0 35.0                                 
Solubility     Sol.   Sol.      Sol. Sol.                                 
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                       SOLUBILITY TABLE 14                                         
______________________________________                                    
          Wt. %                                                           
Formulation 1        2      3      4    5                                 
______________________________________                                    
Short-oil   15.0     10.0   15.0   30.0 60.0                              
alkyd resin                                                               
VM and P naphtha                                                          
            40.0     40.0   70.0   25.0 --                                
PGME        --        5.0   --     --   --                                
DME         45.0     45.0   15.0   45.0 40.0                              
Solubility  Sol.     Sol.   Sol.   Sol. Sol.                              
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                       SOLUBILITY TABLE 15                                         
______________________________________                                    
                  Wt. %                                                   
Formulation         1      2                                              
______________________________________                                    
Short-oil           15.0   10.0                                           
alkyd resin                                                               
VM and P naphtha    40.0   40.0                                           
PGME                --      5.0                                           
FC-22/DME           45.0   45.0                                           
(40/60)                                                                   
Solubility          Sol.   Sol.                                           
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                       SOLUBILITY TABLE 16                                         
______________________________________                                    
                  Wt. %                                                   
Formulation         1      2                                              
______________________________________                                    
Short-oil           15.0   15.0                                           
alkyd resin                                                               
VM and P naphtha    40.0   30.0                                           
PGME                --     10.0                                           
DME/A-70            45.0   45.0                                           
(60/40)                                                                   
Solubility          Sol.   Sol.                                           
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                       SOLUBILITY TABLE 17                                         
______________________________________                                    
          Wt. %                                                           
Formulation 1      2      3     4     5     6                             
______________________________________                                    
Acrylic resin                                                             
            15.0   15.0   15.0  15.0  15.0  30.0                          
VM and P naphtha                                                          
            40.0   45.0   30.0  70.0  60.0  --                            
PGME        --     10.0   10.0  --    --    --                            
DME         45.0   30.0   45.0  15.0  25.0  70.0                          
Solubility  Sol.   Sol.   Sol.  Insol.                                    
                                      Insol.                              
                                            Sol.                          
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                       SOLUBILITY TABLE 18                                         
______________________________________                                    
             Wt. %                                                        
Formulation    1           2      3                                       
______________________________________                                    
Acrylic resin  15.0        15.0   15.0                                    
VM and P naphtha                                                          
               40.0        45.0   30.0                                    
PGME           --          10.0   10.0                                    
FC-22/DME      45.0        30.0   45.0                                    
(40/60)                                                                   
Solubility     Sol.        Sol.   Sol.                                    
______________________________________                                    
 
    
     
                       SOLUBILITY TABLE 19                                         
______________________________________                                    
            Wt. %                                                         
Formulation   1           2       3                                       
______________________________________                                    
Acrylic resin 15.0        15.0    15.0                                    
VM and P naphtha                                                          
              40.0        45.0    30.0                                    
PGME          --          10.0    10.0                                    
DME/A-70      45.0        30.0    45.0                                    
(60/40)                                                                   
Solubility    Insol.      Insol.  Sol.                                    
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                       SOLUBILITY TABLE 20                                         
______________________________________                                    
             Wt. %                                                        
Formulation    1      2         3    4                                    
______________________________________                                    
Silicone-modified                                                         
               15.0   30.0      60.0 15.0                                 
alkyd resin                                                               
VM and P naphtha                                                          
               30.0   --        --   --                                   
PGME           10.0   --        --   10.0                                 
Methyl chloroform                                                         
               --     --        --   40.0                                 
DME            45.0   70.0      40.0 35.0                                 
Solubility     Sol.   Sol.      Sol. Sol.                                 
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                       SOLUBILITY TABLE 21                                         
______________________________________                                    
          Wt. %                                                           
Formulation 1      2       3    4      5    6                             
______________________________________                                    
Vinyl toluene-                                                            
            16.7   16.7    16.7 16.7   16.7 16.7                          
modified alkyd                                                            
resin                                                                     
VM and P naphtha                                                          
            13.3   13.3    13.3 --     --   --                            
Methyl chloroform                                                         
            20.0   30.0    40.0 43.3   53.3 48.3                          
DME         50.0   40.0    30.0 40.0   30.0 35.0                          
Solubility  Sol.   Sol.    Sol. Sol.   Sol. Sol.                          
______________________________________                                    
 
    
     
                       SOLUBILITY TABLE 22                                         
______________________________________                                    
             Wt. %                                                        
Formulation    1      2         3    4                                    
______________________________________                                    
Vinyl toluene- 16.7   16.7      16.7 16.7                                 
modified alkyd                                                            
resin                                                                     
VM and P naphtha                                                          
               13.3   13.3      13.3 --                                   
Methyl chloroform                                                         
               20.0   30.0      40.0 43.3                                 
FC-22/DME      50.0   40.0      30.0 40.0                                 
(40/60)                                                                   
Solubility     Sol.   Sol.      Sol. Sol.                                 
______________________________________                                    
 
    
     
                       SOLUBILITY TABLE 23                                         
______________________________________                                    
             Wt. %                                                        
Formulation    1           2      3                                       
______________________________________                                    
Acrylic resin  15.0        15.0   15.0                                    
VM and P naphtha                                                          
               --          10.0   --                                      
PGME           --          --     10.0                                    
Methyl chloroform                                                         
               50.0        40.0   40.0                                    
DME            35.0        35.0   35.0                                    
Solubility     Sol.        Sol.   Sol.                                    
______________________________________                                    
 
    
     
                       SOLUBILITY TABLE 24                                         
______________________________________                                    
             Wt. %                                                        
Formulation    1           2      3                                       
______________________________________                                    
Acrylic resin  15.0        15.0   15.0                                    
VM and P naphtha                                                          
               --          10.0   --                                      
PGME           --          --     10.0                                    
Methyl chloroform                                                         
               50.0        40.0   40.0                                    
FC-22/DME      35.0        35.0   35.0                                    
(40/60)                                                                   
Solubility     Sol.        Sol.   Sol.                                    
______________________________________                                    
 
    
     
                       SOLUBILITY TABLE 25                                         
______________________________________                                    
                   Wt. %                                                  
Formulation       1                                                       
______________________________________                                    
Nitrocellulose resin                                                      
                  55.0                                                    
DME               45.0                                                    
Solubility        Sol.                                                    
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                       SOLUBILITY TABLE 26                                         
______________________________________                                    
             Wt. %                                                        
Formulation    1      2         3    4                                    
______________________________________                                    
Dow Corning #804                                                          
               15.0   60.0      --   --                                   
Dow Corning #840                                                          
               --     --        15.0 60.0                                 
VM and P naphtha                                                          
               40.0   --        40.0 --                                   
DME            45.0   40.0      45.0 40.0                                 
Solubility     Sol.   Sol.      Sol. Sol.                                 
______________________________________