Patent Publication Number: US-4057657-A

Title: Curable pre-polymer compositions, method of making and method of coating articles therewith

Description:
BACKGROUND OF THE INVENTION 
     The present invention relates to the preparation of U.V. and electron beam curable compositions and to the formation of coatings from such compositions. 
     It is well known that many ethylenically unsaturated monomers may be polymerised upon being suitably activated. This activation may be derived from free radical initiators, by photoinitiation, by thermal initiation or by the use of U.V. or ionising radiation. These polymerisable monomers have been used as coating materials and cured in situ by one of the means referred to above. These coatings have been found to be generally unsatisfactory due to the difficulty of obtaining a complete cure of the coating. It is thought that this difficulty stems largely from the coating layer being too thin to enable a sufficiently high steady state of free radicals to be generated. A further difficulty associated with the in situ curing of the monomers referred to above is that the low viscosity of the monomer makes it difficult to form an even coating on an article and to maintain that coating until curing has taken place. 
     It has been proposed in U.S. Pat. Nos. 3,551,246 and 3,546,002 to form prepolymers thermally and to form U.V. curable coatings from the prepolymers. These thermally produced prepolymers have been found to be of limited use due to the dark colour generated within the prepolymer during its formation; due to the difficulty of curing the prepolymer; and due to the limited number of monomers and monomer blends which will form curable prepolymers without the precipitation of homopolymer from the mixture. 
     The present inventors have found that a very large number of prepolymers which are generally clear, highly viscous and water white in colour and which cure readily under U.V. radiation or an electron beam may be prepared by the use of U.V. or ionising radiation initiation. 
     SUMMARY OF THE INVENTION 
     In a process aspect, this invention relates to a process for the preparations of a prepolymer capable of being cured by ultra-violet or ionising radiation, comprising the steps of subjecting either (a) a polymerisable ethylenically unsaturated monomer, or a mixture of such monomers, or (b) a mixture of one or more such monomers and a long chain organic compound or a polymeric material to ionization radiation or, in the case of (b), to ultra-violet or ionising radiation until the monomer, or monomers, achieves a predetermined but incomplete degree of polymerisation, and removing the prepolymer so formed from the radiation. In a composition aspect, this invention relates to the prepolymers so formed. 
     In another aspect, this invention relates to a method of coating a substrate comprising applying to the substrate a layer of a prepolymer prepared according to the process of this invention and curing the prepolymer by subjecting it to ultra-violet or ionising radiation. In another aspect, this invention relates to a substrate having a coating thereon formed by the foregoing method according to this invention. 
     DETAILED DISCUSSION 
     Any of the very large number of known polymerisable ethylenically unsaturated monomers can be used in the formation of prepolymers according to this invention. The preferred monomers are those which include a vinyl or vinylidene group. The properties of the final coating depend in part upon the monomer or monomers used to form the prepolymer and the most preferred monomers will depend upon the intended end use of the prepolymer. For coating onto paper and cardboard, as in printing inks, where a glossy, water impervious, coating is required the preferred starting materials are styrene and vinyl chloride/ethyl acrylate and vinyl chloride/methyl acrylate blends in ratios of 3:1 to 1:1. For coating onto metals such as copper, aluminium or tin plate where a very hard scratch resistant coating is required styrene, and blends of two or more of the following, styrene, butyl acrylate, methyl methacrylate vinylidene chloride, ethyl acrylate, acrylonitrile, and vinyl acetate, generally in ratios of from 1 to 3 to 3 to 1 have been found to work well. For coating onto polypropylene and other synthetic plastics materials blends of acrylic acid and alkyl acrylate in ratios of 1 to 1 to have formed coatings highly adherent to the substrate. For the coating of the surfaces of concrete structures blends of methyl methacrylate with acrylonitrile or vinyl acetate have been found to perform will in adhering to the substrate and forming a water and acid resistant coating. For the lining of concrete sewerage pipes base coatings of blends of butyl acrylate with methyl methacrylate or vinyl acetate and ter-polymers of isoprene/styrene/acrylonotrile have proved very satisfactory and have shown an ability to flow under applied stresses such that the coating will not be ruptured by cracks in the pipe. In such applications a top coat of blends of two of methyl methacrylate, vinyl acetate, acrylonitrile and styrene will give abrasion resistance and water impermeability to the coating. 
     The starting material may include additionally long chain organic molecules such as natural drying oils e.g. linseed oil, shellac, cellulose acetate and natural resins e.g. gum rosin, or polymeric materials such as polyamides, polyesters including alkyd resins, polycarbonates, epoxy resins, polyvinylalcohols, polyvinyl chlorides, polysiloxanes and polysilanes either with or without solvents. These additional materials may be used with single monomers or with mixtures of monomers. Styrene/Gum resin and Styrene/alkyd resin blends have been found to be advantageous in the formation of printing inks while butyl acrylate/linseed oil prepolymers are useful in forming base coats in concrete sewerage pipes. Blends of linseed oil, alkyd resins and gum rosin with one or more of the following monomers viz. α methyl styrene, styrene and butyl acrylate have formed coatings on metal which exhibit excellent scratch resistance. Mixtures including long chain organic molecules or polymers are preferably prepolymerised using U.V. radiation. 
     The monomers referred to above, when used alone, in mixtures or in blends with long chain compounds or polymers are particularly preferred however the present invention is not limited to the use of these monomers. A large number of other monomers may also be used to form curable prepolymers and these include diallyl phthalate, vinyl ethyl ether, 2-hexyl ethyl acrylate, diallyl isophthalate, allyl glycidyl ether, acrylamide, alkylamine, allylacrylte, vinylpyridine, maleic anhydride, acrylic acid and divinyl benzene. These monomers may be used alone, together in mixtures or, if the prepolymer is to be cured by U.V. radiation, together with long chain molecules or polymers. 
     The formation of the prepolymer is brought about by U.V. or ionising radiation. U.V. and γ-radiation are particularly preferred due both to the relative ease of radiation and the good results achieved however other ionising radiation such as x rays or electron beams may be used. The selection of the source does not appear to be critical however the present inventors have found a 130 w U.V. Wotan lamp set 13 cm. from the centre of a glass reaction vessel to be satisfactory, similarly for γ radiation doses of from 0.01 to 5 M rads frm a spent fuel rod source have proven satisfactory. For any given starting material and any given source simple experimentation will be required to find the optimum duration of irradiation. The duration will also depend upon the intended end use of the prepolymer. In general the radiation will be continued until the prepolymer will have a suitable viscosity once it has cooled to ambient temperature after the irradiation. What is a suitable viscosity will largely depend upon how the prepolymer is to be coated onto the substrate and the nature of the substrate itself. If the prepolymer is to be sprayed on or if the substrate is to be dipped into the prepolymer then the prepolymer should not be unduly viscous. If the prepolymer is to be brushed, rolled or spread with a scraper onto the substrate then the prepolymer is preferably very viscous. Absorbant substrates such as wood and paper require viscous prepolymers so that the prepolymer will not be absorbed into the substrate before it can be cured. As a rough guide the present inventors used a magnetic stirrer of conventonal type to stir the monomer mixture and found that for most applications it was satisfactory to remove the prepolymer from the radiation when the viscosity of the prepolymer was such that the stirrer no longer rotated. It should be stressed that the prepolymer must be removed from the radiation while it still has a capacity for chain propogation i.e. before polymerisation has been completed. 
     The formation may be carried out at room temperature or may be carried out at an elevated temperature. The application of heat is possible within the limits of the boiling point of the monomer or monomers used to form the prepolymer and their tendency upon heating to form solid homopolymers rather than liquid prepolymers. Heating has been found to be particularly advantageous where the prepolymer is formed by U.V. initiation as the increased temperature allows a shorter period of U.V. initiation resulting in less colouration of the prepolymer due to oxidation. The high energies available with commercial γ ray sources render temperature effects with γ ray initiation negligible. 
     Additives which can be used to modify prepolymer formation and/or curing of the prepolymer, include sensitisers, solvents, chain transfer agents and inhibitors. 
     U.V. initiation of prepolymer formation is generally enhanced by the presence of from 1 to 20% by weight of a conventional photo-sensitizer such as benzoin ethers, uranyl nitrates, benzophenone or Michler&#39;s ketone. This photosensitiser is preferably added to the monomers before the prepolymer formation however additional photosensitiser may be added prior to the U.V. cure of the prepolymer coating. It appears to be desirable to avoid photosensitiser additions if the prepolymer is to be cured using an electron beam. 
     Solvents are preferably avoided in the present invention for economic and environmental reasons however for spraying some prepolymers it is desirable to dissolve the prepolymer in a compatible solvent. Solvents may also be added to maintain one phase systems with otherwise incompatible monomers. 
     Chain transfer agents of conventional types such as carbon tetrachloride or carbon tetrabromide may be added to the prepolymer to enhance the curing of the prepolymer under U.V. or electron beam initiation. Chain transfer agents are particularly desirable when the prepolymer is pigmented with a U.V. opaque pigment. 
     Conventional pigments may be added to the system either at the prepolymer formation stage or at the curing stage by conventional means. Dyes may also be added provided that they are not destroyed by the curing process. 
     If necessary conventional inhibitors may be added to the prepolymer to prevent change in the prepolymer during storage. Inhibitors such as methyl ethyl hydroquinone may be used in amounts of up to 2000p.p.m. 
     The prepolymers formed by the process according to the present invention may be applied to any suitable substrate such as paper, cardboard and other cellulosic materials such as wood, particle board and the like; metals such as copper, aluminium, tin plate and mild steel; concrete products such as building blocks, pipes and concrete buildings; synthetic plastics such as polypropylene; natural polymers such as leather; and glass. 
     The coating of the substrate may be achieved by dipping, spraying, brushing, rolling, spreading with a blade or by any other suitable means such as by a printing press. 
     The curing of the prepolymers is achieved either using U.V. or ionising radiation, the ionising radiation preferably being an electron beam. The time of cure is proportional to the incident radiation and accordingly where rapid cure is desired a high intensity source is preferred. The present inventors used a 6 inch 200 w/inch Hanovia U.V. lamp at a distance of 30 cm from the substrate to achieve curing times of from 1 to 50 minutes; subsequent use of a 36 inch lamp of 20 w/inch fitted with a reflector and at a shorter distance from the lamp showed cure times approximately 300 times faster. Electron beam irradiations of the order of 1 M rad or more were generally necessary to achieve surface or through cure of prepolymer coatings. If electron beam curing is to be used it is desirable to carry out the cure under nitrogen to avoid oxygen at the coating surface acting as a radical scavenger and reducing the rate of cure of the prepolymer. 
     Hereinafter given by way of example only are preferred examples of the present invention and comparative examples showing the advantages of the present invention over the prior art. 
     The following examples show use of prepolymers prepared by the γ radiation of the monomers listed. The prepolymers were cured on the substrates listed using a U.V. lamp of 200 watts/inch at a distance of 30 cm from the sample. The solvent nominated was used solely to enable the prepolymer to be sprayed on to the substrate using a low viscosity spray gun. 
     
