Sensitizing dye and silver halide photographic material

Abstract

Spectral sensitizing dyes represented by the following formulas ( 1 ) to ( 4 ) are disclosed; silver halide photographic materials and thermally developable photosensitive materials containing the dyes are also disclosed.

What is claimed is:  
     
         1 . A spectral sensitizing dye represented by the following formulas (1) to (4):  
       
         
           
           
               
               
           
         
       
       wherein Y 1 , Y 2  and Y 11  each are independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring between Ra and Rb; Z 1  is an atomic group necessary to form a 5- or 6-membered ring; R is a hydrogen atom, a lower alkyl, a cycloalkyl group, an aralkyl group, a lower alkoxy group, an aryl group, a hydroxy group or a halogen atom; W 1 , W 2 , W 3 , W 4 , W 11 , W 12 , W 13  and W 14  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 1  and W 2  or W 11  and W 12 ; R 1  and R 11  are each an aliphatic group or a non-metallic atom group necessary to form a condensed ring by bonding between R 1  and W 3  or R 11  and W 14 ; V 1  to V 9 , and V 11  to V 13  each are independently a hydrogen atom, a halogen atom, an amino group, an alkylthio group, an arylthio group, a lower alkyl group, a lower alkoxy group, an aryl group, an aryloxy group, a heterocyclic group or a non-metallic atom group necessary to form a 5- to 7-membered ring by bonding between V 1  and V 3 , V 2  and V 4 , V 3  and V 5 , V 2  and V 6 , V 5  and V 7 , V 6  and V 8 , V 7  and V 9 , or V 11  and V 13 , provided that at least one of V 1  to V 9  and at least one of V 11  to V 13  are a group other than a hydrogen atom; X 1  and X 11  each are an ion necessary to compensate for an intramolecular charge; l1 and l11 each an ion necessary to compensate for an intramolecular charge; k1 and k2 each are 0 or 1; p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2, provided that the sum of p1 and q1 and the sum of p11 and q11 are respectively not more than 2; 
       
         
           
           
               
               
           
         
       
       wherein Y 21 , Y 22  and Y 31  each are independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring between Ra and Rb; R 21 , R 22 , R 31  and R 32  each are independently an aliphatic group; Rc and Rd each are independently an unsubstituted lower alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a heterocyclic group; W 21 , W 22 , W 23 , W 24 , W 31 , W 32 , W 33  and W 34  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 21  and W 22 , W 23  and W 24 , W 31  and W 32 , or W 33  and W 34 ; V 21  to V 29 , and V 31  to V 33  each are independently a hydrogen atom, a halogen atom, an amino group, an alkylthio group, an arylthio group, a lower alkyl group, a lower alkoxy group, an aryl group, an aryloxy group, a heterocyclic group or a non-metallic atom group necessary to form a 5- to 7-membered ring by bonding between V 21  and V 23 , V 22  and V 24 , V 23  and V 25 , V 24  and V 26 , V 25  and V 27 , V 26  and V 28 , V 27  and V 29 , or V 31  and V 33 ; X 21  and X 31  each are an ion necessary to compensate for an intramolecular charge; l21 and l31 each an ion necessary to compensate for an intramolecular charge; k21 and k22 each are 0 or 1; n21, n22, n31 and n32 each are 0, 1 or 2, provided that n21 and n22, or n31 and n32 are not 0 at the same time.  
     
     
         2 . The spectral sensitizing dye of  claim 1 , wherein said dye is represented by formula (1) or (2).  
     
