Abstract:
A non aqueous dispersion is disclosed containing: a shell polymer; a core polymer, and a continuous phase solvent, wherein said shell polymer is soluble and said core polymer is insoluble in the continuous solvent. Also disclosed is a method for improving the setting properties of a sheet fed offset ink by adding to the ink the above non aqueous dispersion.

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
     This application is the United States national phase filing of the corresponding international application number PCT/US2009/047059, filed on Jun. 11, 2009, which claims priority to and benefit of U.S. Application No. 61/073,214, filed Jun. 17, 2008, which applications are hereby incorporated by reference in their entirety. 
    
    
     FIELD OF THE INVENTION 
     The invention relates to non aqueous dispersions containing latex core and shell polymers in an organic solvent and to methods of using said non aqueous dispersions to improve the setting properties of sheet fed offset inks. 
     BACKGROUND OF THE INVENTION 
     Sheet fed offset inks generally contain a vehicle prepared by dissolving an alkyd resin, petroleum resin, phenolic resin or modified resin thereof in a drying oil such as linseed oil or dehydrated castor oil or in a petroleum derived solvent boiling at a higher temperature. 
     Because the mechanism of drying is oxidation whose kinetics is relatively slow, it has not been possible so far to obtain an instant drying sheets similar to those obtained in Xerography which can be further processed such as cutting and binding. 
     SUMMARY OF THE INVENTION 
     The present invention provides a non aqueous dispersion comprising:
         (a) a shell polymer;   (b) a core polymer; and   (c) a continuous phase solvent,   wherein said shell polymer is soluble and said core polymer is insoluble in the continuous solvent.       

     The present invention also provides a method for improving the setting properties of a sheet fed offset ink comprising adding to said ink a non aqueous dispersion comprising:
         (a) a shell polymer;   (b) a core polymer; and   (c) a continuous phase solvent,   wherein said shell polymer is soluble and said core polymer is insoluble in the continuous solvent.       

     Other objects and advantages of the present invention will become apparent from the following description and appended claims. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     It has now been discovered that incorporation of non aqueous dispersions (NADs) of acrylic polymers in a sheet fed ink results in inks that dry dramatically faster than conventional inks. 
     Non aqueous dispersions (NADs) are comprised of insoluble latexes dispersed in some organic medium. They are attractive additives for ink due to their controlled size, incompatibility, and dispersibility. They have been used successfully in paint to control body, encapsulate pigment, and to provide emulsion-like dispersions in water-free environments. 
     Previous work focused on generating non aqueous dispersions (NAD) through the use of a solvent control technique. In each case, vinyl monomers (primarily methyl methacrylate, MMA) were polymerized in a good solvent. The solvent chosen was either one in which the monomer was soluble and the resulting polymer was not, or one in which both monomer and polymer were soluble necessitating a solvent switch in order to form dispersion. In either case, the rapid kinetics of the MMA reaction often led to an over gelled, non dispersible product. Also, though many approaches were attempted, a stable, homogeneous NAD product was never obtained. 
     Given the repeated failure of the solvent-switch mechanism, the current work utilizes a different approach to NAD formation. Here, the NAD is formed by generating a core-shell polymer where the shell is soluble in the continuous phase solvent while the core is insoluble in the solvent yet soluble in the shell polymer. This structure is obtained through a two step polymerization where the shell is formed first and then the core polymer is “filled in”, generating a dispersion. 
     In the preparation of the NAD, the monomers used to make the polymers may comprise a functional group selected from the group consisting of carboxyl group, and hydroxyl group. 
     Preferably, the carboxyl group containing monomers are selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and maleic acid. Also preferably, the hydroxyl group containing monomers are selected from the group consisting of 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy propyl acrylate and 2-hydroxy propyl methacrylate. 
     The NAD polymers may also be prepared from monomers which comprise a functional group containing vinyl monomer. Preferably, the vinyl monomer is selected from the group consisting of glycidyl acrylate, glycidal methacrylate, and dimethyl amino methacrylate. 
     Preferably the amount of NAD present in the sheet fed offset ink is at least from about 1% to about 15%, more preferably about 5% and most preferably about 10%. The inclusion of NAD leads to improved drying and processability as indicated by guillotine test. 
     NAD Formation 
     The continuous phase used is preferably a common hydrocarbon solvent (such for example Magie #47 oil or Magie N-40 oil). Preferably, the shell polymer is made up of a copolymer of isobutyl methacrylate and dodecyl methacrylate in a ratio of approximately 3:1. The long hydrocarbon chains on these monomers make the resulting polymer readily soluble in Magie oil. Also preferably, approximately 2% of acetic acid is added to aid in efficient polymer formation. In addition, a small amount of glycidylmethacrylate may be added because the epoxy groups in this monomer increase the attraction between the shell and core polymers. Most preferably, the core polymer is primarily methylmethacrylate with 10% N-butyl methacrylate. 
     EXAMPLE 1 
     NAD Synthesis 
     A shell polymer was synthesized containing the ingredients in Table 1 as follows: 
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Shell polymer ingredients and synthesis 
               