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1. STYRENE/DIALLYL PHTHALATE (2:1)                                        
______________________________________                                    
Solvent:    Benzene                                                       
Prepolymer Prep:                                                          
            2M Rad at 37,632 rad/hr produced a clear                      
            viscous prepolymer.                                           
Copper:     1 coat, 25 min cure produced a crazed                         
            finish with excellent scratch resistance.                     
Cardboard:  3 coats, 3 min cure/coat produced a slight                    
            gloss.                                                        
Polypropylene:                                                            
            1 coat, 15 min cure produced a spotty finish                  
            with good scratch resistance.                                 
Solvent Resistance:                                                       
            Nil                                                           
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2. STYRENE/DIALLYL ISOPHTHALATE (1:1)                                     
______________________________________                                    
Solvent:    Benzene                                                       
Prepolymer Prepn:                                                         
            2 M Rad at 37,632 rad/hr produced a                           
            clear viscous prepolymer.                                     
Copper:     1 coat, 25 min cure produced a matt                           
            finish with excellent scratch resistance.                     
Cardboard:  3 coats, 3 min cure/coat produced no                          
            gloss.                                                        
Polypropylene:                                                            
            1 coat, 25 min cure produced a spotty                         
            finish with good scratch resistance.                          
Solvent Resistance:                                                       
            Nil                                                           
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3. STYRENE/VINYL ETHYL ETHER (2:1)                                        
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            2.0 M Rad at 37,632 rad/hr produced a                         
            clear slightly viscous prepolymer.                            
Copper:     1 coat, 25 min cure produced an excellent                     
            glossy finish with very good scratch                          
            resistance.                                                   
Cardboard:  1st coat, 5 min cure, 2nd coat, 10 min                        
            cure produced no gloss.                                       
Polypropylene:                                                            
            1 coat, 25 min cure produced a spotty                         
            finish with excellent scratch resistance.                     
Solvent Resistance:                                                       
            Nil                                                           
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         ______________________________________                                    
4. STYRENE/VINYL ACETATE (1:1)                                            
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn.:                                                        
            2.0 Rad at 37,632 rad/hr produced a                           
            clear slightly viscous prepolymer.                            
Copper:     1 coat, 35 min cure produced an excell-                       
            ent glossy finish with very good scratch                      
            resistance.                                                   
Cardboard:  2 coats, 5 min cure/coat produced a                           
            slight gloss.                                                 
Polypropylene:                                                            
            1 coat, 35 min cure produced a spotty                         
            finish with excellent scratch resistance.                     
Solvent Resistance:                                                       
            Nil                                                           
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5. STYRENE/2-HEXYL ETHYL ACRYLATE (2:1)                                   
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            1.0 Rad at 37,632 rad/hr produced a clear                     
            very viscous prepolymer.                                      
Copper:     1 coat, 30 min cure produced an excellent                     
            glossy finish with excellent scratch                          
            resistance.                                                   
Cardboard:  3 coats, 5 min cure/coat produced no                          
            gloss.                                                        
Polypropylene:                                                            
            1 coat, 30 min cure produced a spotty                         
            finish with excellent scratch resistance.                     
Solvent Resistance:                                                       
            Partial Resistance for coating on copper.                     
            Good Resistance for coating on polyprop-                      
            ylene.                                                        
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6. DIALLYL PHTHALATE/DIALLYL ISOPHTHALATE                                 
(1:1)                                                                     
______________________________________                                    
Solvent:    Acetone.                                                      
Prepolymer Prepn:                                                         
            2.0 M Rad at 37,632 rad/hr produced a                         
            clear slightly viscous prepolymer.                            
Copper:     1 coat, 30 min cure produced a crazed                         
            finish with excellent scratch resistance.                     
Cardboard:  1st coat, 5 min cure, 2nd coat 10 min                         
            cure, produced no gloss.                                      
Polypropylene:                                                            
            1 coat, 20 min cure produced a spotty                         
            finish with very good scratch resistance.                     
Solvent Resistance:                                                       
            Copper Coating - partial resistance.                          
            Polypropylene Coating - good resistance.                      
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7. DIALLYL PHTHALATE/VINYL ETHYL ETHER (1:1)                              
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            2.0 M Rad at 37,632 rad/hr produced a                         
            yellowish clear viscous prepolymer.                           
Copper:     1 coat, 25 min cure produced a green                          
            crazed matt finish with excellent scratch                     
            resistance.                                                   
Cardboard:  1 coat, 10 min cure produced no gloss.                        
Polypropylene:                                                            
            1 coat, 25 min cure produced a spotty                         
            finish with good scratch resistance.                          
Solvent Resistance:                                                       
            Copper coating - nil                                          
            Polypropylene coating - nil                                   
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8. DIALLYL PHTHALATE/2-HEXYL ETHYL ACRYLATE                               
(2:1)                                                                     
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            1.0 M Rad at 37,632 rad/hr produced a                         
            clear viscous prepolymer.                                     
Copper:     1 coat 45 min cure produced a gloss &amp;                         
            matt finish with excellent scratch                            
            resistance.                                                   
Cardboard:  3 coats, 5 min cure/coat produced no                          
            gloss.                                                        
Polypropylene:                                                            
            1 coat, 45 min cure produced a spotty                         
            finish with poor scratch resistance.                          
Solvent Resistance:                                                       
            Copper coating - partial resistance.                          
            Polypropylene coating - partial resistance.                   
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9. DIALLYL PHTHALATE/ALLYL GLYCIDYL ETHER                                 
(1:1)                                                                     
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            2.0 M Rad at 37,632 rad/hr produced a                         
            clear slightly viscous prepolymer.                            
Copper:     1 coat 40 min cure produced a soft                            
            crazed finish.                                                
Cardboard:  3 coats, 5 min cure/coat produced no                          
            gloss.                                                        
Polypropylene:                                                            
            1 coat 40 min cure produced a spotty                          
            finish with good scratch resistance.                          
Solvent Resistance:                                                       
            Copper Coating - nil                                          
            Polyprpylene coating - partial resistance.                    
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10. DIALLYL ISOPHTHALATE/VINYL ETHYL ETHER                                
(1:1)                                                                     
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            1.5 M Rad at 37,632 rad/hr produced a                         
            clear silghtly viscous prepolymer.                            
Copper:     1 coat 30 min cure produced an excellent                      
            glossy finish with excellent scratch                          
            resistance.                                                   
Cardboard:  2 coats, 5 min cure/coat gave no gloss.                       
Polypropylene:                                                            
            1 coat, 30 min cure produced a spotty                         
            finish with excellent scratch resistance.                     
Solvent Resistance:                                                       
            Copper coating - good resistance.                             
            Polypropylene coating - good resistance.                      
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11. DIALLYL ISOPHTHALATE/VINYL ACETATE (2:1)                              
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            2.0 M Rad at 37,632 rad/hr produced a                         
            clear slightly viscous prepolymer.                            
Copper:     1st coat, 15 min cure, 2nd coat 35 min                        
            cure gave a crazed finish with very good                      
            scratch resistance.                                           
Cardboard:  2 coats, 15 min cure/coat gave no gloss.                      
Polypropylene:                                                            
            2 coats, 15 min cure/coat gave a spotty                       
            finish with excellent scratch resistance.                     
Solvent Resistance:                                                       
            Copper coating - good                                         
            Polypropylene coating - good                                  
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12. DIALLYL ISOPHTHALATE/2-HEXYL ETHYL                                    
ACRYLATE (2:1)                                                            
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            1.0 M Rad at 37,632 rad/hr gave a clear                       
            yellow viscous prepolymer.                                    
Copper:     1 coat, 40 min cure produced a matt                           
            finish with good scratch resistance.                          
Cardboard:  1st coat, 5 min cure, 2nd &amp; 3rd coats,                        
            10 min cure/coat produced a good gloss.                       
Polypropylene:                                                            
            1 coat, 40 min cure produced a spotty                         
            finish with poor scratch resistance.                          
Solvent Resistance:                                                       
            Copper Coating - very good resistance.                        
            Polypropylene Coating - very good                             
            resistance.                                                   
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13. DIALLYL ISOPHTHALATE/ALLYL GLYCIDYL                                   
ETHER (1:1)                                                               
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            2.0 M Rad at 37,632 rad/hr gave a clear                       
            slightly viscous prepolymer.                                  
Copper:     1 coat, 40 min cure produced a matt                           
            crazed finish which was soft.                                 
Cardboard:  3 coats, 5 min cure/coat gave no gloss.                       
Polypropylene:                                                            
            1 coat 40 min cure produced a smooth                          
            finish with good scratch resistance.                          
Solvent Resistance:                                                       
            Nil                                                           
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14. VINYL ETHYL ETHER/2-HEXYL ETHYL ACRYLATE                              
(1:1)                                                                     
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            1.0 M Rad at 37,632 rad/hr gave a clear                       
            viscous prepolymer.                                           
Copper:     2 coats, 10 min cure/coat gave an                             
            excellent gloss and excellent scratch                         
            resistance.                                                   
Cardboard:  2 coats, 10 min cure/coat gave no gloss.                      
Polypropylene:                                                            
            2 coats, 10 min cure/coat gave a soft                         
            spotty finish.                                                
Solvent Resistance:                                                       
            Nil                                                           
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15. STYRENE/ALLYL GLYCIDYL ETHER (1:1)                                    
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            1.5 M Rad at 37,632 rad/hr gave a clear                       
            very viscous prepolymer.                                      
Copper:     1 coat, 15 min cure gave an excellent                         
            glossy finish with excellent scratch                          
            resistance.                                                   
Cardboard:  1 coat, 5 min cure gave no gloss.                             
Polypropylene:                                                            
            1 coat, 15 min cure gave an excellent                         
            glossy finish with poor scratch resist-                       
            ance.                                                         
Solvent Resistance:                                                       
            Nil                                                           
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16. ACRYLAMIDE/ACRYLIC ACID (1:1)                                         
______________________________________                                    
Solvent:    Methanol                                                      
Prepolymer Prepn:                                                         
            1.0 M Rad at 37,632 rad/hr gave a clear                       
            slightly viscous prepolymer                                   
Copper:     2 coats, 5 min cure/coat gave a green                         
            glossy finish with very good scratch                          
            resistance.                                                   
Cardboard:  2 coats, 5 min cure/coat gave no gloss                        
Polypropylene:                                                            
            2 coats, 5 min cure/coat gave a spotty                        
            finish with very good scratch resistance.                     
Solvent Resistance:                                                       
            Partial resistance.                                           
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17. ACRYLAMIDE/VINYL ETHYL ETHER (1:1)                                    
______________________________________                                    
Solvent:    Methanol                                                      
Prepolymer Prepn:                                                         
            1.0 M Rad at 37,632 rad/hr gave a                             
            liquid and a white solid mass.                                
Copper:     1 coat, 5 min cure gave an excellent                          
            glossy finish with excellent scratch                          
            resistance.                                                   
Cardboard:  Omitted.                                                      
Polypropylene:                                                            
            1 coat, 5 min cure gave a spotty finish                       
            with average scratch resistance.                              
Solvent Resistance:                                                       
            Very good solvent resistance.                                 
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18. ACRYLAMIDE/ALLYLAMINE (1:1:)                                          
______________________________________                                    
Solvent:    Methanol                                                      
Prepolymer Prepn:                                                         
            2.0 M Rad at 37,632 rad/hr gave a clear                       
            slightly viscous prepolymer.                                  
Copper:     1 coat, 35 min cure produced a sticky                         
            dark brown finish.                                            
Cardboard:  1 coat, 15 min cure produced no gloss                         
Polypropylene:                                                            
            1 coat, 35 min cure produced a sticky                         
            dark brown finish.                                            
Solvent Resistance:                                                       
            Nil                                                           
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19. ACRYLAMIDE/ALLYLACRYLATE (1:1)                                        
______________________________________                                    
Solvent:    Methanol                                                      
Prepolymer Prepn:                                                         
            2.0 M Rad at 37,632 rad/hr gave a                             
            liquid and white solid mass.                                  
Copper:     1 coat, 10 min cure produced a glossy                         
            finish with good scratch resistance.                          
Cardboard:  Omitted.                                                      
Polypropylene:                                                            
            1 coat, 10 min cure produced a smooth                         
            glossy finish with good scratch resist-                       
            ance.                                                         
            cure, gave a matt finish with excellent                       
            scratch resistance.                                           
Cardboard:  2 coats, 2 min cure/coat gave no gloss.                       
Polypropylene:                                                            
            1st coat, 2 min cure, 2nd coat, 7 min                         
            cure, produced a spotty finish with poor                      
            scratch resistance.                                           
Solvent Resistance:                                                       
            Nil                                                           
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23. MALEIC ANHYDRIDE/ALLYL ACRYLATE (1:1)                                 
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            1.5 M Rad at 37,255 rad/hr produced a                         
            clear extremely viscous prepolymer.                           
Copper:     1 coat, 10 min cure produced a matt                           
            finish with excellent scratch resistance.                     
Cardboard:  2 coats, 5 min cure per coat produced                         
            no gloss.                                                     
Polypropylene:                                                            
            1 coat, 10 min cure produced a spotty                         
            finish with excellent scratch resistance.                     
Solvent Resistance:                                                       
            Nil                                                           
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24. ACRYLIC ACID/VINYL ACETATE (1:1)                                      
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            0.5 M Rad at 37,255 rad/hr produced a                         
            slightly viscous clear solution plus                          
            some whate precipitate.                                       
Copper:     1 coat, 10 min cure produced a gloss                          
            finish with average scratch resistance.                       
Cardboard:  2 coats, 5 min cure/coat produced no                          
            gloss.                                                        
Polypropylene:                                                            
            1 coat, 10 min cure produced a spotty                         
            finish with good scratch resistance.                          
Solvent Resistance:                                                       
            Good                                                          
Solvent Resistance:                                                       
            Nil                                                           
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20. MALEIC ANHYDRIDE/ACRYLIC ACID (1:1)                                   
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            1.5 M Rad at 37,632 rad/hr gave a                             
            clear slightly viscous solution.                              
Copper:     1 coat, 10 min cure produced a glossy                         
            finish with good scratch resistance.                          
Cardboard:  Omitted                                                       
Polypropylene:                                                            
            1 coat, 10 min cure produced a smooth                         
            glossy finish with average scratch                            
            resistance.                                                   
Solvent Resistance:                                                       
            Nil                                                           
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21. MALEIC ANHYDRIDE/VINYL ETHYL ETHER (1:1)                              
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            2.0 M Rad at 37,632 rad/hr gave a                             
            slightly viscous red solution.                                
Copper:     1st coat, 2 min cure, 2nd coat, 7 min                         
            cure, produced a matt finish with av-                         
            erage scratch resistance.                                     
Cardboard:  1st coat, 2 min cure, 2nd coat, 3 min                         
            cure produced no gloss.                                       
Polypropylene:                                                            
            1st coat, 2 min cure, 2nd coat, 7 min                         
            cure gave a spotty finish with poor                           
            scratch resistance.                                           
Solvent Resistance:                                                       
            Nil                                                           
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22. MALEIC ANHYDRIDE/VINYL ACETATE (1:1)                                  
______________________________________                                    
Solvent:    Acetone.                                                      
Prepolymer Prepn:                                                         
            2.0 M Rad at 37,632 rad/hr gave a                             
            slightly viscous red solution.                                
Copper:     1st coat, 2 min cure, 2nd coat, 7 min                         
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25. ACRYLIC ACID/ALLYL ACRYLATE (1:1)                                     
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            0.5 M Rad at 37,255 rad/hr produced a                         
            slightly viscous yellowish prepolymer                         
Copper:     1 coat, 10 min cure produced an excellent                     
            gloss and excellent scratch resistance.                       
Cardboard:  2 coats, 5 min cure/coat gave no gloss.                       
Polypropylene:                                                            
            1 coat, 10 min cure produced a spotty                         
            finish with good scratch resistance.                          
Solvent Resistance:                                                       
            Excellent                                                     
______________________________________                                    
 
