Patent Publication Number: US-4547397-A

Title: Tintable scratch resistant coating

Description:
This application is a continuation-in-part application of Ser. No. 671,535 filed Nov. 15, 1984. 
    
    
     The present invention relates to a hard, tintable, scratch resistant organopolysiloxane coating for a transparent substrate such as a polycarbonate lens. 
     BACKGROUND OF THE INVENTION 
     In the prior art, the commercially used tintable coatings for polycarbonate lens and the like provide only a 10-20% absorbency pick-up (single side) and the time required for the pick-up is at least 45 minutes. 
     Hence there is a need for a hard tintable scratch resistant coating for a transparent substrate such as a polycarbonate lens. The desired coating would have more dye pick-up than the present systems and the pick-up would be made in less time without sacrifice of reasonable hardness and good scratch resistance. 
     OBJECTS OF THE INVENTION 
     It is an object of the present invention to provide an organopolysiloxane coating for a transparent base such as a polycarbonate lens, the coating being more easily and effectively applied, the coating being applied in less time and resulting in a harder, more scratch and abrasion resistant coating with a high degree of tintability. 
     It is an object of the present invention to provide an organopolysiloxane coating for a transparent base such as a polycarbonate lens in which the coating is hard, scratch and abrasion resistant and highly tinted, the coating composition tinting to 70 to 80% absorbency in a short time of about 10 to 20 minutes. 
     It is an object of the present invention to provide an organopolysiloxane coating for a transparent base such as a polycarbonate lens in which the organopolysiloxane can be easily prepared on a commercial basis, the coating composition easily made up and used, the cured coating being effectively tinted with either water or solvent soluble azo dyes normally used to tint fibers, the tinting rate being fast (10-20 minutes) and the degree of tintability being very high (up to 80% absorbency-single side) without sacrificing hardness or scratch resistance or abrasion resistance. 
     It is an object of the present invention to provide a hard, scratch resistant coating for a base, the coating being an organopolysiloxane made from ethyl ortho silicate and one or both of methacryloxypropyltrimethoxy silane and vinyl triethoxysilane and hydrolyzing the same with phenylphosphonic acid to provide a coating, when cured, that is easily tinted. 
     THE INVENTION 
     The present invention provides a composition for providing a scratch resistant, tintable coating for a transparent substrate, the composition comprising: (A) a further curable, solvent soluble organopolysiloxane that is a hydrolysis reaction product of ethyl ortho silicate with methacryloxypropyltrimethoxy and/or vinyl triethoxysilane and water; (B) phenylphosphonic acid as an additive before coating the curable substrate or used in the hydrolysis as a starting ingredient; (C) an organic azo dye for tinting the cured composition; (D) an organic solvent for (A) and (B), the solution being adapted for curing and the coating subsequently receiving an application of the azo dye to form a scratch resistant tinted coating upon heating at about 240° to 270° F. 
     The present invention also provides a method of producing a scratch resistant tinted coating on a transparent substrate without reducing the tinting (measured by % absorbency), the method comprising the steps of (A) hydrolyzing methacryloxypropyltrimethoxy silane (MPMTS) and vinyl triethoxy silane (VTS) and/or ethyl ortho silicate (EOS) with about 1 to 7 moles of water and phenylphosphonic acid (PPA) to provide a solvent soluble, further curable organopolysiloxane; (B) dissolving the organopolysiloxane of step (A) in an organic solvent; (C) adding PPA to the solution of (B); (D) coating a transparent substrate with the solution of (C); (E) heating the coating to cure the organopolysiloxane; (F) applying an azo dye to tint the material to provide a tinted scratch resistant coating. 
     The hydrolysis and concentration steps of preparing the low molecular weight (about 1000 or 1500 up to about 2000 to 3000) organopolysiloxane are well known and commercially feasible, such steps being shown for trialkoxy silanes in U.S. Pat. No. 3,389,114, for an invention of Burzynski and Martin. 
     As is noted in the present invention the silane has organofunctional groups (methacrylo- and vinyl) for providing the improved tintability, adhesion and scratch resistance for the coatings on polycarbonate and the like. 
     PPA is used generally in amounts of about 1/2 to 1 up to 6 or 7 wt.% based on the silane monomer, the PPA apparently assisting the hydrolysis and polymerization reactions. PPA is preferably used in amounts of about 2 to 5% and most preferably about 21/2 to 4%. Generally, at least about 40 to 60 wt.% and preferably about 50% of the total PPA is used in the hydrolysis. In the event VTS is used, PPA need only be used in the hydrolysis and is often used in hydrolysis and for final curing. When used only for hydrolysis or only for final curing, the PPA can be used in only half the amount normally used. 