     
         3 . The spectral sensitizing dye of  claim 2 , wherein said dye is represented by the following formula (1-1) or (2-1):  
       
         
           
           
               
               
           
         
       
       wherein Y 1 , Y 2  and Y 11  each are independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring when Ra and Rb are linked with each other; Z 1  is an atomic group necessary to form a 5- or 6-membered ring; R is a hydrogen atom, a lower alkyl, a cycloalkyl group, an aralkyl group, a lower alkoxy group, an aryl group, a hydroxy group or a halogen atom; W 1 , W 2 , W 3 , W 4 , W 11 , W 12 , W 13  and W 14  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 1  and W 2  or W 11  and W 12 ; R 1  and R 11  are each an aliphatic group or a non-metallic atom group necessary to form a condensed ring by bonding between R 1  and W 3  or R 11  and W 14 ; L 1  to L 9 , and L 11  to L 15  each are independently a methine group; X 1  and X 11  each are an ion necessary to compensate for an intramolecular charge; l1 and l11 each an ion necessary to compensate for an intramolecular charge; m1 to m3 each are 0 or 1; p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2, provided that the sum of p1 and q1 and the sum of p11 and q11 are respectively not more than 2.  
     
     
         4 . The spectral sensitizing dye of  claim 1 , wherein said dye is represented by formula (3) or (4).  
     
     
         5 . The spectral sensitizing dye of  claim 4 , wherein said dye is represented by formula (3).  
     
     
         6 . A silver halide photographic material comprising a support having thereon at least a photosensitive layer containing a silver halide emulsion layer, wherein said photosensitive layer contains a compound represented by the following formulas (1) to (4):  
       
         
           
           
               
               
           
         
       
       wherein Y 1 , Y 2  and Y 11  each are independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring between Ra and Rb; Z 1  is an atomic group necessary to form a 5- or 6-membered ring; R is a hydrogen atom, a lower alkyl, a cycloalkyl group, an aralkyl group, a lower alkoxy group, an aryl group, a hydroxy group or a halogen atom; W 1 , W 2 , W 3 , W 4 , W 11 , W 12 , W 13  and W 14  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 1  and W 2  or W 11  and W 12 ; R 1  and R 11  are each an aliphatic group or a non-metallic atom group necessary to form a condensed ring by bonding between R 1  and W 3  or R 11  and W 14 ; V 1  to V 9 , and V 11  to V 13  each are independently a hydrogen atom, a halogen atom, an amino group, an alkylthio group, an arylthio group, a lower alkyl group, a lower alkoxy group, an aryl group, an aryloxy group, a heterocyclic group or a non-metallic atom group necessary to form a 5- to 7-membered ring by bonding between V1 and V 3 , V 2  and V 4 , V 3  and V 5 , V 2  and V6, V 5  and V 7 , V6 and V8, V 7  and V 9 , or V 11  and V 13 , provided that at least one of V1 to V 9  and at least one of V 11  to V 13  are a group other than a hydrogen atom; X 1  and X 11  each are an ion necessary to compensate for an intramolecular charge; l1 and l11 each an ion necessary to compensate for an intramolecular charge; k1 and k2 each are 0 or 1; p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2, provided that the sum of p1 and q1 and the sum of p11 and q11 are respectively not more than 2; 
       
         
           
           
               
               
           
         
       
       wherein Y 21 , Y 22  and Y 31  each are independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring between Ra and Rb; R 21 , R 22 , R 31  and R 32  each are independently an aliphatic group; Rc and Rd each are independently an unsubstituted lower alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a heterocyclic group; W 21 , W 22 , W 23 , W 24 , W 31 , W 32 , W 33  and W 34  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 21  and W 22 , W 23  and W 24 , W 31  and W 32 , or W 33  and W 34 ; V 21  to V 29 , and V 31  to V 33  each are independently a hydrogen atom, a halogen atom, an amino group, an alkylthio group, an arylthio group, a lower alkyl group, a lower alkoxy group, an aryl group, an aryloxy group, a heterocyclic group or a non-metallic atom group necessary to form a 5- to 7-membered ring by bonding between V 21  and V 23 , V 22  and V 24 , V 23  and V 25 , V 24  and V 26 , V 25  and V 27 , V 26  and V 28 , V 27  and V 29 , or V 31  and V 33 ; X 21  and X 31  each are an ion necessary to compensate for an intramolecular charge; l21 and l31 each an ion necessary to compensate for an intramolecular charge; k21 and k22 each are 0 or 1; n21, n22, n31 and n32 each are 0, 1 or 2, provided that n21 and n22, or n31 and n32 are not 0 at the same time.  
     