    
     
         ______________________________________                                    
26. VINYL ETHYL ETHER/ALLYL ACRYLATE (1:1)                                
______________________________________                                    
Solvent:    Acetone                                                       
Prepolymer Prepn:                                                         
            1.0 M Rad at 37,255 rad/hr produced a                         
            slightly viscous clear prepolymer.                            
Copper:     1 coat, 20 min cure produced an excellent                     
            gloss and excellent scratch resistance.                       
Cardboard:  2 coats, 5 min cure/coat produced no                          
            gloss.                                                        
Polypropylene:                                                            
            1 coat, 20 min cure produced a spotty                         
            finish with average scratch resistance.                       
Solvent Resistance:                                                       
            Poor                                                          
______________________________________                                    
 
    
     The following examples show the use of prepolymers prepared by U.V. radiation of the monomers listed. The prepolymers were cured on the substrates listed in the manner described for the previous examples. The solvents used were solely to enable the prepolymer to be sprayed onto the substrate using a low viscosity spray gun. 
     27. STYRENE 
     13 hour irradiation produced a clear viscous prepolymer. The viscosity did not change much after an initial viscosity increase and so the preparation time is arbitrary. 
     
         ______________________________________                                    
Solvent:    Benzene                                                       
Cardboard:  2 coats, 1 min cure/coat produced a                           
            good gloss.                                                   
Aluminum:   1 coat, 1 min cure produced an excellent                      
            glossy finish with excellent scratch                          
            resistance.                                                   
Copper:     Same as aluminum.                                             
Solvent Resistance:                                                       
            Poor solvent resistance for coatings                          
            on aluminium and copper, complete re-                         
            moval of gloss from cardboard.                                
______________________________________                                    
 
    
     
         ______________________________________                                    
28. STYRENE/BUTYL ACRYLATE                                                
Same method of preparation as for 27.                                     
Solvent:                                                                  
        Benzene                                                           
Cardboard:                                                                
        3 coats, 1 min cure/coat gave a glossy                            
        finish.                                                           
Aluminium:                                                                
        2 coats, 2 min cure/coat produced a glossy                        
        homogeneous finish with excellent scratch                         
        resistance.                                                       
Copper: Same as Aluminium, except good scratch                            
        resistance                                                        
______________________________________                                    
 
    
     
         ______________________________________                                    
29. STYRENE/METHYL METHACRYLATE                                           
(1:1) Clear viscous liquid                                                
(2:1) Clear viscous liquid                                                
(1:2) Yellowish viscous liquid                                            
Irradiation Times                                                         
(1:1) 23 hours irradiation                                                
(2:1) 23 hours irradiation                                                
(1:2) 241/4 hours irradiation                                             
Solvent:    Acetone                                                       
Cardboard (1:1)                                                           
            2 coats, 2 min cure/coat produced a poor                      
            gloss.                                                        
Copper (1:1):                                                             
            1 coat, 5 min cure produced an excellent                      
            gloss with good scratch resistance.                           
Cardboard (2:1):                                                          
            3 coats, 3 min cure/coat produced a slight                    
            gloss.                                                        
Copper (2:1):                                                             
            1 coat, 5 min cure/coat produced an excell-                   
            ent gloss with good scratch resistance.                       
Cardboard (1:2):                                                          
            2 coats, 3 min cure/coat produced a slight                    
            gloss                                                         
Copper (1:2):                                                             
            1 coat, 5 min cure produced an excellent                      
            gloss with good scratch resistance.                           
Solvent Resistance:                                                       
            Nil                                                           
______________________________________                                    
 
    
     
         ______________________________________                                    
30. STYRENE/VINYLEDENE CHLORIDE                                           
(7:3) Slightly yellow viscous prepolymer                                  
(1:1) Slightly yellow viscous prepolymer                                  
______________________________________                                    
Irradiation Times                                                         
(7:3) 28 hours irradiation                                                
(1:1) 17 hours irradiation                                                
Solvent:    Benzene                                                       
Cardboard (7:3):                                                          
            3 coats, 5 min cure/coat produces a slight                    
            gloss.                                                        
Copper (7:3):                                                             
            1 coat, 5 min cure produced an excellent                      
            gloss with good scratch resistance.                           
Cardboard (1:1):                                                          
            2 coats, 2 min cure/coat produced a glossy                    
            finish.                                                       
Copper (1:1):                                                             
            1 coat, 5 min cure produced an excellent                      
            gloss with good scratch resistance.                           
Solvent Resistance:                                                       
            Nil                                                           
______________________________________                                    
 
    
     
         ______________________________________                                    
31. BUTYL ACRYLATE/METHYL METHACRYLATE                                    
Mixtures of ratios 1:1, 2:1 and 1:2 produced very viscous                 
clear one phase prepolymers.                                              
Irradiation Times                                                         
(1:1) 23/4 hours irradiation                                              
(2:1) 23/4 hours irradiation                                              
(1:2) 31/2 hours irradiation                                              
Solvent:    Acetone                                                       
Cardboard:  2 coats, 1 min cure/coat gave no gloss                        
Aluminium:  1 coat, 1 min cure/coat gave a glossy                         
            homogeneous finish with excellent scratch                     
            resistance.                                                   
Copper:     Same as Aluminium                                             
Solvent Resistance:                                                       
Aluminium and Copper coatings: Poor resistance to acetone                 
Cardboard coating: Nil resistance.                                        
______________________________________                                    
 
    
     
         ______________________________________                                    
32. BUTYL ACRYLATE/ACRYLONITRILE                                          
(1:1) Clear slightly green one phase prepolymer                           
(2:1) Clear slightly yellow one phase prepolymer                          
(1:2) White liquid opaque mass produced after 13/4 hours                  
    irradiation.                                                          
Irradiation Times                                                         
(1:1) 2 hours irradiation                                                 
(2:1) 21/4 hours irradiation                                              
(1:2) 13/4 hours irradiation (see above)                                  
Testing on Cardboard, Aluminium and Copper to be done.                    
______________________________________                                    
 
    
     
         ______________________________________                                    
33. BUTYL ACRYLATE/VINYLEDENE CHLORIDE                                    
1:3   Yellow clear viscous one phase prepolymer                           
1:2                                                                       
1:1   Yellowish slightly opaque one phase prepolymer                      
2:1   Yellow clear extremely viscous one phase prepolymer                 
Irradiation Times                                                         
(1:3) 17 hours irradiation                                                
(1:2)                                                                     
(1:1) 93/4 hours irradiation                                              
(2:1) 183/4 hours irradiation                                             
Solvent:    Acetone                                                       
Cardboard (1:1):                                                          
            1st coat 2 min cure, 2nd coat 5 min                           
            cure produced a very good gloss (with a                       
            tendency to bubble)                                           
Copper (1:1):                                                             
            1 coat 4 min cure produced a patchy                           
            finish with very good gloss.                                  
Cardboard (1:3):                                                          
            1st coat, 3 min cure, 2nd coat 6 min                          
            cure produced an excellent gloss.                             
Copper (1:3):                                                             
            1 coat, 5 min cure produced a glossy                          
            wrinkled finish.                                              
Solvent Resistance:                                                       
            Nil                                                           
______________________________________                                    
 
    
     
         ______________________________________                                    
34. BUTYL ACRYLATE/VINYL ACETATE                                          
(1:1) Slightly cloudy, slightly yellow one phase                          
      prepolymer.                                                         
(2:1) &amp; Clear slightly yellow one phase prepolymer.                       
(1:2) &#34;                                                                   
Irradiation Time                                                          
(1:1) 11/2 hours irradiation                                              
(2:1) 13/4 hours irradiation                                              
(1:2) 13/4 hours irradiation                                              
Solvent:    Acetone                                                       
Cardboard (1:1):                                                          
            1 coat, 5 mins cure/coat produced a poor                      
            gloss                                                         
Aluminium and                                                             
            1 coat, 2 min cure/coat produced a rough                      
Copper (1:1):                                                             
            matt homogeneous finish with good scratch                     
            resistance.                                                   
Cardboard (2:1):                                                          
            2 coats, 11/2 mins cure for 1st coat,                         
            4 mins for second, produced no gloss                          
Aluminium and                                                             
            1 coat, 4 min cure/coat for Aluminium,                        
Copper (2:1):                                                             
            6 min cure/coat for Copper, produced                          
            a matt finish with average scratch                            
            resistance.                                                   
Cardboard (1:2):                                                          
            2 coats, 1 min for 1st coat, 2 mins for                       
            2nd, produced a glossy finish                                 
Aluminium and                                                             
            1 coat, 4 mins cure produced a matt                           
Copper (1:2):                                                             
            homogeneous finish with average scratch                       
            resistance.                                                   
Solvent resistance:                                                       
            Poor solvent resistance to acetone for                        
            coatings on Aluminium and Copper at 1:1,                      
            2:1, and 1:2 ratios. Complete gloss                           
            removal from coardboard at 1:1, 2:1 and                       
            1:2 ratios                                                    
______________________________________                                    
 
    
     
         ______________________________________                                    
35. METHYL METHACRYLATE/VINYLEDENE                                        
  CHLORIDE                                                                
Mixtures of ratios 1:1, 2:1 and 1:2 produced clear yellow                 
viscous one phase prepolymers.                                            
(1:1) Yellow                                                              
(2:1) Very slightly yellow                                                
(1:2) Slighty yellow                                                      
Irradiation Time                                                          
(1:1) 15 hours irradiation                                                
(2:1)  8 hours irradiation                                                
(1:2) 131/2 hours irradiation                                             
Solvent:    Acetone                                                       
Cardboard (1:1):                                                          
            3 coats, 2 min cure/coat produced a                           
            glossy but speckeldy finish.                                  
Aluminimum (1:1):                                                         
            1 coat, 5 mins cure/coat produced a                           
            yellow glossy homogenous coat with                            
            excellent scratch resistance                                  
Copper (1:1)                                                              
            Same as Aluminium                                             
Cardboard (2:1)                                                           
            3 coats, 2 mins cure/coat gave a glossy                       
            but speckeldy finish                                          
Aluminium (2:1):                                                          
            1 coat, 5 min cure/coat produced a smooth                     
            matt finish with no gloss, but excellent                      
            scratch resistance.                                           
Copper (2:1):                                                             
            Same as Aluminium                                             
Cardboard (1:2):                                                          
            2 coats, 2 mins cure/coat produced a                          
            glossy speckeldy finish better than                           
            (1:1) and (2:1).                                              
Aluminium (1:2):                                                          
            1 coat 4 min cure, 2nd coat, 5 min cure                       
            produced a slighly yellow speckeldy                           
            finish with excellent scratch resistance.                     
Copper (1:2):                                                             
            Same as Aluminium                                             
Solvent Resistance:                                                       
            All ratios have poor resistance to acetone.                   
______________________________________                                    
 
    
     