     The azo dye is generally a mixture of azo dyes normally used to tint textiles and fibers, such azo dyes including mono-, di- and tri-azo dyes such as set forth in Kirk-Othmer, Vol. 3, pages 387-399. Useful specific dyes are set forth in the Kirk-Othmer including Congo Red: ##STR1## 
     Suitable azo dye mixtures include those with Acid Yellow 13, Acid Red 1 and Diamond Black PV. 
     As previously indicated the azo dyes and organosiloxane polymers make the coating highly tintable and the dyes are picked-up 65 or 70% up to as high as about 75 to 80% absorbency in only 10 to 20 minutes and preferably only 12 to 15 minutes. Although not wishing to be bound by theory, the azo dyes and organopolysiloxane coating in the coating composition apparently coact to bring out the rich tinting effect, the good adhesion, and the fast rate of tinting. 
     The abrasion resistance tests are performed with 000 steel wool and the adhesion tests are performed with a groove and scotch tape. The abrasion resistance and adhesion were excellent for the coatings of the invention especially when about 40 to 60 parts by weight of VTS is used per 100 parts by weight of total silane monomer. 
     As indicated, the azo dyes are preferably a mixture of azo dyes such as a mixture of mono- and di-azo dyes or a mixture of mono- and tri-azo or a mixture of di- and tri-azo dyes. The mixture can be a mixture of just mono-azo dyes or a mixture of tri-azo dyes, etc. A suitable dye is BPI Molecular Catalytic Dye, a mixture of dyes sold by Brain Power Incorporated, Miami, Fla. 
     In general, the azo dyes are dyes normally used as textile dyes and are made by Kodak and BASF-Wyandot. The hard transparent substrate is preferably an aliphatic or aromatic polycarbonate such as a CR39 polycarbonate lens (P.P.G. or Lexan™, General Electric), although glass and polyacrylics are suitable as long as adhesion is obtained. Translucent substrates for some applications can be used including decorative color applications such as metals with decorations. 
    
    
     The following examples are intended to illustrate rather than limit the present invention. 
     EXAMPLE 1 
     A hard, tintable scratch resistant coating was prepared by making a tintable resin for coating a polycarbonate lens by reacting 1 mole of (248.1 g) methacryloxypropyltrimethoxy silane (MPTMS) with 2.3 moles (41.4 g) water and 21/2% by wt. of phenylphosphonic acid (PPA) based on the weight of the silane monomer to hydrolyze the silane. The ingredients are added to a flask. The solution is cleared immediately with a slight exotherm (or the reaction can be started in two phases). The flask (a 3-neck 500 ml flask) is equipped with a stir bar, a heating mantle, a thermometer, and a take-off condenser. After clearing and reaching reflux temperature (72° to 74° C.), the reaction mixture is refluxed for 4 hours. After the reflux period, some alcohol and water by-products are removed by distillation. A total of 60 ml is collected in this reaction. 
     Heating is stopped and the reaction mixture allowed to cool to room temperature. Tests for % by weight solids are run to make sure to provide a solids content of 72 to 78 wt.% depending upon the quantity of alcohol removed. The partially hydrolyzed further curable, solvent soluble organopolysiloxane resin is then diluted to the desired coating concentration, (40% by wt. solids) with n-butanol as the solvent. 
     EXAMPLE 2 
     The coating solution of Example 1 and an additional 21/2% by weight of phenylphosphonic acid (PPA) to make a total of 5% by weight of the resin solids content are mixed until the PPA is dissolved, with external heating used to add the dissolving of the PPA. The solution is filtered through a 0.2 micron filter to remove all foreign materials such as dust and gels. 
     An acrylic base primer was used to prime coat a transparent polycarbonate lens. 
     The resultant above described filtered coating solution is applied by dipping (or by flow coating or spraying) to the prime coated transparent polycarbonate lens. After air drying the wet coating, the coating and lens are placed in an oven at 250° to 265° F. and heated for 21/2 hours. 
     The resultant cured organopolysiloxane coating is securely attached to the lens and is dipped and immersed in a bath of a mixture of azo dyes (textile dyes--also used for lens coating) to provide a tinted, hard scratch resistant coating on the lens. The coating (single side) tints to 80+% absorbency in only 10 to 20 minutes. The prior art technique used for tintable coatings allows generally only a 10 to 20-30% (sometimes 30% to 40%) absorbency (single side) pick-up of the azo dye mixture and this pick-up requires at least 30 to 45 minutes. 