     
         7 . The photographic material of  claim 6 , wherein said compound is represented by formula (1) or (2).  
     
     
         8 . The photographic material of  claim 7 , wherein said compound is represented by the following formula (1-1) or (2-1):  
       
         
           
           
               
               
           
         
       
       wherein Y 1 , Y 2  and Y 11  each are independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring when Ra and Rb are linked with each other; Z 1  is an atomic group necessary to form a 5- or 6-membered ring; R is a hydrogen atom, a lower alkyl, a cycloalkyl group, an aralkyl group, a lower alkoxy group, an aryl group, a hydroxy group or a halogen atom; W 1 , W 2 , W 3 , W 4 , W 11 , W 12 , W 13  and W 14  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 1  and W 2  or W 11  and W 12 ; R 1  and R 11  are each an aliphatic group or a non-metallic atom group necessary to form a condensed ring by bonding between R 1  and W 3  or R 11  and W 14 ; L 1  to L 9 , and L 11  to L 15  each are independently a methine group; X 1  and X 11  each are an ion necessary to compensate for an intramolecular charge; l1 and l11 each an ion necessary to compensate for an intramolecular charge; m1 to m3 each are 0 or 1; p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2, provided that the sum of p1 and q1 and the sum of p11 and q11 are respectively not more than 2.  
     
     
         9 . The photographic material of  claim 6 , wherein said compound is represented by formula (3) or (4).  
     
     
         10 . The photographic material of  claim 9 , wherein said compound is represented by formula (3).  
     
     
         11 . The photographic material of  claim 10 , wherein said photosensitive layer further contains a compound represented by the following formula (5):  
       
         
           
           
               
               
           
         
       
       wherein Y 4  and Y 42  each are independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring together with Ra and Rb; R 41  and R 42  each are independently an aliphatic group; Re and Rf each are independently an unsubstituted lower alkyl group, cycloalkyl group, aralkyl group, aryl group or heterocyclic group; W 41 , W 42 , W 43 , and W 44  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 41  and W 42 , W 43  and W 44 ; L 41  to L 49  are each a methine group; X 41  is an ion necessary to compensate for an intramolecular charge; l41 is an ion necessary to compensate for an intramolecular charge; m42 and m43 each are 0 or 1; n41 and n42 each are 0, 1 or 2, provided that n41 and n42 are not 0 at the same time.  
     
     
         12 . The photographic material of  claim 9 , wherein said compound is represented by formula (4).  
     
     
         13 . The photographic material of  claim 12 , wherein said photosensitive layer further contains a compound represented by formula (6):  
       
         
           
           
               
               
           
         
       
       wherein Y 51  is independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring together with Ra and Rb; R 51  and R 52  each are independently an aliphatic group; Re and Rf each are independently an unsubstituted lower alkyl group, cycloalkyl group, aralkyl group, aryl group or heterocyclic group; W 51 , W 52 , W 53  and W 54  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 51  and W 52 , or W 53  and W 54 ; L 51  to L 55  are each a methine group; X 51  is an ion necessary to compensate for an intramolecular charge; l51 is an ion necessary to compensate for an intramolecular charge; n51 and n52 each are 0, 1 or 2, provided that n51 and n52 are not 0 at the same time.  
     
     
         14 . The photographic material of  claim 6 , wherein said photosensitive layer further contains an organic silver salt and a reducing agent.  
     
     
         15 . The photographic material of  claim 14 , wherein said compound is represented by formula (1) or (2).  
     
