Novel Fluorinated silicon (IV) phthalocyanines and naphthalocyanines for electrophoretic, magnetophoretic or electromagnetophoretic display

Abstract

This invention relates to stable colorants of high extinction coefficient and high solubility or dispersibility for an electrophoretic, magnetophoretic or electromagnetophoretic display. More particularly, it relates to stable colorants for a microcup-based electrophoretic or electromagnetophoretic display the cells of which are filled with charged and/or magnetic particles dispersed in a halogenated, preferably a fluorinated, solvent. The use of the stable colorants allows the display to be of superior contrast ratio and longevity, and suitable for high-quality imagery applications.

What is claimed is:  
     
         1 . A fluorinated silicon phthalocyanine or silicon naphthalocyanine compound represented by the following formulas:  
       
         
           
           
               
               
           
         
       
       wherein: 
 each n is individually 0-4 for silicon phthalocyanine (I) or 0-6 for silicon naphthalocyanine (II);  
 R 1  is independently R f -A- (wherein R f  is as defined below and A is a single bond, —CH 2 O—, —CH 2 CH 2 O— or —CO—), alkyl, heteroalkyl, aryl, heteroaryl, heteroalkylaryl, alkyl-heteroaryl; heteroarylalkyl, aryl-heteroalkyl R′O—, R′S—, R′R″N—, R′CO—, R′OCO—, R′COO—, R′CONR″—, R′R″NCO—, R′NHCONR″—, R′SO 2 NR″— or R′R″NSO 2 — (in which R′ and R″ are independently hydrogen, R f  (as defined below), alkyl, heteroalkyl, aryl, heteroaryl, heteroarylalkyl, aryl-heteroalkyl, heteroalkylaryl or alkyl-heteroaryl) or halogenated, particularly fluorinated derivatives thereof;  
 Z is O or NR′ wherein R′ is defined as above;  
 R 2  is hydrogen, R f  (wherein Rf is as defined below and B is a single bond, —CH 2 — or —CH 2 CH 2 —), alkyl, heteroalkyl or halogenated, particularly fluorinated derivatives thereof, or —SiR 3 R 4 R 5  wherein R 3 , R 4 , and R 5  are independently an alkyl or fluoroalkyl group of 1 to 20 carbon atoms or alkoxy or fluoralkoxy of 2 to 40 carbon atoms;  
 R f  is a low molecular weight (100-100,000) fluorinated polymeric or oligomeric moiety prepared from one or more types of the fluorinated monomers, and where the fluorine content of the compound is at least 20% by weight.  
 
     
     
         2 . The compound of  claim 1  wherein the fluorine content is at least 30% by weight.  
     
     
         3 . The compound of  claim 2  wherein the fluorine content is at least 50% by weight.  
     
     
         4 . The compound of  claim 1  wherein R f  is prepared from one or more types of the fluorinated monomers selected from a group consisting of epoxide, hydrofuran, cyclolactone, cyclolactam, acrylate, methacrylate, styrene, vinylether and vinylalkane.  
     
     
         5 . The compound of  claim 1  wherein A is —CH 2 O—, —CH 2 CH 2 O— or —CO—.  
     
     
         6 . The compound of  claim 1  wherein B is —CH 2 —.  
     
     
         7 . The compound of  claim 1  wherein n is 0-2.  
     
     
         8 . The compound of  claim 1  wherein R 1  is an alkyl, fluoroalkyl, alkoxy or fluoralkoxy group having from 1 to 20 carbon atoms.  
     
     
         9 . The compound of  claim 1  wherein R 1  is an alkyl, fluoroalkyl, alkoxy or fluoralkoxy group having 1 to 12 carbon atoms.  
     
     
         10 . The compound of  claim 1  wherein Z is oxygen.  
     
     
         11 . The compound of  claim 1  wherein R 2  is hydrogen, R f —CH 2 —, alkyl, fluoroalkyl or —SiR 3 R 4 R 5  wherein R 3 , R 4  and R 5  are independently an alkyl group, a fluorinated alkyl chain of 6 to 12 carbon atoms or a fluorinated alkoxy of 6 to 18 carbon atoms.  
     