         ______________________________________                                    
36.  METHYL METHACRYLATE/ACRYLONITRILE                                    
Mixtures of ratios 1:1, 2:1 and 1:2 produced slightly yellow              
and opaque one phase prepolymers.                                         
Irradiation Times                                                         
(1:1) 41/2 hours irradiation                                              
(2:1) 31/4 hours irradiation                                              
(1:2) 31/2 hours irradiation                                              
Cardboard:   1 coat, 1 min cure/coat produced no                          
(1:1, 2:1, 1:2)                                                           
             gloss.                                                       
Aluminium:   Rough matt finish with best scratch                          
(1:1, 2:1, 1:2)                                                           
             resistance found in all experiments                          
             1 minute cure/coat.                                          
Copper:      Same as aluminium.                                           
(1:1), 2:1, 1:2)                                                          
Solvent:     Acetone                                                      
Solvent resistance:                                                       
             Poor solvent resistance to coatings                          
             on Aluminium and Copper. Complete                            
             removal of coatings on cardboard.                            
______________________________________                                    
 
    
     
         ______________________________________                                    
37. METHYL METHACRYLATE/VINYL ACETATE                                     
(1:1)  produced a slightly opaque one phase system                        
(2:1)  produced a clear one phase system                                  
(1:2)  produced a slighty yellow one phase system                         
Irradiation Times                                                         
(1:1)  5 hours irradiation                                                
(2:1)  3 hours irradiation                                                
(1:2)  22 hours irradiation                                               
Solvent:    Acetone                                                       
Cardboard (1:1):                                                          
            1 coat, 1 minute cure/coat produced no                        
            gloss.                                                        
Aluminium (1:1):                                                          
            Rough matt finish with good scratch                           
            resistance.                                                   
Copper (1:1):                                                             
            Same as aluminium                                             
Cardboard (2:1):                                                          
            1 coat, 1 min cure/coat produced no gloss.                    
Aluminium (2:1):                                                          
            1 coat, 1 min cure/coat produced a rough                      
            matt finish with excellent scratch                            
            resistance.                                                   
Copper (2:1):                                                             
            Same as aluminium.                                            
Cardboard (1:2):                                                          
            1 coat, 1 min cure/coat, produced a gloss                     
            finish.                                                       
Aluminium (1:2):                                                          
            1 coat, 1 min cure/coat produced a rough                      
            matt finish with excellent scratch                            
            resistance.                                                   
Copper (1:2):                                                             
            Same as aluminium                                             
Solvent Resistance:                                                       
            Aluminium and copper coatings completely                      
            removed by acetone.                                           
            Cardboard coating at (1:2) ration                             
            partially removed by acetone.                                 
            Cardboard coating at (1:1), (2:1) ratios                      
            completely removed by acetone.                                
______________________________________                                    
 
    
     
         ______________________________________                                    
38. VINYLEDENE CHLORIDE/ACRYLONITRILE                                     
(1:1) White opaque appearances after 45 mins. irradiation,                
      homopolymerisation evident after 31/4 hours irradiation.            
      Discarded.                                                          
(2:1) White opaque appearance after 45 mins, almost clear                 
      at 31/4 hours irradiation. -(1:2) White opaque appearance after 30  
      mins irradiation,                                                   
      homopolymerisation evident after 4 hours irradiation.               
      Discarded.                                                          
______________________________________                                    
 
    
     
         ______________________________________                                    
39. VINYLEDENE CHLORIDE/VINYL ACETATE                                     
(1:1)                                                                     
     White opaque appearance after 45 mins irradiation,                   
     homopolymerisation evident after 63/4 hours irradiation.             
     Discarded.                                                           
(2:1)                                                                     
     Homopolymerisation evident after 14 hours irradiation.               
     Discarded.                                                           
(1:2)                                                                     
     57 hours irradiation produces a yellow viscous pre-                  
     polymer.                                                             
(1:3)                                                                     
     Clear yellow viscous prepolymer after 23 hours                       
     irradiation.                                                         
______________________________________                                    
 
    
     
         ______________________________________                                    
40. ETHYL ACRYLATE/VINYLEDENE CHLORIDE                                    
(1:3)                                                                     
     Sample allowed to stand without inhibitor in lab.,                   
     and polymerised to a viscous mass in 5 days.                         
(1:2)                                                                     
     Yellow clear viscous one phase prepolymer                            
(1:1)                                                                     
     Yellow clear viscous one phase prepolymer                            
(2:1)                                                                     
     Yellow clear viscous one phase prepolymer                            
Irradiation Times                                                         
(1:3)                                                                     
     See above                                                            
(1:2)                                                                     
     16 hours irradiation                                                 
(1:1)                                                                     
     121/2 hours irradiation                                              
(2:1)                                                                     
     14 hours irradiation                                                 
Solvent:    Acetone                                                       
Cardboard (1:3):                                                          
            1st coat 2 min cure, 2nd coat, 3 min                          
            cure produced a speckeldy glossy finish                       
Copper (1:3):                                                             
            2 coats, 3 min cure produced a glossy                         
            speckeldy finish with very good scratch                       
            resistance.                                                   
Cardboard (1:2):                                                          
            1st coat, 4 min cure, 2nd coat, 10 min                        
            cure produced an excellent gloss.                             
Copper (1:2):                                                             
            1 coat, 15 min cure produced an excellent                     
            glossy finish with excellent scratch                          
            resistance.                                                   
Cardboard (1:1):                                                          
            1st coat, 3 min cure, 2nd coat, 6 min.                        
            cure produced an excellent gloss.                             
Copper (1:1):                                                             
            1st coat, 3 min cure produced an excellent                    
            gloss with very good scratch resistance.                      
Cardboard (3:1):                                                          
            3 coats, 5 min cure/coat produced a                           
            speckeldy gloss.                                              
Copper (3:1):                                                             
            1 coat, 15 min, cure produced a speckeldy                     
            glossy finish with excellent scratch                          
            resistance.                                                   
Solvent Resistance:                                                       
            Nil                                                           
______________________________________                                    
 
    
     
         ______________________________________                                    
41. ACRYLONITRILE/VINYL ACETATE                                           
Mixtures of (1:1), (2:1) and (1:2) all homopolymerised after              
1 hour&#39;s irradiation and were discarded.                                  
______________________________________                                    
 
    
     
         ______________________________________                                    
42. ACRYLONITRILE/STYRENE                                                 
Mixtures of ratios 1:1, 2:1, 1:2, 4:1 and (1:2), (2:1), -slightly yellow  
clear viscous one phase prepolymers. The -acrylonitrile/styrene (8:1)     
mixture homopolymerised.                                                  
Irradiation times                                                         
(1:1)  6 hours irradiation                                                
(1:2)  51/2 hours irradiation                                             
(2:1)  6 hours irradiation                                                
(4:1)  5 hours irradiation                                                
(6:1)  61/2 hours irradiation                                             
Solvent:                                                                  
            Acetone                                                       
Curing conditions for all mixtures:                                       
Cardboard:  3 coats, 2 mins. cure/coat                                    
Aluminium:  2 coats, 4 mins. cure/coat                                    
Copper:     2 coats, 5 mins. cure/coat                                    
Cardboard (1:1):                                                          
            Slightly glossy spotty finish                                 
Aluminium (1:1):                                                          
            Rough matt finish with excellent scratch                      
            resistance.                                                   
Copper (1:1):                                                             
            Same as aluminium                                             
Cardboard (1:2):                                                          
            Same as (1:1)                                                 
Aluminium (1:2):                                                          
            Rough matt finish with average scratch                        
            resistance.                                                   
Copper (1:2):                                                             
            Same as Aluminium                                             
Cardboard (2:1):                                                          
            Same as (1:1)                                                 
Aluminium and                                                             
            Same as (1:2)                                                 
Copper (2:1):                                                             
Cardboard (4:1):                                                          
            Same as (1:1)                                                 
Aluminium (4:1):                                                          
            Rough matt finish with good scratch                           
            resistance.                                                   
Copper (4:1):                                                             
            Same as aluminium                                             
Cardboard (6:1):                                                          
            Same as (1:1)                                                 
Aluminium and                                                             
Copper (6:1):                                                             
            Same as (4:1)                                                 
Prepolymer of Acrylonitrile/Styrene (8:1) was attempted                   
but homopolymerised.                                                      
Solvent Resistance:                                                       
            Poor to acetone given by coatings at                          
            (1:1), (1:2), (2:1), (4:1), and (6:1)                         
            on Aluminium and Copper.                                      
            Coating removed from cardboard at ratios                      
            of (1:1), (2:1), (1:2), (4:1) and (6:1).                      
______________________________________                                    
 
    
     
         ______________________________________                                    
43. LINSEED OIL/STYRENE PREPOLYMERS                                       
(1:1) On standing at about 0° C a two phase system is              
      evident. This consists of a yellowish liquid and                    
      a white solid. On shaking these produced a one-                     
      phase opaque white viscous mass.                                    
(2:1) One phase system. A yellowish opaque viscous                        
(1:2) mass is produced.                                                   
Irradiation Times                                                         
1:1   24 hours, 1% Divinyl Benzene added, further 71/2 hours =            
      311/2 hours.                                                        
2:1   24 hours, 1% Divinyl Benzene added, further 71/2 hours =            
      311/2 hours                                                         
1:2   17 hours, 1% Divinyl Benzene added, further 7 hours =               
      24 hours.                                                           
Solvent:    Acetone                                                       
Cardboard (1:1):                                                          
            3 coats, 3 min cure/coat produced a slight                    
            gloss.                                                        
Aluminium (1:1):                                                          
            1 coat, 8 mins cure produced a hard                           
            glossy homogeneous finish.                                    
Copper (1:1):                                                             
            Same as Aluminium, except 10 min cure                         
Cardboard (2:1):                                                          
            Same as (1:1)                                                 
Aluminium (2:1):                                                          
            Same as 1:1 except 4 min cure.                                
Copper (2:1):                                                             
            Same as 1:1 except 7 min cure.                                
Cardboard (1:2):                                                          
            Same as (1:1).                                                
Aluminium (1:2):                                                          
            Same as 1:1 except 31/2 min cure.                             
Copper (1:2):                                                             
            Same as 1:1 except 131/2 min cure.                            
Solvent Resistance:                                                       
            Poor solvent resistance to acetone                            
            by coatings on Aluminium and Copper.                          
            Acetone produces slight coating removal                       
            at (1:1), and (1:2) though complete                           
            removal occurs at (2:1) on cardboard.                         
______________________________________                                    
 