     EXAMPLE 3 
     A curable tintable resin was prepared using 50 parts by weight of MPTMS and 50 parts by weight of vinyl triethoxy silane (VTS) as the silane starting material to provide a copolymeric organopolysiloxane in which the main polymer chains contain moities of both reaction monomers of MPTMS and the VTS. 
     VTS (0.5 moles) 95 g (available from Union Carbide as A-151™ silane material) and MPTMS (0.5 moles) 124 g (available from Union Carbide as A-174™ silane material) were hydrolyzed with water (2.3 moles) 41.4 g and 5.5 g PPA (21/2% by wt. based on the silane monomers) as described in Example 1. The resultant further curable resin was coated on a polycarbonate substrate as described in the previous Example. The tinting, abrasion resistance and adhesion were excellent. 
     A number of examples were prepared as described in Examples 1, 2 and 3 to provide hard cured tinted coatings on a polycarbonate substrate. The examples are set forth in Tables 1 and 2 that follow, the first adhesion value being before tinting and the second adhesion value being after tinting and TMAH meaning tetramethylammonium hydroxide. 
     
                                           TABLE 1                                 
__________________________________________________________________________
          Moles                                                           
Example                                                                   
     Moles                                                                
          A-174 PPA    H.sub.2 O                                          
                            W/O Additional PPA W/Additional PPA           
No.  VTES (MPMTS)                                                         
                %      Ratio                                              
                            AR  Tint                                      
                                    Adhesion                              
                                         Cure  AR    Tint Adhesion        
__________________________________________________________________________
1    1    --    1.0    2.3  poor                                          
                                10 (1)                                    
                                     0   1 hr. at                         
                                                --   --   --              
                                         250° F.                   
2    1    --    1.0    2.3   --  -- --   1 hr. at                         
                                               poor  10                   
                                                          10 (B)          
                                         250° F.                   
3    1    --    1.0    2.3  poor                                          
                                10 (1)                                    
                                     0   2 hrs. at                        
                                                --   --   --              
                                         250° F.                   
4    1    --    1.0    2.3   --  -- --   2 hrs. at                        
                                               fair  10                   
                                                          10 (8)          
                                         250° F.                   
5    1    1     21/2   2.3  good+                                         
                                10  10 (10)                               
                                         21/2 hrs.                        
                                                --   --   --              
                                         at 250° F.                
6    1    1     21/2   2.3   --  -- --   21/2 hrs.                        
                                               good+ 10   10 (8)          
                                         at 250° F.                
7    1    3     21/2   2.3  good-                                         
                                10  10 (10)                               
                                         21/2 hrs.                        
                                                --   --   --              
                            good+        at 250° F.                
8    2    1     21/2   2.3  good-                                         
                                10  10 (10)                               
                                         21/2 hrs.                        
                                                --   --   --              
                            good+        at 250° F.                
9    2    1     21/2   2.3   --  -- --   21/2 hrs.                        
                                               good+ 10   10 (10)         
                                         at 250° F.                
10   1    1     21/2   2.3  good                                          
                                10  10   21/2 hrs.                        
                                                --   --   --              
                                         at 250° F.                
11   1    2     21/2   2.3  good                                          
                                10  10 (10)                               
                                         21/2 hrs.                        
                                                --   --   --              
                                         at 250° F.                
12   1    2     21/2   2.5  good                                          
                                10  10 (10)                               
                                         21/2 hrs.                        
                                                --   --   --              
                                         at 250° F.                
13   1    1     21/2   2.5  good                                          
                                10# 10 (10)                               
                                         21/2 hrs.                        
                                                --   --   --              
                                         at 250° F.                
14   1    2     5.0    2.3  good                                          
                                10  10 (10)                               
                                         21/2 hrs.                        
                                                --   --   --              
                                         at 250° F.                
15   1    1     5.0    2.3  good-                                         
                                10  10 (10)                               
                                         21/2 hrs.                        
                                                --   --   --              
                            good+        at 250° F.                
16   1    2     5.0    2.5  fair-                                         
                                10  10 (8)                                
                                         21/2 hrs.                        
                                                --   --   --              
                            good         at 250° F.                
17   1    1     5.0    2.5  good-                                         
                                10  10 (0)                                
                                         21/2 hrs.                        
                                                --   --   --              
                            good+        at 250° F.                
18   1    1     21/2   2.0  good                                          
                                10  10 (10)                               
                                         21/2 hrs.                        
                                                --   --   --              
                                         at 250° F.                