     
         12 . The compound of  claim 11  wherein R 2  is —SiR 3 R 4 R 5  in which one, two or all three R 3 , R 4  and R 5  are methyl.  
     
     
         13 . The compound of  claim 11  wherein the fluoroalkyl chain is —(CH 2 ) 2 (CF 2 ) 5 CF 3  or —(CH 2 ) 2 (CF 2 ) 7 CF 3 .  
     
     
         14 . The compound of  claim 11  wherein the fluoroalkoxy is —OCH 2 (CF 2 ) 12 CF 3  or —OCH 2 (CF 2 ) 6 CF 3 .  
     
     
         15 . The compound of  claim 1  wherein Rf is a low molecular weight (200-20,000) fluorinated polymer or oligomer.  
     
     
         16 . The compound of  claim 15  wherein R f  is a low molecular weight (400-10,000) fluorinated polymer or oligomer.  
     
     
         17 . The compound of  claim 15  wherein R f  is perfluoropolyether or hydrofluoropolyether.  
     
     
         18 . The compound of  claim 15  wherein R f  is poly(chlorotrifluoroethylene).  
     
     
         19 . The compound of  claim 15  wherein R f  is a polymeric chain derived from fluorinated epoxides.  
     
     
         20 . The compound of  claim 19  wherein R f  is —CF(CF 3 )[OCF 2 CF(CF 3 )] n F.  
     
     
         21 . The compound of  claim 1  wherein n is 0, Z is oxygen and R 2 —CH 2 CF(CF 3 )[OCF 2 CF(CF 3 )] n F.  
     
     
         22 . The compound of  claim 1  wherein n is 0, Z is oxygen and R 2  is —SiR 3 R 4 R 5  in which R 3  is —(CH 2 ) 2 (CF 2 ) 7 CF 3  and R 4  and R 5  are both —OCH 2 (CF 2 ) 12 CF 3 .  
     
     
         23 . The compound of  claim 1  wherein n is 0, Z is oxygen and R 2  is —SiR 3 R 4 R 5  in which R 3 , R 4  and R 5  are all —(CH 2 ) 2 (CF 2 ) 5 CF 3 .  
     
     
         24 . The compound of  claim 1  wherein n is 1, R 1  is n-C 8 F 17 , Z is oxygen and R 2  is hydrogen.  
     
     
         25 . The compound of  claim 1  wherein n is 1, R 1  is n-C 8 F 17 , Z is oxygen and R 2  is —SiR 3 R 4 R 5  in which R 3  and R 4  both methyl and R 5  is —(CH 2 ) 2 (CF 2 ) 7 CF 3 .  
     
     
         26 . A display composition comprising pigment particles dispersed in a solvent colored by a silicon phthalocyanine compound, a silicon naphthalocyanine compound or a mixture thereof, represented by the following formulas:  
       
         
           
           
               
               
           
         
       
       wherein: 
 each n is individually 0-4 for silicon phthalocyanine (I) or 0-6 for silicon naphthalocyanine (II);  
 R 1  is independently R f -A- (wherein R f  is as defined below and A is a single bond, —CH 2 O—, —CH 2 CH 2 O— or —CO—), alkyl, heteroalkyl, aryl, heteroaryl, heteroalkylaryl, alkyl-heteroaryl, heteroarylalkyl, aryl-heteroalkyl, R′O—, R′S—, R′R″N—, R′CO—, R′OCO—, R′COO—, R′CONR″—, R′R″NCO—, R′NHCONR″—, R′SO 2 NR″— or R′R″NSO 2 — (in which R′ and R″ are independently hydrogen, R f  (as defined below), alkyl, heteroalkyl, aryl, heteroaryl, heteroarylalkyl, aryl-heteroalkyl, heteroalkylaryl or alkyl-heteroaryl) or halogenated, particularly fluorinated derivatives thereof;  
 Z is O or NR′ wherein R′ is defined as above;  
 R 2  is hydrogen, R F —B— (wherein R f  is as defined below and B is a single bond, —CH 2 — or —CH 2 CH 2 —), alkyl, heteroalkyl or halogenated, particularly fluorinated derivatives thereof, or —SiR 3 R 4 R 5  wherein R 3 , R 4 , and R 5  are independently an alkyl or fluoroalkyl group of 1 to 20 carbon atoms or alkoxy or fluoralkoxy of 2 to 40 carbon atoms; and  
 R f  is a low molecular weight (100-100,000) fluorinated polymeric or oligomeric moiety prepared from one or more types of the fluorinated monomers and where the fluorine content of the compound is at least 20% by weight.  
 