     
         16 . The photographic material of  claim 15 , wherein said compound is represented by the following formula (1-1) or (2-1):  
       
         
           
           
               
               
           
         
       
       wherein Y 1 , Y 2  and Y 11  each are independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring when Ra and Rb are linked with each other; Z 1  is an atomic group necessary to form a 5- or 6-membered ring; R is a hydrogen atom, a lower alkyl, a cycloalkyl group, an aralkyl group, a lower alkoxy group, an aryl group, a hydroxy group or a halogen atom; W 1 , W 2 , W 3 , W 4 , W 11 , W 12 , W 13  and W 14  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 1  and W 2  or W 11  and W 12 ; R 1  and R 11  are each an aliphatic group or a non-metallic atom group necessary to form a condensed ring by bonding between R 1  and W 3  or R 11  and W 14 ; L 1  to L 9 , and L 11  to L 15  each are independently a methine group; X 1  and X 11  each are an ion necessary to compensate for an intramolecular charge; l1 and l11 each an ion necessary to compensate for an intramolecular charge; m1 to m3 each are 0 or 1; p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2, provided that the sum of p1 and q1 and the sum of p11 and q11 are respectively not more than 2.  
     
     
         17 . The photographic material of  claim 14 , wherein said compound is represented by formula (3) or (4).  
     
     
         18 . The photographic material of  claim 17 , wherein said compound is represented by formula (3).  
     
     
         19 . The photographic material of  claim 18 , wherein said photosensitive layer further contains a compound represented by the following formula (5):  
       
         
           
           
               
               
           
         
       
       wherein Y 4  and Y 42  each are independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring together with Ra and Rb; R 41  and R 42  each are independently an aliphatic group; Re and Rf each are independently an unsubstituted lower alkyl group, cycloalkyl group, aralkyl group, aryl group or heterocyclic group; W 41 , W 42 , W 43 , and W 44  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 41  and W 42 , W 43  and W 44 ; L 41  to L 49  are each a methine group; X 41  is an ion necessary to compensate for an intramolecular charge; l41 is an ion necessary to compensate for an intramolecular charge; m42 and m43 each are 0 or 1; n41 and n42 each are 0, 1 or 2, provided that n41 and n42 are not 0 at the same time.  
     
     
         20 . The photographic material of  claim 17 , wherein said compound is represented by formula (4).  
     
     
         21 . The photographic material of  claim 20 , wherein said photosensitive layer further contains a compound represented by formula (6):  
       
         
           
           
               
               
           
         
       
       wherein Y 51  is independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring together with Ra and Rb; R 51  and R 52  each are independently an aliphatic group; Re and Rf each are independently an unsubstituted lower alkyl group, cycloalkyl group, aralkyl group, aryl group or heterocyclic group; W 51 , W 52 , W 53  and W 54  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 51  and W 52 , or W 53  and W 54 ; L 51  to L 55  are each a methine group; X 51  is an ion necessary to compensate for an intramolecular charge; l51 is an ion necessary to compensate for an intramolecular charge; n51 and n52 each are 0, 1 or 2, provided that n51 and n52 are not 0 at the same time.  
     
     
         22 . The photographic material of  claim 14 , wherein the photographic material further has a non-photosensitive layer, said non-photosensitive layer containing a binder, a phthalazine compound, a benzenepolycarboxylic acid or an acid anhydride compound.  
     
     
         23 . An image forming method comprising exposing a photosensitive material to laser, the photosensitive material comprising a support having thereon at least a photosensitive layer containing a compound represented by the following formulas (1) to (4):  
       
         
           
           
               
               
           