19   1    2     21/2   2.0  good                                          
                                10  10 (9)                                
                                         21/2 hrs.                        
                                         at 250° F.                
20   1    1      20 ppm H+                                                
                       2.3  poor                                          
                                 5  10 (10)                               
                                         21/2 hrs.                        
                                               +5% PPA                    
                                                     10   10 (10)         
                (No PPA)        poor     at 250° F.                
                                               good  some                 
                                streaky              red                  
21   1    2      20 ppm H+                                                
                       2.3  fair                                          
                                poor                                      
                                    10 (10)                               
                                         21/2 hrs.                        
                                               +5% PPa                    
                                                     10   10 (10)         
                (No PPA)                 at 250° F.                
                                               good- some                 
                                               good+ red                  
22   1    --    21/2   2.0  poor                                          
                                10  10 (10)                               
                                         21/2 hrs.                        
                                               +5% PPA                    
                                                     10   10 (10)         
                                spotty   at 250° F.                
                                               poor  purple &amp;             
                                                     spotty,              
                                                     blisters             
23   1    1     1.0    2.3  good                                          
                                10  10 (10)                               
                                         21/2 hrs.                        
                                               good  10   10 (10)         
                                         at 250° F.                
24   1    2     1.0    2.3  poor-                                         
                                10  10 (10)                               
                                         21/2 hrs.                        
                                               fair- 10   10 (10)         
                            fair         at 250° F.                
                                               good                       
25   1    --    21/2   2.3  poor                                          
                                10  10 (10)                               
                                         21/2 hrs.                        
                                               poor  10   10 (10)         
                                blue-    at 250° F.                
                                                     purple               
                                purple                                    
26   1    1     21/2   3.0  good-                                         
                                10  10 (10)                               
                                         21/2 hrs.                        
                                               good- 10   10 (10)         
                            good+                                         
                                blue-    at 250° F.                
                                               good+                      
                                gray                                      
27   1    2     21/2   3.0:1                                              
                            fair                                          
                                10  10 (10)                               
                                         21/2 hrs.                        
                                               fair  10    0              
                                         at 250° F.                
28     1.5                                                                
          1     21/2   2.3:1                                              
                            good                                          
                                10  10 (10)                               
                                         21/2 hrs.                        
                                               good  10   10 (0)          
                                         at 250° F.                
29   2    1     21/2   2.3:1                                              
                            good-                                         
                                10  10 (9)                                
                                         21/2 hrs.                        
                                               good  10   10 (0)          
                            good+        at 250° F.                
30     1.25                                                               
          1     21/2   2.3:1                                              
                            good-                                         
                                10  10 (10)                               
                                         21/2 hrs.                        
                                               fair- 10   10 (0)          
                            good+        at 250° F.                
                                               good                       
31   1.5 M-                                                               
          --    21/2   1.4:1                                              
                             -- --  --    --   --    --   --              
     MTS-32                                                               
32   1    2     500 ppm H+                                                
                       2.3:1                                              
                            fair-                                         
                                Blue                                      
                                    10 (0)                                
                                         21/2 hrs.                        
                                               good  10   10 (0)          
                (No PPA)    good                                          
                                Streaks  at 250° F.                
                                 5                                        
                                orange                                    
                                peel                                      
33   --   1     21/2   2.3:1                                              
                            good                                          
                                10  10 (0)                                
                                         21/2 hrs.                        
                                               good  10   10 (0)          
                                         at 250° F.                
34   1    1     21/2   2.3:1                                              
                            good                                          
                                10  10 (10)                               
                                         21/2 hrs.                        
                                               good  10   10 (0)          
                                         at 250° F.                
35   1.5 M-                                                               
          --    21/2   1.25:1                                             
                            poor                                          
                                10  10 (0)                                
                                         21/2 hrs.                        
                                               poor  10    0              
     MTS-32                              at 250° F.                
__________________________________________________________________________
 
    
     
                       TABLE 2                                                     
______________________________________                                    
Comments for each of the examples of Table 1 are                          
shown below in Table 2.                                                   
Example No.                                                               
         Comment                                                          
______________________________________                                    
1        Tints very well - more blue than gray -                          
         no red - excellent color.                                        
2         .sup.○8   Adhesion after tinting drops to 8.             