     
     
         27 . The display composition of  claim 26  comprising a mixture of a fluorinated silicon phthalocyanine and a fluorinated silicon naphthalocyanine of  claim 1 .  
     
     
         28 . The display composition of  claim 26  further comprising a fluorinated non-silicon phthalocyanine dye.  
     
     
         29 . The display composition of  claim 28  wherein said fluorinated non-silicon phthalocyanine dye is a fluorinated metal phthalocyanine dye.  
     
     
         30 . The display composition of  claim 29  wherein said metal is Cu, Mg or Zn.  
     
     
         31 . The display composition of  claim 30  wherein said metal is Cu.  
     
     
         32 . The display composition of  claim 31  wherein the ratio of the fluorinated silicon phthalocyanine or the fluorinated silicon naphthalocyanine to the fluorinated copper phthalocyanine dye is 1/10 to 10/1.  
     
     
         33 . The display composition of  claim 31  wherein the ratio of the fluorinated silicon phthalocyanine or the fluorinated silicon naphthalocyanine to the fluorinated copper phthalocyanine dye is 1/5 to 5/1.  
     
     
         34 . The display composition of  claim 31  wherein the ratio of the fluorinated silicon phthalocyanine or the fluorinated silicon naphthalocyanine to the fluorinated copper phthalocyanine dye is 1/3 to 3/1.  
     
     
         35 . The display composition of  claim 26  wherein said pigment particles are charged and/or magnetic.  
     
     
         36 . The display composition of  claim 35  wherein said pigment is TiO 2 .  
     
     
         37 . The display composition of  claim 26  wherein said pigment is density matched to the solvent by coating or microencapsulation.  
     
     
         38 . The display composition of  claim 26  wherein said solvent is selected from a group consisting of perfluoroalkanes, perfluorocycloalkanes, perfluoroarylalkanes, perfluoro-tert-amines, perfluoropolyethers, hydrofluoropolyethers and poly(chlorotrifluoroethylene).  
     
     
         39 . The display composition of  claim 38  wherein said perfluoropolyethers and hydrofluoropolyethers are selected from a group consisting of Ausimont HT-170, HT-200, HT-230, ZT-180 and Dupont trifluoro(trifluoromethyl)-oxirane homopolymers K-6 and K-7 fluids.  
     
     
         40 . A electrophoretic, magnetophoretic or electromagnetophoretic display comprising display cells filled with a display composition which comprises pigment particles dispersed in a solvent colored by a silicon phthalocyanine or silicon naphthalocyanine compound represented by the following formulas:  
       
         
           
           
               
               
           
         
       
       wherein: 
 each n is individually 0-4 for silicon phthalocyanine (I) or 0-6 for silicon naphthalocyanine (II);  
 R 1  is independently R f -A- (wherein R f  is as defined below and A is a single bond, —CH 2 O—, —CH 2 CH 2 — or —CO—), alkyl, heteroalkyl, aryl, heteroaryl, heteroalkylaryl, alkyl-heteroaryl, heteroarylalkyl, aryl-heteroalkyl, R′O—, R′, R′R″N—, R′CO—, R′OCO—, R′COO—, R′CONR″—, R′R″NCO—, R′NHCONR″—, R′SO 2 NR″— or R′R″NSO 2 — (in which R′ and R″ are independently hydrogen, R f  (as defined below), alkyl, heteroalkyl, aryl, heteroaryl, heteroarylalkyl, aryl-heteroalkyl, heteroalkylaryl or alkyl-heteroaryl) or halogenated, particularly fluorinated derivatives thereof;  
 Z is O or NR′ wherein R′ is defined as above;  
 R 2  is hydrogen, R f —B— (wherein R f  is as defined below and B is a single bond, —CH 2 — or —CH 2 CH 2 —), alkyl, heteroalkyl or halogenated, particularly fluorinated derivatives thereof, or —SiR 3 R 4 R 5  wherein R 3 , R 4 , and R 5  are independently an alkyl or fluoroalkyl group of 1 to 20 carbon atoms or alkoxy or fluoralkoxy of 2 to 40 carbon atoms; and  
 R f  is a low molecular weight (100-100,000) fluorinated polymeric or oligomeric moiety prepared from one or more types of the fluorinated monomers and where the fluorine content of the compound is at least 20% by weight.  
 