         
       
       wherein Y 1 , Y 2  and Y 11  each are independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring between Ra and Rb; Z 1  is an atomic group necessary to form a 5- or 6-membered ring; R is a hydrogen atom, a lower alkyl, a cycloalkyl group, an aralkyl group, a lower alkoxy group, an aryl group, a hydroxy group or a halogen atom; W 1 , W 2 , W 3 , W 4 , W 11 , W 12 , W 13  and W 14  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 1  and W 2  or W 11  and W 12 ; R 1  and R 11  are each an aliphatic group or a non-metallic atom group necessary to form a condensed ring by bonding between R 1  and W 3  or R 11  and W 14 ; V 1  to V 9 , and V 11  to V 13  each are independently a hydrogen atom, a halogen atom, an amino group, an alkylthio group, an arylthio group, a lower alkyl group, a lower alkoxy group, an aryl group, an aryloxy group, a heterocyclic group or a non-metallic atom group necessary to form a 5- to 7-membered ring by bonding between V 1  and V 3 , V 2  and V 4 , V 3  and V 5 , V 2  and V 6 , V 5  and V 7 , V 6  and V 8 , V 7  and V 9 , or V 11  and V 13 , provided that at least one of V 1  to V 9  and at least one of V 11  to V 13  are a group other than a hydrogen atom; X 1  and X 11  each are an ion necessary to compensate for an intramolecular charge; l1 and l11 each an ion necessary to compensate for an intramolecular charge; k1 and k2 each are 0 or 1; p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2, provided that the sum of p1 and q1 and the sum of p11 and q11 are respectively not more than 2;  
       
         
           
           
               
               
           
         
       
       wherein Y 21 , Y 22  and Y 31  each are independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring between Ra and Rb; R 21 , R 22 , R 31  and R 32  each are independently an aliphatic group; Rc and Rd each are independently an unsubstituted lower alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a heterocyclic group; W 21 , W 22 , W 23 , W 24 , W 31 , W 32 , W 33  and W 34  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 21  and W 22 , W 23  and W 24 , W 31  and W 32 , or W 33  and W 34 ; V 21  to V 29 , and V 31  to V 33  each are independently a hydrogen atom, a halogen atom, an amino group, an alkylthio group, an arylthio group, a lower alkyl group, a lower alkoxy group, an aryl group, an aryloxy group, a heterocyclic group or a non-metallic atom group necessary to form a 5- to 7-membered ring by bonding between V 21  and V 23 , V 22  and V 24 , V 23  and V 25 , V 24  and V 26 , V 25  and V 27 , V 26  and V 28 , V 27  and V 29 , or V 31  and V 33 ; X 21  and X 31  each are an ion necessary to compensate for an intramolecular charge; l21 and l31 each an ion necessary to compensate for an intramolecular charge; k21 and k22 each are 0 or 1; n21, n22, n31 and n32 each are 0, 1 or 2, provided that n21 and n22, or n31 and n32 are not 0 at the same time.  
     
     
         24 . The image forming method of  claim 23 , wherein said compound is represented by formula (1) or (2).  
     
     
         25 . The image forming method of  claim 24 , wherein said compound is represented by the following formula (1-1) or (2-1):  
       
         
           
           
               
               
           
         
       
       wherein Y 1 , Y 2  and Y 11  each are independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a hydrogen atom, a lower alkyl group or an atomic group necessary to form an aliphatic spiro ring when Ra and Rb are linked with each other; Z 1  is an atomic group necessary to form a 5- or 6-membered ring; R is a hydrogen atom, a lower alkyl, a cycloalkyl group, an aralkyl group, a lower alkoxy group, an aryl group, a hydroxy group or a halogen atom; W 1 , W 2 , W 3 , W 4 , W 11 , W 12 , W 13  and W 14  each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W 1  and W 2  or W 11  and W 12 ; R 1  and R 11  are each an aliphatic group or a non-metallic atom group necessary to form a condensed ring by bonding between R 1  and W 3  or R 11  and W 14 ; L 1  to L 9 , and L 11  to L 15  each are independently a methine group; X 1  and X 11  each are an ion necessary to compensate for an intramolecular charge; l1 and l11 each an ion necessary to compensate for an intramolecular charge; m1 to m3 each are 0 or 1; p1 and p11 are each 0 or 1; q1 and q11 each are 1 or 2, provided that the sum of p1 and q1 and the sum of p11 and q11 are respectively not more than 2.