3          --                                                             
4          --                                                             
5        No red - good blue-gray.                                         
6        Some red - still fairly good - looses                            
         adhesion with extra PPA - both coating                           
         appearances good.                                                
7        25% primer instead of 50% - 3 &amp; 4 hours                          
         no improvement.                                                  
8        50% primer - conc soln as prepared -                             
         gelled 9/6/84                                                    
9        Color very good for both - had some red                          
         with additional 5% PPA.                                          
10       25% primer instead of 50%; 3 &amp; 4 hr cure                         
         no improvement - (blue-gray - no red)                            
11       25% primer instead of 50%; 3 &amp; 4 hr cure -                       
         no improvement (blue-gray - no red)                              
12       25% primer instead of 50%; gave darker                           
         color.                                                           
13       Not as dark as 12.                                               
14       Very faint hint of red - lower portion.                          
15       Very good color - slight hint of red on                          
         lower portion.                                                   
16       Very good color - faint red color                                
         throughout coating.                                              
17       Faint tint of red throughout lense -                             
         blue-gray                                                        
18       Deep blue rather than blue-gray - no red -                       
         better dye uptake                                                
19       Deep blue rather than blue-gray - better                         
         dye uptake                                                       
20       Also 21/2% PPA - AR - fair; tint 10 - blue-gray;                 
         adhesion 10(10)                                                  
21       Also 21/2% PPA - AR good; tint 10 blue-gray;                     
         10(10)                                                           
22       Also 11/2% TMAH - AR poor; tint 10 roughly                       
         50% light blue; adhesion 10(10)                                  
23       Some red color at 5% PPA                                         
24       Some red color at 5% PPA                                         
25       Tint bluish purple w/o additional PPA;                           
         Purple with additional 5% PPA                                    
26       Additional 5% PPA tint has slight red.                           
27       Additional 5% PPA - tint has a little red                        
         to it.                                                           
28       Loss adhesion after tinting (5% PPA)                             
29       Loss adhesion after tinting (5% PPA)                             
30       Loss adhesion after tinting; some red color.                     
31       Undiluted sample gels on standing.                               
32       Additional 5% PPA - tint has red to it.                          
33       PPA dissolved in H.sub.2 O and added to A-174 -                  
         5% PPA; some red color.                                          
34       PPA dissolved in H.sub.2 O and added to A-174 -                  
         5% PPA; some red color.                                          
35       Both as received + 5% PPA - tint light purple                    
         approximately 50% tintability                                    
______________________________________                                    
 
    
     In the tables, an adhesion of 10 is very good. A tint of 10 is very good, representing high absorbency. 
     It has been found that the use of ethyl ortho silicate (EOS) with MPTMS or UTS or both enhances the tintability of the cured coating and the abrasion resistance of the final tinted coated substrate. Based on 100 parts by weight of total silane, the amount of EOS is generally about 5 to 40 and preferably 15 to 30 parts when used with MPTMS or VTS. When EOS is used with both MPTMS and VTS the preferred ratio of MPTMS/VTS/EOS is about 1/1/0.5. Generally, when about 30 to 45 parts of each of the MPTMS and VTS is used, the amount of VTS is generally about 5 to 30 parts. 
     A number of examples were prepared in Examples 1, 2 and 3 using EOS to provide tinted coatings on a polycarbonate substrate. The examples are set forth in Tables 3 and 4. In the Tables, DMF equals dimethyl formate. 
     
                                           TABLE 3                                 
__________________________________________________________________________
Tintable Coating Reactions and Variables                                  
Example                                                                   
     Moles                                                                
         Moles                                                            
             PPA   H.sub.2 O                                              
                       W/O Additional PPA      W/O Additional PPA         
No.  VTES                                                                 
         A-174                                                            
             %     Ratio                                                  
                       AR   Tint    Adhesion                              
                                          Cure AR   Tint Adhesion         
__________________________________________________________________________
8827-66                                                                   
     1   1   21/2  2.3:1                                                  
                       good-                                              
                            10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                       good+                                              
                            blue-         250° F.                  
                            gray          +A-500                          
8827-68                                                                   
     .5  .5  21/2  2.3:1                                                  
                       good+                                              
                            10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                            blue-         250° F.                  
                            gray          +A-500                          
8827-69                                                                   
     1   --  21/2  2.3:1                                                  
                       poor 10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                            deep          250° F.                  
                            purple        +A-500                          
8827-70                                                                   
     .5  .5  21/2  2.3:1                                                  
                       good++                                             
                            10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                            blue-         250° F.                  
                            gray          +A-500                          
8827-71                                                                   
      .75                                                                 
         --  21/2  2.3:1                                                  
                       poor 10      10 (10)                               
                                          1 hr.                           
                                               poor 10   10 (10)          
                            blue-         250° F.                  
                            purple                                        
8827-72                                                                   
     .5  .5  21/2  2.5:1                                                  
                       good++                                             
                            10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                            blue-         250° F.                  