    
     
         ______________________________________                                    
44. LINSEED OIL/STYRENE + SARTOMER                                        
   MONOMERS 444 PREPOLYMERS                                               
(1:1)                                                                     
     On standing at 0° C a two phase system is evident.            
     This consists of a yellowish liquid and a white                      
     solid. On shaking these produced a yellow opaque                     
     one phase viscous mass. Similar to 1:1 with 1%                       
     Divinyl Benzene                                                      
(2:1)                                                                     
     Yellow liquid with a small amount of white solid.                    
     White solid does not dissolve in the yellow liquid.                  
(1:2)                                                                     
     A slightly opaque viscous liquid which is one phase.                 
Irradiation Times                                                         
(1:1)                                                                     
     1% Sartomer monomers 444 added, 30 hours irradiation                 
(2:1)                                                                     
     &#34;                                                                    
(1:2)                                                                     
     &#34;                                                                    
Solvent:    Acetone for 1:1, 2:1 and 1:2                                  
Cardboard (1:1):                                                          
            3 coats, 3 mins cure/coat produced rough                      
            finish with a slight gloss.                                   
Aluminium (1:1):                                                          
            One coat, 15 mins cure produced an                            
            inhomogeneous rough matt finish with                          
            average scratch resistance                                    
Copper (1:1):                                                             
            One coat, 20 mins cure time. Same                             
            finish as Aluminium                                           
Cardboard (2:1):                                                          
            4 coats, 3 mins. cure/coat produced a                         
            slight gloss.                                                 
Aluminium (2:1):                                                          
            1 coat, 10 min. cure produced an excellent                    
            glossy homogenous finish with excellent                       
            scratch resistance.                                           
Copper (2:1):                                                             
            1 coat, 15 min cure. Same finish as                           
            aluminium.                                                    
Cardboard (1:2):                                                          
            3 coats, 3 mins. cure/coat produced a                         
            good but speckeldy gloss.                                     
Aluminium (1:2):                                                          
            1 coat, 15 mins cure produced a very good                     
            gloss which is slightly speckeldy.                            
            Excellent scratch resistance.                                 
Copper (1:2):                                                             
            Same as Aluminium.                                            
Solvent Resistance:                                                       
            Poor solvent resistance of ratios 1:1,                        
            2:1 and 1:2 to Acetone                                        
______________________________________                                    
 
    
     
         ______________________________________                                    
45. LINSEED OIL/STYRENE + 10% SARTOMER                                    
  MONOMERS 444 PREPOLYMERS                                                
(1:1) On standing at 0° C a two phase system is evident.           
      This consists of a yellow liquid and a white solid.                 
(2:1) On standing at 0° C a white opaque solid mass is             
      evident.                                                            
(1:2) Same as (2:1) ratio.                                                
Irradiation Times                                                         
(1:1)                                                                     
     10% Sartomer Monomers 444 added, 2 hours irradiation                 
(2:1)                                                                     
     &#34;                                                                    
(1:2)                                                                     
     &#34;                                                                    
______________________________________                                    
 
    
     