             
          
           
               
                   
                   
                   
                 Charge 
                   
                   
               
               
                 Formulation 
                   
                 % 
                 (g) 
                 Actual 
                 Actual % 
               
               
                   
               
             
          
           
               
                   
                 A 
                 Magie N-40 
                 34.05 
                 157 
                 157.4 
                 34.05 
               
               
                   
                   
                 ink oil 
               
               
                 MP 
                 B 
                 Isobutyl 
                 39.58 
                 182.5 
                 182.5 
                 39.48 
               
               
                   
                   
                 methacrylate 
               
               
                   
                 C 
                 Dodecyl 
                 13.56 
                 62.5 
                 63.4 
                 13.71 
               
               
                   
                   
                 methacrylate 
               
               
                   
                 D 
                 Arcylic acid 
                 1.08 
                 5 
                 5 
                 1.08 
               
               
                 CP 
                 E 
                 Magie N-40 
                 10.84 
                 50 
                 49.9 
                 10.79 
               
               
                   
                   
                 ink oil 
               
               
                   
                 F 
                 t-butyl 
                 0.43 
                 2 
                 2 
                 0.43 
               
               
                   
                   
                 peroctoate 
               
               
                   
                 G 
                 t-butyl 
                 0.11 
                 0.5 
                 0.5 
                 0.11 
               
               
                   
                   
                 peroxybenzoate 
               
               
                   
                 H 
                 Glycidyl- 
                 0.33 
                 1.5 
                 1.5 
                 0.32 
               
               
                   
                   
                 methacrylate 
               
               
                   
                 I 
                 Triphenyl- 
                 0.02 
                 0.075 
                 0.077 
                 0.02 
               
               
                   
                   
                 phosphine 
               
               
                   
                 J 
                 p- 
                 0.00 
                 0.0075 
                 0.014 
                 0.00 
               
               
                   
                   
                 Methoxyphenol 
                   
               
               
                   
                   
                 TOTAL 
                 100 
                 461.082 
                 462.291 
                 100 
               
               
                   
               
             
          
         
       
     
     Briefly, ingredient A was charged to a reactor and heated to 120° C. and held in nitrogen gas. Ingredients B, C and D were pre-mixed(Monomer premixture; MP) as well as ingredients E, F and G(Catalyst premixture; CP). Thereafter, premixtures MP and CP were separately charged to the reactor for 4 hours and held at 120° C. for 4 hours. Then, the nitrogen gas was changed to air and ingredients H, and J were charged and the temperature was again held at 120° C. for 4 hours. The air was then vacuumed for 30 minutes and the temperature cooled to 100° C. followed by discharging the resulting product (shell polymer). 
     The formation of the core polymer and NAD was carried out as described in Table 2 and as follows: 
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 NAD ingredients and synthesis: 
               
             
          
           
               
                   
                   
                   
                 Charge 
                   
                   
               
               
                 Formulation 
                   
                 % 
                 (g) 
                 Actual 
                 Actual % 
               
               
                   
               
             
          
           
               
                   
                 A 
                 Magie #N-40 
                 32.69 
                 140 
                 140.1 
                 32.64 
               
               
                   
                   
                 ink oil 
               
               
                   
                 B 
                 Shell 
                 31.75 
                 136 
                 135.1 
                 31.47 
               
               
                   
                   
                 polymer 
               
               
                 MP 
                 C 
                 Methyl- 
                 13.31 
                 57 
                 57.1 
                 13.30 
               
               
                   
                   
                 methacrylate 
               
               
                   
                 D 
                 N-butyl 
                 5.37 
                 23 
                 23 
                 5.36 
               
               
                   
                   
                 methacrylate 
               
               
                   
                 E 
                 N-butyl acrylate 
                 6.28 
                 26.9 
                 28.2 
                 6.57 
               
               
                 CP1 
                 F 
                 Magie #N-40 
                 5.19 
                 22.23 
                 22.5 
                 5.24 
               