                            gray          +A-500                          
8827-74                                                                   
     .5  .5  21/2  2.3:1                                                  
                       good-                                              
                            10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                       good+                                              
                            bluish        250° F.                  
                            purple        +A-500                          
8827-75                                                                   
     .5  .5  21/2  2.5:1                                                  
                       good+                                              
                            10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                            blue-         250° F.                  
                            gray          +A-500                          
8827-76                                                                   
     .5  .5  21/2  2.3:1                                                  
                       good+                                              
                            10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                            blue-         250° F.                  
                            gray          +A-500                          
8827-77                                                                   
     .5  .5  21/2  2.5:1                                                  
                       good 10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                            blue-         250° F.                  
                            gray          +A-500                          
8827-78                                                                   
     .5  .5  1% H.sub.3 PO.sub.4                                          
                   2.3:1                                                  
                       good?                                              
                            10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                            blue-         250° F.                  
                            gray          +A-500                          
8827-83                                                                   
     .5  .5  21/2 PPA                                                     
                   2.5:1                                                  
                       good 10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                            blue-         250° F.                  
                            gray          +A-500                          
8827-84                                                                   
     .5  .5  21/2  2.5:1                                                  
                       good 10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                            blue-         250° F.                  
                            gray          +A-500                          
8827-85                                                                   
     .5  .5  21/2  2.5:1                                                  
                       good 10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                            blue-         250° F.                  
                            gray          +A-500                          
8827-86                                                                   
     .5  .5  21/2  2.3:1                                                  
                       good-                                              
                            10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                       good+                                              
                            blue-         250° F.                  
                            gray          +A-500                          
8827-87                                                                   
     .5  .5  21/2  2.5:1                                                  
                       good-                                              
                            10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                       good+                                              
                            blue-         250° F.                  
                            gray          +A-500                          
8827-88                                                                   
     .5  .5  21/2  2.5:1                                                  
                       good-                                              
                            10      10 (10)                               
                                          21/2 hrs. -                     
                                               --   --   --               
                       good+                                              
                            blue-         250° F.                  
                            gray          +A-500                          
8827-93                                                                   
     1   2   21/2  2.3:1                                                  
                       good-                                              
                            gray    10 (10)                               
                                          21/2 hrs. -                     
                                               good gray 10 (10)          
                       good+                                              
                            color         250° F.                  
                                          +A-500                          
8827-94                                                                   
     1   3   21/2  2.3:1                                                  
                       good gray    10 (10)                               
                                          21/2 hrs. -                     
                                               good-                      
                                                    gray 10 (10)          
                                          250° F.                  
                                               good+                      
                                          +A-500                          
8827-95                                                                   
     --  1   21/2  2.3:1                                                  
                       good 10      10 (10)                               
                                          21/2 hrs. -                     
                                               good+                      
                                                    10 blue-              
                                                         10 (10)          
                            blue-         250° F.                  
                                                    gray                  
                            gray          +A-500                          
8827-96                                                                   
     --  1   21/2  2.3:1                                                  
                       good 10      10 (10)                               
                                          21/2 hrs. -                     
                                               good+                      
                                                    10 blue-              
                                                         10 (10)          
                            blue-         250° F.                  
                                                    gray                  
                            gray          +A-500                          
8827-97                                                                   
     --  1   21/2  2.3:1                                                  
                       good-                                              
                            10      10 (10)                               
                                          21/2 hrs. -                     
                                               good+                      
                                                    10 blue-              
                                                         10 (10)          
                       good+                                              
                            blue-         250° F.                  
                                                    gray                  
                            gray          +A-500                          
8827-98                                                                   
     --  1   21/2  2.5:1                                                  
                       good 10      10 (10)                               
                                          21/2 hrs. -                     
                                               good 10 blue-              
                                                         10 (10)          
                            blue-         250° F.                  
                                                    gray                  
                            gray          +A-500                          
8827-101                                                                  
     --  1   21/2  2.5:1                                                  
                       good+                                              
                            10      10 (10)                               
                                          21/2 hrs. -                     
                                               good+                      
                                                    10 blue-              
                                                         10 (10)          
                            blue-         250° F.                  
                                                    gray                  
                            gray          +A-500                          
8827-102                                                                  
     --  1   21/2  2.5:1                                                  
                       good 10      10 (10)                               
                                          21/2 hrs. -                     
                                               good 10 blue-              
                                                         10 (10)          
                            blue-         250° F.                  