         ______________________________________                                    
46. LINSEED OIL/METHYLSTYRENE                                             
Mixtures of 1:1, 2:1 and 1:2 produces yellow very liquid                  
one phase prepolymers.                                                    
Irradiation Time                                                          
1:1  24 hours, 1% Divinyl Benzene added, further 34 hours                 
     irradiaton = 58 hours.                                               
2:1  24 hours, 1% Divinyl Benzene added, further 241/2 hours              
     irradiation = 481/2 hours.                                           
1:2  151/2 hours, 1% Divinyl Benzene added, further 411/2 hours           
     irradiation = 57 hours                                               
Solvent:    Benzene                                                       
Cardboard (1:1):                                                          
            3 coats, 3 mins cure/coat produced a                          
            non-gloss finish                                              
Aluminium (1:1):                                                          
            1st coat, 10 min cure, 2nd coat, 20 mins                      
            cure produced a glossy homogeneous finish                     
            with excellent scratch resistance.                            
Copper (1:1):                                                             
            Same as Aluminium                                             
Cardboard (2:1):                                                          
            Same as 1:1                                                   
Aluminium (2:1):                                                          
            Same as 1:1 except 2nd coat cured in                          
            30 mins.                                                      
Copper (2:1):                                                             
            1 coat, 20 min cure produced a smooth                         
            glossy finish with excellent scratch                          
            resistance.                                                   
Cardboard (1:2):                                                          
            Same as (1:1) and (2:1).                                      
Aluminium (1:2):                                                          
            Same as (1:1).                                                
Copper (1:2):                                                             
            1 coat, 15 mins. cure produced a smooth                       
            glossy finish with excellent scratch                          
            resistance.                                                   
Solvent Resistance:                                                       
            Poor solvent resistance to acetone.                           
            Coating at (2:1) better than (1:1),                           
            which is better than (1:2).                                   
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         ______________________________________                                    
47. LINSEED OIL/BUTYL ACRYLATE                                            
(1:1)                                                                     
     Precipitate present which can be dissolved into                      
     liquid phase. A clear very liquid prepolymer.                        
(2:1)                                                                     
     Same 1:1.                                                            
(1:2)                                                                     
     Precipitate present which can be dissolved into                      
     liquid phase. A yellow very liquid prepolymer.                       
Irradiation Time                                                          
(1:1)                                                                     
     19 hours, 1% Divinyl Benzene added, further 12                       
     hours irradiation = 31 hours.                                        
(2:1)                                                                     
     15 hours, 1% Divinyl Benzene added, further 8                        
     hours irradiaion = 23 hours.                                         
(1:2)                                                                     
     15 hours, 1% Divinyl Benzene added, further 8                        
     hours irradiation = 23 hours.                                        
Solvent:    Acetone                                                       
Cardboard (1:1):                                                          
            2 coats, 1 min cure/coat produced a                           
            matt finish.                                                  
Aluminium and                                                             
            1 coat, 20 mins cure produced a soft                          
Copper (1:1):                                                             
            glossy homogeneous finish.                                    
Cardboard (2:1):                                                          
            2 coats, 1 min cure/coat produced a                           
            very slight gloss.                                            
Aluminium (2:1):                                                          
            1 coat, 10 min cure produced a hard                           
            glossy homogeneous finish.                                    
Copper (2:1):                                                             
            1 coat, 19 min. cure produced a soft                          
            glossy homogeneous finish.                                    
Cardboard (1:2):                                                          
            2 coats, 11/2 min cure/coat produced a                        
            very slight gloss.                                            
Aluminium (1:2):                                                          
            1 coat, 4 min cure produced a glossy                          
            homogeneous finish with average scratch                       
            resistance.                                                   
Copper (1:2):                                                             
            Same as Aluminium, 10 min cure produced                       
            a soft finish                                                 
Solvent Resistance:                                                       
            Poor solvent resistance of coatings on                        
            Aluminium and Copper. Acetone has very                        
            little effect on coating on cardboard.                        
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48. ALKYD RESIN/STYRENE                                                   
(1:1)                                                                     
     White opaque very viscous one phase prepolymer                       
(2:1)                                                                     
     Yellowish white opaque very viscous one phase prepolymer             
(1:2)                                                                     
     Yellowish liquid layer, white solid mass capable of                  
     dissolving in liquid layer.                                          
Irradiation Times                                                         
(1:1)                                                                     
     48 hours, 1% Divinyl Benzene added, further 12 hours                 
     irradiation = 68 hours                                               
(2:1)                                                                     
     38 hours, 1% Divinyl Benzene added, further 25 hours                 
     irradiaton = 73 hours.                                               
(1:2)                                                                     
     42 hours, 1% Divinyl Benzene added, further 18 hours                 
     irradiation = 60 hours                                               
Solvent:    Acetone and Benzene                                           
Cardboard (1:1):                                                          
            1 coat, 2 min cure produced an excellent                      
            gloss.                                                        
Aluminium (1:1):                                                          
            1 coat, 2 min cure produced a glossy                          
            homogeneous finish with excellent scratch                     
            resistance.                                                   
Copper (1:1):                                                             
            Same as Aluminium                                             
Prepolymer does not completely dissolve in acetone                        
Cardboard (2:1):                                                          
            A white ppte. produced. 2 coats, 2 min                        
            cure/coat produced a glossy speckeldy                         
            finish with white spots of homopolymer.                       
Aluminium (2:1):                                                          
            1 coat, 7 min cure produced a glossy                          
            homogeneous finish with excellent                             
            Sartomer monomers, but with white                             
            spots of homopolymer.                                         
Copper (2:1):                                                             
Cardboard (1:2):                                                          
            3 coats, 1 min cure/coat produced an                          
            average gloss.                                                
Aluminium (1:2):                                                          
            2 coats, 2 mins cure/coat produced a                          
            glossy homogeneous finish with excellent                      
            scratch resistance.                                           
Copper (1:2):                                                             
            Same as Aluminium.                                            
Solvent Resistance:                                                       
            Acetone - poor solvent resistance to                          
            acetone though 1:1 is marginally better                       
            than 1:2 on aluminium.                                        
            Benzene - Complete removal of gloss                           
            coating at ratios of 1:1 and 1:2.                             
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         ______________________________________                                    
49. ALKYD RESIN/METHYLSTYRENE                                             
All mixtures 1:1, 2:1 and 1:2 produced yellow very liquid                 
one phase systems.                                                        
Irradiation Time                                                          
(1:1)                                                                     
     61 hours, 1% Divinyl Benzene added, further 22 hours                 
     irradiation = 83 hours.                                              
(2:1)                                                                     
     56 hours, 1% Divinyl Benzene added, further 25 hours                 
     irradiation = 81 hours.                                              
(1:2)                                                                     
     60 hours, 1% Divinyl Benzene added, further 22 hours                 
     irradiaton = 82 hours.                                               
Cardboard (1:1):                                                          
            3 coats, 1 min cure/coat produced a poor                      
            gloss.                                                        
Aluminium (1:1):                                                          
            1 coat, 2 min cure produced an excellent                      
            glossy homogeneous finish with excellent                      
            scratch resistance.                                           
Copper (1:1):                                                             
            1 coat, 3 min cure, produced a finish                         
            same as Aluminium.                                            
Cardboard (2:1):                                                          
            3 coats, 1 min cure/coat produced an                          
            excellent glossy finish.                                      
Aluminium (2:1):                                                          
            1 coat, 2 min cure/coat produced a                            
            glossy homogeneous finish with excellent                      
            scratch resistance.                                           
Copper (2:1):                                                             
            1 coat, 4 min cure. Same finish as                            
            Aluminium.                                                    
Cardboard (1:2):                                                          
            2 coats, 1 min cure/coat produced no gloss.                   
Aluminium (1:2):                                                          
            Same as (1:1).                                                
Copper (1:2):                                                             
            Same as (1:1).                                                
Solvent Resistance                                                        
            : Poor solvent resistance to acetone for                      
            coatings on Aluminium and Copper.                             
            Complete removal of gloss coat at 1:1,                        
            2:1 and 1:2.                                                  
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         ______________________________________                                    
 50. ALKYD RESIN/BUTYL ACRYLATE + 1%                                      
   SARTOMER MONOMERS 444                                                  
(1:1)                                                                     
(2:1)   Yellow very viscous one phase prepolymers.                        
(1:2)                                                                     
Irradiation Time (hours)                                                  
(1:1)                                                                     
     1% Divinyl Benzene added 51/2 hours irradiation = 51/2 hours         
(2:1)                                                                     
     1% Divinyl Benzene added 81/2 hours irradiation = 81/2 hours         
(1:2)                                                                     
     23/4 hours 1% Divinyl Benzene added 3 hours irradiation              
     = 53/4 hours                                                         
Testing on Cardboard, Aluminium and Copper                                
BENZENE AS SOLVENT                                                        
Cardboard (1:1):                                                          
            1st coat, 2 min cure, 2nd coat, 7 min                         
            cure, produced a good gloss.                                  
Aluminium (1:1):                                                          
            2 coats, 5 min cure/coat produced a                           
            smooth glossy finish which is soft.                           
Copper (1:1):                                                             
            1 coat, 5 min cure produced a smooth glossy                   
            finish with excellent scratch resistance.                     
Solvent Resistance:                                                       
            Poor solvent resistance to acetone for                        
            coatings at 1:1 and 1:2 on Copper and                         
            Alluminium though 2:1 is marginally better                    
            on Aluminium.                                                 
Cardboard (2:1):                                                          
            2 coats, 3 min cure/coat produced an                          
            excellent gloss.                                              
Aluminium (2:1):                                                          
            1 coat, 10 min cure produced a smooth glossy                  
            finish with excellent scratch resistance.                     
Copper (2:1):                                                             
            Same as Aluminium except 20 min cure.                         
Cardboard (1:2):                                                          
            3 coats 3 min cure/coat produced a very                       
            slight gloss.                                                 