               
                   
                   
                 ink oil 
               
               
                   
                 G 
                 t-butyl peroctoate 
                 0.26 
                 1.11 
                 1.1 
                 0.26 
               
               
                   
                 H 
                 t-butyl peroctoate 
                 0.13 
                 0.56 
                 0.6 
                 0.14 
               
               
                   
                 I 
                 Methyl- 
                 2.57 
                 11 
                 11 
                 2.56 
               
               
                   
                   
                 methacrylate 
               
               
                 CP3 
                 J 
                 t-butyl peroctoate 
                 0.12 
                 0.5 
                 0.54 
                 0.13 
               
               
                   
                 K 
                 Magie #N-40 
                 2.33 
                 10 
                 10 
                 2.33 
               
               
                   
                   
                 ink oil 
                   
               
               
                   
                   
                 TOTAL 
                 100.00 
                 428.3 
                 429.24 
                 100.00 
               
               
                   
               
             
          
         
       
     
     Ingredients A and B were charged to a reactor and heated to 85° C. and held in nitrogen gas. Ingredients C and D and E were pre-mixed(Monomer premixture; MP) as well as ingredients F and G (Catalyst premixture 1; CP1) and ingredients J and K (Catalyst premixture 1; CP3). Thereafter, premixtures MP and CP1 were separately charged to the reactor for 4 hours and held at 85° C. for 3 hours. Then, ingredient I was charged followed by premixture CP3 drip wise and the mixture was held for 3 hours. The presence of residual monomers was checked with Gas Chromatography and the resultant product (NAD) was brought to room temperature and discharged. 
     EXAMPLE 2 
     Preparation of Sheet Fed Inks and Testing Thereof 
     A 4 color set of sheet fed inks were prepared containing the NAD prepared in Example 1 and as described in Table 3: 
     
       
         
               
             
               
               
             
               
               
               
               
               
             
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Ingredients of 4 color set of sheet fed inks 
               
             
          
           
               
                   
                 Color 
               
             
          
           
               
                   
                 BLACK 
                 CYAN 
                 MAGENTA 
                 YELLOW 
               
             
          
           
               
                   
                 Formula # 
               
             
          
           
               
                   
                 FRE31- 
                 FRE31- 
                 FRE31- 
                 FRE31- 
               
               
                   
                 1-JB 
                 1-JB 
                 1-JB 
                 1-JB 
               
               
                   
                   
               
             
          
           
               
                 Carbon black 
                 24.6 
                   
                   
                   
               
               
                 Pthalo Blue 
                   
                 18.5 
               
               
                 Magenta pigment 
                   
                   
                 19.5 
               
               
                 Yellow pigment 
                   
                   
                   
                 12.5 
               
               
                 Varnish 
                 50.8 
                 53.6 
                 54.6 
                 61.1 
               
               
                 Oil 
                 4.0 
                 3.5 
                 2.8 
                 5.0 
               
               
                 NAD(Non aqueous 
                 10.0 
                 10.0 
                 10.0 
                 10.0 
               
               
                 dispersion) 
               
               
                 Wax Conpound 
                 4.0 
                 4.0 
                 4.0 
                 4.0 
               
               
                 Anti Skin 
                 0.6 
                 0.4 
                 0.6 
                 0.4 
               
               
                 Drier 
                 2.0 
                 2.0 
                 2.0 
                 2.0 
               
               
                 Estorob 68 
                 4.0 
                 8.0 
                 6.5 
                 5.0 
               
               
                 Total 
                 100.0 
                 100.0 
                 100.0 
                 100.0 
               
               
                   
               
             
          
         
       
     
     The above inks were tested on a Heidelberg MO sheet fed press versus a standard set that did not contain any NAD. The paper used was Magnostar (115 gm basis weight). The optical densities of the various colors were: (B=1.90; C=1.45; M=1.50; Y=1.30) as well as for the fountain solution (50/50 tap water/de-ionized water with 3% Sunfount 410). 
     The rub resistance was done using an industry standard Sutherland rub tester. The guillotine test consisted of cutting a pile of 5000 sheets and seeing if any ink residue is left on the blades. 
     Fast rub resistance and guillotine test were significantly improved in all inks tested. In addition, the experimental inks were processable after 15 minutes vs almost 1 hr for standard set. 
     The invention has been described in terms of preferred embodiments thereof, but is more broadly applicable as will be understood by those skilled in the art. The scope of the invention is only limited by the following claims.