                                                    gray                  
                            gray          +A-500                          
8827-103                                                                  
     --  1   11/2  2.3:1                                                  
                       fair streaky 10 (0)                                
                                          21/2 hrs. -                     
                                               fair-                      
                                                    10 blue-              
                                                         10 (10)          
                            10            250° F.                  
                                               good gray                  
                            blue-         +A-500                          
                            gray                                          
8827-104                                                                  
     .5  .5  11/2  2.3:1                                                  
                       good 10      10 (10)                               
                                          21/2 hrs. -                     
                                               good+                      
                                                    10 blue-              
                                                         10 (10)          
                            blue-         250° F.                  
                                                    gray                  
                            gray          +A-500                          
8827-105                                                                  
     .5  .5  11/2  2.3:1                                                  
                       good-                                              
                            uniform 10 (10)                               
                                          21/2 hrs. -                     
                                               good+                      
                                                    10 blue-              
                                                         10 (10)          
                       good+                                              
                            10            250° F.                  
                                                    gray                  
                            blue-         +A-500                          
                            gray                                          
8827-106                                                                  
     .5  .5  11/2  2.5:1                                                  
                       good-                                              
                            10 Min                                        
                                20 Min                                    
                                    10 (10)                               
                                          21/2 hrs. -                     
                                               good-                      
                                                    uniform               
                                                         10 (10)          
                       good+                                              
                            10  10        250° F.                  
                                               good+                      
                                                    10 blue-              
                                          +A-500    gray                  
8827-107                                                                  
     --  1   21/2  2.3:1                                                  
                       good+                                              
                            10 Min                                        
                                20 Min                                    
                                    10 (10)                               
                                          21/2 hrs. -                     
                                               good+                      
                                                    10   10 (10)          
                            10            250° F.                  
                                                    deep                  
                                          +A-500    color                 
8827-108                                                                  
     --  1   21/2  2.0:1                                                  
                       good 10 Min  10 (10)                               
                                          21/2 hrs. -                     
                                               good 20 min                
                                                         10 (10)          
                            10            250° F.                  
                                                    10 deeper             
                            blue-         +A-500                          
                            gray                                          
8827-109                                                                  
     .5  .5  21/2  2.5:1                                                  
                        --  --      --     --  --   --   --               
8827-112                                                                  
     .5  .5  21/2  2.3:1                                                  
                        --  --      --     --  --   --   --               
8827-113                                                                  
     .5  .5  21/2  2.0:1                                                  
                        --  --      --     --  --   --   --               
8827-121                                                                  
     --  5.0 21/2  2.3:1                                                  
                       good 10 blue-                                      
                                    10 10 (10)                            
                                          21/2 hrs. -                     
                                               good-                      
                                                    10 blue-              
                                                         10 10 (10)       
                            gray          250° F.                  
                                               good+                      
                                                    gray                  
                                          +A-500                          
8827-122                                                                  
     --  5.0 21/2  2.3:1                                                  
                       good-                                              
                            10 blue-                                      
                                    10 10 (10)                            
                                          21/2 good- -                    
                                                    10 blue-              
                                                         10 10 (10)       
                       good+                                              
                            gray          250° F.                  
                                               good+                      
                                                    gray                  
                                          +A-500                          
8827-123                                                                  
     --  4.5 21/2  2.3:1                                                  
                       good-                                              
                            10 blue-                                      
                                    10 10 (10)                            
                                          21/2 hrs. -                     
                                               good+                      
                                                    10 blue-              
                                                         10 10 (10)       
                       good+                                              
                            gray    250° F.                        
                                               gray                       
                                          +A-500                          
8827-124                                                                  
     --  4.4 21/2  2.3:1                                                  
                       good++                                             
                            10      10 10 (10)                            
                                          21/2 hrs. -                     
                                               good++                     
                                                    10 blue-              
                                                         10 10 (10)       
                            blue-         250° F.                  
                                                    gray                  
                            gray          +A-5000                         
8827-126                                                                  
     --  1   21/2  2.3:1                                                  
                       good Hazy    10 10 (10)                            
                                          21/2 hrs. -                     
                                               good 10 blue-              
                                                         10 10 (10)       
                            10            250° F.                  
                                                    gray                  
                            blue-         +A-500                          
                            gray                                          
8827-127                                                                  
     --  1   21/2  2.3:1                                                  
                        --  --      --    21/2 --rs. -                    
                                                    --   --               
                                          250° F.                  