Aluminium (1:2):                                                          
            2 coats, 10 min cure/coat produced a smooth                   
            glossy finish with excellent scratch                          
            resistance.                                                   
Copper (1:2):                                                             
            Same as Aluminium except 20 min cure.                         
Solvent Resistance:                                                       
            Complete gloss removal for ratios of 1:1,                     
            2:1 and 1:2.                                                  
(1:1)                                                                     
(2:1)   Yellow very viscous phase prepolymers.                            
(1:2)                                                                     
                             Results                                      
                             for 1%                                       
                             Divinyl                                      
                             Ben-                                         
Prepolymer Irradiation Time (hours)                                       
                             zene                                         
______________________________________                                    
(1:1) 1% Sartomer Monomers 444, then 6 hrs irradiation                    
                             51/2                                         
(2:1) 1% Sartomer Monomers 444, then 8 hrs irradiation                    
                             81/2                                         
(1:2) 1% Sartomer Monomers 444, then 31/2 hrs irradiaion                  
                             53/4                                         
Testing on Cardboard, Aluminium and Copper                                
Cardboard (1:1):                                                          
            Not fully tested due to difficulty in                         
            dissolving prepolymer because of its high                     
            degree of polymerisation.                                     
Aluminium (1:1):                                                          
            1 coat, 10 min cure, 2nd coat, 15 min                         
            cure produced an excellent glossy finish                      
            with good scratch resistance.                                 
Copper (1:1):                                                             
            Same as Aluminium.                                            
Cardboard (2:1):                                                          
            3 coats, 3 mins cure/coat produced a                          
            very good gloss which was slighly                             
            inhomogeneous.                                                
Aluminium (2:1):                                                          
            1 coat, 15 min cure produced a glossy                         
            finish with good scratch resistance.                          
Copper (2:1):                                                             
            Same as Aluminium.                                            
Cardboard (1:2):                                                          
            3 coats, 3 mins cure/coat produced no                         
            gloss.                                                        
Aluminium (1:2):                                                          
            1 coat 25 min cure produced a smooth matt                     
            finish with good scratch resistance.                          
Copper (1:2):                                                             
            1 coat, 25 min cure, produced a smooth                        
            glossy finish with average scratch                            
            resistance.                                                   
Solvent Resistance:                                                       
            Pour solvent resistance to Acetone                            
            though better than other prepolymers                          
            tested. Possibly due to high molecular                        
            weight.                                                       
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51. GUM ROSIN/STYRENE                                                     
(1:1)                                                                     
     Yellow prepolymer with solid matter in liquid phase.                 
(2:1)                                                                     
     Yellow prepolymer with more solid matter than 1:1 in                 
     the solid phase.                                                     
(1:2)                                                                     
     Clear one phase prepolymer.                                          
Irradiation Times (hours)                                                 
(1:1) 1% Divinyl Benzene added 731/2 hours irradiation                    
(2:1) 1% Divinyl Benzene added 291/2 hours irradiation                    
(1:2) 1% Divinyl Benzene added 41 hours irradiation                       
Cardboard (1:1):                                                          
            3 coats, 1 min cure/coat produced a                           
            glossy finish.                                                
Aluminium (1:1):                                                          
            1 coat, 2 min cure, produced an                               
            excellent glossy finish with very                             
            good scratch resistance.                                      
Copper (1:1):                                                             
            1 coat, 3 min cure, same finish as                            
            Aluminium.                                                    
Benzene as Solvent                                                        
Cardboard (2:1):                                                          
            4 coats, 3 min cure/coat produced a                           
            slight gloss.                                                 
Aluminium (2:1):                                                          
            1 coat, 5 min cure, produced an                               
            excellent glossy finish with excellent                        
            scratch resistance.                                           
Copper (2:1):                                                             
            1 coat, 6 min cure, same finish as                            
            Aluminium.                                                    
Benzene                                                                   
Cardboard (1:2):                                                          
            2 coats, 1 min cure/coat produced a                           
            glossy finish.                                                
Aluminium (1:2):                                                          
            1 coat, 2 min cure, better finish than                        
            (1:1) but only very good scratch                              
            resistance.                                                   
Copper (1:2):                                                             
            1 coat, 3 min cure, same as Aluminium.                        
Benzene                                                                   
Solvent Resistance:                                                       
            Pour solvent resistance to acetone                            
            for coatings on Aluminium and Copper                          
            1:1 and 1:2                                                   
            Complete removal of gloss coat at 1:1                         
            and 1:2                                                       
(1:1.5)     Clear yellow liquid prepolymer                                
(1:10)      Clear slightly yellow slightly                                
            opaque liquid prepolymer.                                     
Irradiation Times (hours)                                                 
(1:1.5)                                                                   
       1% Divinyl Benzene added, 48 hours irradiation.                    
(1:10) 1% Divinyl Benzene added, 441/4 hours irradiation.                 
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         ______________________________________                                    
52. GUM ROSIN/α  METHYL STYRENE                                     
(1:1) Yellow very liquid one phase prepolymer                             
(2:1) yellow opaque solid mass.                                           
(1:2) Yellow very liquid one phase prepolymer                             
Irradiation Times                                                         
(1:1)  24 hours, 1% Divinyl Benzene added                                 
further 34 hrs. = 58 hrs                                                  
(2:1)  9 hours, 1% Divinyl Benzene added                                  
further 15 hrs. = 24 hrs                                                  
(1:2) 151/2 hrs. 1% Divinyl Benzene added                                 
further- 411/2 hrs. = 571/2 hrs                                           
Testing on Cardboard, Aluminium and Copper                                
Benzene as Solvent                                                        
Cardboard (1:1):                                                          
            3 coats, 1 min cure/coat produced a                           
            non-gloss finish.                                             
Aluminium (1:1):                                                          
            1st coat 6 min cure, 2nd coat 8 min                           
            cure produced a glossy yellow finish                          
            which was soft.                                               
Copper (1:1):                                                             
            1st coat 23 min cure, 2nd coat 23                             
            min cure produced a glossy yellow                             
            finish which was soft.                                        
Cardboard (2:1):                                                          
            3 coats 2 min cure/coat produced a                            
            non-gloss finish.                                             
Aluminium (2:1):                                                          
            1 coat, 30 min cure produced a glossy                         
            yellow finish which was soft.                                 
Copper (2:1):                                                             
            Same as Aluminium.                                            
Cardboard (1:2):                                                          
            Same as (2:1).                                                
Aluminium (1:2):                                                          
            1st coat, 15 min cure, 2nd coat                               
            30 min cure, produced a smooth                                
            glossy, finish with poor scratch                              
            resistance.                                                   
Copper (1:2):                                                             
            Same as Aluminium.                                            
Solvent Resistance:                                                       
            Poor solvent resistance to acetone                            
            for coatings on Aluminium and Copper                          
            at 1:1, 2:1, and 1:2.                                         
            Complete gloss removal at ratios of                           
            2:1 and 1:2 wetting of cardboard                              
            covers at (1:2) ratio.                                        
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         ______________________________________                                    
53. GUM ROSIN/BUTYL ACRYLATE                                              
(1:1) Two phase system small amount of dark yellow.                       
(2:1) Liquid and large amount of solid matter.                            
(1:2) Clear yellow viscous liquid.                                        
Irradiation Times                                                         
(1:1)                                                                     
     151/2 hrs irradiation, 1% Divinyl Benzene added further              
     20 hrs = 351/2 hrs.                                                  
(2:1)                                                                     
     151/2 hrs irradiation, 1% Divinyl Benzene added further              
     20 hrs = 351/2 hrs.                                                  
(1:2)                                                                     
     1% Divinyl Benzene added, 30 hrs irradiation.                        
Testing on Cardboard, Aluminium and Copper                                
Cardboard (1:1):                                                          
            3 coats, 1 min cure/coat produced                             
            very little gloss.                                            
Aluminium (1:1):                                                          
            1 coat, 1 min cure, produced a glossy                         
            yellow homogeneous finish with                                
            excellent scratch resistance.                                 
Copper (1:1):                                                             
            1 coat, 2 min cure, produced a glossy                         
            yellow homogeneous finish with very                           
            good scratch resistance.                                      
Benzene as Solvent                                                        
Cardboard (2:1):                                                          
            3 coats, 1 min cure/coat produced an                          
            excellent gloss.                                              
Aluminium (2:1):                                                          
            1 coat, 11/2 min cure, glossy homogeneous                     
            finish with excellent scratch resistance.                     
Copper (2:1):                                                             
            1 coat, 3 min cure, glossy homogeneous                        
            finish with excellent scratch resistance.                     
Cardboard (1:2):                                                          
            2 coats, 2 min cure/coat produced a                           
            poor gloss.                                                   
Aluminium (1:2):                                                          
            1 coat, 1 min cure produced a glossy                          
            homogeneous finish with good scratch                          
            resistance.                                                   
Copper (1:2):                                                             
            1 coat, 3 min cure produced a glossy                          
            homogeneous finish with average                               
            scratch resistance.                                           
Solvent Resistance:                                                       
            Poor solvent resistance to acetone for                        
            coating on Aluminium and Copper at 1:1                        
            2:1 and 1:2 Complete removal of gloss                         
            coat from cardboard at 1:1 2:1 and 1:2.                       
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         ______________________________________                                    
54. GUM ROSIN/BUTYL ACRYLATE                                              
(1:10) Ratio A clear yellow liquid prepolymer.                            
Irradiation Time                                                          
1% Divinyl Benzene added, 133/4 hours irradiation.                        
Cardboard:  3 coats, 2 min cure/coat produced no                          
            gloss.                                                        
Aluminium:  1 coat, 5 min cure produced an excellent                      
            glossy finish with excellent scratch                          
            resistance.                                                   
Copper:     1 coat, 8 min cure produced the same                          
            finish as Aluminium.                                          
Solvent Resistance to Acetone: NIL                                        
(1:1.5) Ratio. A clear dark yellow liquid prepolymer.                     
______________________________________                                    
 