     
     
         41 . The display of  claim 40  wherein said cells are prepared by the microcup technology.  
     
     
         42 . The display of  claim 41  wherein said cells are individually sealed with a polymeric sealing layer.  
     
     
         43 . The display of  claim 42  wherein said polymeric sealing layer is formed from a composition comprising a material selected from a group consisting of thermoplastics, thermosets and precursors thereof.  
     
     
         44 . A process of the preparation of a silicone phthalocyanine or naphthalocyanine compound represented by the following formulas:  
       
         
           
           
               
               
           
         
       
       wherein: 
 each n is individually 0-4 for silicon phthalocyanine (I) or 0-6 for silicon naphthalocyanine (II);  
 R 1  is independently R f -A- (wherein R f  is as defined below and A is a single bond, —CH 2 O—, —CH 2 CH 2 O— or —CO—), alkyl, heteroalkyl, aryl, heteroaryl, heteroalkylaryl, alkyl-heteroaryl, heteroarylalkyl, aryl-heteroalkyl, R′O—, R′S—, R′R″N—, R′CO—, R′OCO—, R′COO—, R′CONR″—, R′R″NCO—, R′NHCONR″—, R′SO 2 NR″— or R′R″NSO 2 — (in which R′ and R″ are independently hydrogen, R f  (as defined below), alkyl, heteroalkyl, aryl, heteroaryl, heteroarylalkyl, aryl-heteroalkyl, heteroalkylaryl or alkyl-heteroaryl) or halogenated, particularly fluorinated derivatives thereof;  
 Z is 0 or NR′ wherein R′ is defined as above;  
 R 2  is hydrogen, R f —B— (wherein R f  is as defined below and B is a single bond, —CH 2 — or —CH 2 CH2—), alkyl, heteroalkyl or halogenated, particularly fluorinated derivatives thereof, or —SiR 3 R 4 R 5  wherein R3, R 4 , and R 5  are independently an alkyl or fluoroalkyl group of 1 to 20 carbon atoms or alkoxy or fluoralkoxy of 2 to 40 carbon atoms; and  
 R f  is a low molecular weight (100-100,000) fluorinated polymeric or oligomeric moiety prepared from one or more types of the fluorinated monomers and where the fluorine content of the compound is at least 20% by weight, which process comprises: 
 a) reacting a compound of Formula III or IV  
                     
 wherein n and R 1  are as defined above and X is halogen or hydroxy with a compound of Formula V  
 Y—Z—R 2   (V)  
 
  wherein Z and R 2  is as defined above and Y is hydrogen or an alkali metal to form a compound of Formula I or II respectively, or 
 b) reacting a compound of Formula III or IV wherein n and R 1  are as defined above and X is hydroxy with SiR 3 R 4 R 5 Cl or SiR 3 R 4 R 5 Br wherein R 3 , R 4  and R 5  are as defined above to form a compound of Formula I wherein Z is oxygen and R 2  is —SiR 3 R 4 R 5  in which R 3 , R 4  and R 5  are as defined above; or  
 c) reacting a compound of Formula III or IV wherein n and R 1  are as defined above and X is hydroxy with SiR 3 Cl 3 , followed by R 4 OH, wherein R 3  and R 4  are as defined above to form a compound of Formula I wherein Z is oxygen and R 2  is —SiR 3 R 4 R 5  in which R 3  and R 4  are as defined above and R 5  is the same as R 4 ; or  
 d) converting a compound of Formula I or II wherein n and R 1  are as defined above and Z—R 2  is a group convertible to a hydroxy group to form a compound of Formula I or II wherein Z is oxygen and R 2  is hydrogen; or  
 e) converting a compound of Formula I or II wherein n is 0 to a compound of Formula I or II wherein n is at least 1 and R 1  is other than hydrogen.