                                          +A-500                          
8827-132                                                                  
     --  1   21/2  2.3:1                                                  
__________________________________________________________________________
 
    
     
                                           TABLE 4                                 
__________________________________________________________________________
Tintable Coating Reactions and Variables                                  
       Moles                                                              
Example No.                                                               
       EOS % Solids                                                       
                Comments                                                  
__________________________________________________________________________
8827-66                                                                   
       .1       25% A-505 primer - excellent color                        
8827-68                                                                   
       .2       very uniform blue-gray color                              
8827-69                                                                   
        .25     25% A-505 primer - very deep purple                       
8827-70                                                                   
       .4       very good abrasion resistance                             
8827-71                                                                   
        .75     good tint - bluish purple - both samples crazed           
8827-72                                                                   
       .2       20 min tint good - excellent - faint red tear drop        
8827-74                                                                   
       --       VTES - Kay Fries - as received                            
8827-75                                                                   
       .4       VTES - UC &amp; Stauffer EOS redistilled - 10 min slight      
                craze; 20 min completely crazed                           
8827-76                                                                   
       .3       coated flat stock - no crazing until flexed - 20 min      
                deep blue hint red                                        
8827-77                                                                   
       .3       20 min tint - adhesion 10 (10), AR - good - deep purple   
                -                                                         
                AR with .3 EOS at 2.3:1 better than 2.5:1 - good color    
                depth - no crazing until flexed - flat stock              
8827-78                                                                   
blue gray -     20 min tint - adhesion 10 (0); AR - good?                 
                blistered - not as good as PPA                            
8827-83                                                                   
       .2       1 qt sample - shelf life study - slight red, dye bath     
                will be changed                                           
8827-84                                                                   
       .2       UC = VTS - redistilled; EOS - 99+% as received -          
                slight red - will recheck                                 
8827-85                                                                   
        .25     EOS &amp; VTS redistilled - slight red - will be rechecked    
8827-86                                                                   
       --       Kay Fries redist VTS; 20 min - adhesion 10 (10);          
                AR - good; 10 blue gray                                   
8827-87                                                                   
       .2       20 min tint - adhesion 10 (10); AR - tint (10) blue       
                gray - color intensity less 8827-86 - Kay Fries VTES;     
                all monomers as received                                  
8827-88                                                                   
       .2       20 min - adhesion 10 (9.5); AR - good-good+ tint          
                10 blue-gray - Kay Fries redistilled VTES; EOS redist.    
                color intensity better than 8827-87 - not as good as      
                8827-26                                                   
8827-93                                                                   
       --       with additional 5% PPA gray - not uniform                 
8827-94         gray with &amp; without additional PPA                        
8827-95                                                                   
       .2  75.7 blue-gray color - 5% PPA - maybe slightly red             
8827-96                                                                   
       .3  72.8 blue-gray color - 5% PPA - maybe slightly red             
8827-97                                                                   
       .4  70.1 blue-gray color - 5% PPA - maybe slightly red             
8827-98                                                                   
       .2  75.5 blue-gray - 5% PPA                                        
8827-101                                                                  
       .3  71.3 blue-gray - 5% PPA                                        
8827-102                                                                  
       .4  70.2 blue-grey - 5% PPA                                        
8827-103                                                                  
       --  76.7 blue-gray - streaky - more blue than gray with 5% PPA     
8827-104                                                                  
       --  71.5 blue-gray with 5% PPA                                     
8827-105                                                                  
       .2  61.5 blue-gray - slightly darker color with 5% PPA             
8827-106                                                                  
       .2  68.8 uniform blue-gray - slightly dark with 5% PPA             
8827-107                                                                  
       .5  68.6 10 &amp; 20 min runs - deeper color                           
8827-108                                                                  
       .5  67.9 20 min + 5% PPA grey blue - deeper color                  
8827-109                                                                  
       .2  --   gelled -                                                  
8827-112                                                                  
       .2  --   precured to 100° C. in beaker - gels               
8827-113                                                                  
       --  --   precured to 95° C. - gels                          
8827-121                                                                  
       1.0 71.8 Shelf life studies                                        
8827-122                                                                  
       1.5 71.7 Shelf life studies                                        
8827-123                                                                  
       1.8 69.4 Shelf life studies                                        
8827-124                                                                  
       2.2 68.8 Shelf life studies - darkest blue-gray of all             
8827-126                                                                  
       --       add 18 g DMF, distill - cool 60° C. - add 106 g    
                n-propanal -                                              
                better with PPA                                           
8827-127                                                                  
       --       precure to 105, add DMF - resin gels                      
8827-132                                                                  
       --       precure 105 in beaker - add DMF, cool 60° C. -     
                add                                                       
                106 g n-propanal                                          
__________________________________________________________________________