    
     Irradiation Time. 
     1% Divinyl Benzene added, 391/4 hours irradiation. 
     55. The following example shows the use of a printing ink based on a prepolymer according to this invention; 
     64% by weight of a prepolymer formed from a 1:1 mixture of acrylanitrile and methyl methacrylate by U.V. initiation was mixed with; 
     14% by weight trimethylal propane triacrylate 
     6% by weight benzaphenone 
     2% by weight michelers ketone 
     14% by weight phthalocyanine blue. 
     The ink was printed onto paper and cured by one pass at the rate of 85 feet/minute beneath a 200 w/inch U.V. lamp at a distance of 7 cm from the paper. The ink cured to a hard dry coating. 
     The following examples show the advantages accruing from the use of U.V. initiation as against thermal initiation. The U.V. initiation preferably takes place at an elevated temperature to give short prepolymerisation times, and clear viscous prepolymers which are relatively light in colour. 
     
         ______________________________________                                    
56. GUM ROSIN/STYRENE (1:1)                                               
(a) Thermal at 110° C produces in 151/2 hours a clear              
    liquid prepolymer which was much darker than that                     
    produced by (b).                                                      
(b) U.V. and Thermal at 110° C produces in 16 hours a              
    prepolymer of extremely high viscosity and clarity.                   
    The prepolymers produced by processes (a) and (b)                     
    were coated onto Copper and cured using U.V.                          
    radiation. Prepolymer (a) cured in 5 minutes                          
    while prepolymer (b) cured in 2 minutes using                         
    an identical U.V. source.                                             
______________________________________                                    
 
    
     57 STYRENE 
     a. U.V. at 25° C produces in 13 hours a slightly viscous clear one phase prepolymer. 
     b. Thermal at 110° C produces in 2 hours a clear one phase very viscous prepolymer. 
     c. Thermal and U.V. at 110° C produces in 11/4 hours a clear very viscous prepolymer. 
     58 STYRENE/BUTYL ACRYLATE (1:1) 
     a. Thermal at 110° C produces in 21/2 hours a clear very viscous prepolymer. 
     b. Thermal and U.V. at 110° C produces in 11/4 hours a clear very viscous prepolymer. 
     59 LINSEED OIL/γ-METHYL STYRENE (1:1) 
     a. Thermal at 110° C produces in 121/2 hours a yellow slightly viscous one phase prepolymer 
     b. Thermal and U.V. at 110° C produces in 13 hours a yellow viscous prepolymer. 
     60 LINSEED OIL/BUTYL ACRYLATE (1:1) 
     a. Thermal at 110° C produces in 101/2 hours a clear yellow slightly viscous prepolymer. 
     b. Thermal and U.V. at 110° C produces in 101/2 hours a clear yellow very viscous prepolymer. 
     61 GUM ROSIN/STYRENE (1:1) 
     a. Thermal at 110° C produces in 151/2 hours a slightly viscous dark brown one phase prepolymer. 
     b. Thermal and U.V. at 110° C produces in 16 hours a light brown one phase very viscous prepolymer. 
     62. METHYL METHACRYLATE/ACRYLONITRILE (1:1) 
     a. U.V. at 25° C produces in 41/2 hours a slightly yellow slightly opaque one phase viscous prepolymer 
     b. Thermal at 60° C produces in 40 hours a clear yellow one phase viscous prepolymer 
     c. Thermal and U.V. at 60° C produces in 21/4 hours a clear yellow one phase viscous prepolymer. 
     63. METHYL METHACRYLATE/BUTYL ACRYLATE (1:1) 
     a. U.V. at 25° C produces in 23/4 hours a clear very viscous prepolymer. 
     b. Thermal at 80° C produces in 5 hours a slightly yellow viscous one phase prepolymer 
     c. U.V. and Thermal at 80° C produces in 11/2 hours a clear viscous one phase prepolymer. 
     In addition to the monomers referred to above the following monomers have been found to be useful in the present invention; 
     Allyl Acrylate 
     Allylamine 
     Acrolein 
     Allyl Isophthalyl Cyanate 
     Cyclo - hexene 
     Bis Phenol A Bis 2 Hydroxy Propyl Methacrylate 
     Ethoxylated Bis Phenol A Diacrylate/Ethoxylated Bis 
     Phenol A Demethacrylate/Diallyl Fumorate 
     Cyclo Hexyl Methacrylate 
     Halogenated Olefines such as 2, 3 Dichloro 1, 3 
     Butadiene 
     2 Ethyl Hexyl Acrylate 
     1, 6 Hexane Diol Diacrylate 
     Hydroxy Ethyl Acrylate 
     Hydroxy Ethyl Methacrylate 
     Diethyleneglycol Diacrylate 
     Diethylene Glycol Dimethacrylate 
     Dimethyl Amino Ethyl Acrylate 
     Dimethyl Amino Ethyl Methacrylate 
     Isapropenyl Acetate 
     Cetyl Vinyl Ether 
     Dodecyl Vinyl Ether 
     Methylene Bis Acrylamide 
     Maleice Anlhydrid 
     N-methylol Acrylamide 
     Methacrylic Acid 
     Neo Pentyl Glycol Diacrylate 
     Pentaerythritol Triacrylate 
     Pentacrythritol Tetracrylate 
     Trimethylol Propane Triacrylate 
     Halogenated Styrenes 
     Glycidyl Methacrylate 
     The following example illustrates the use of an electron beam to cure a prepolymer according to the present invention. 
     64. A 1:1 acrylonitrile/styrene prepolymer prepared using γ-rays initiation was coated onto a clear copper shut. The coating was subjected to six passes beneath a 400,000 e.V. electron beam under a nitrogen atmosphere. A hard, clear, scratch resistant film was produced.