Fogged direct positive silver halide emulsion containing a cyanine dye having at least one benzoxazole or benzothiazole nucleus substituted with halogen atoms

• US 4,110,116 A
• Filed: 03/16/1977
• Issued: 08/29/1978
• Est. Priority Date: 06/18/1973
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Valbusa, Luigi, Beretta, Paolo
• Primary Examiner(s): Louie, Jr., Won H.
• Application Number:
  US05/778,135
• Time in Patent Office: 531 Days
• Field of Search: 96/130, 96/137, 96/101, 96/100, 96/107-108, 96/131-138, 96/129, 96/139, 96/140, 260/240.5, 260/240.6, 260/240.65, 542/441, 542/442, 542/443, 542/400, 542/476, 542/474, 542/475, 542/452, 542/473
• US Class Current: 430/547
• CPC Class Codes: C09B 23/06 three >CH- groups, e.g. carbocyanines
• CPC Class Codes: C09B 23/083 five >CH- groups
• CPC Class Codes: C09B 23/086 more than five >CH- groups
• CPC Class Codes: C09B 23/10 The polymethine chain containing an even number of >CH- groups styryl dyes C09B23/14, C09B23/14 takes precedence
• CPC Class Codes: C09B 23/105 two >CH- groups
• CPC Class Codes: C09B 23/107 four >CH- groups
• CPC Class Codes: C09B 23/145 the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
• CPC Class Codes: G03C 1/4853 polymethine dyes

Abstract

New cyanine dyes derived from di-halogen-benzoxazoles and benzothiazoles are desensitizers for silver halide negative emulsions and useful electron acceptor spectral sensitizers for direct positive silver halide emulsions.

Claims

1. A light-sensitive fogged direct positive silver halide emulsion containing a sensitizing amount of at least one cyanine dye selected from the formulae:

wherein

Y is an oxygen or sulfur atom,

n is 2, 3, or 4,

m is 1 or 2,

R and R₁ are independently halogen atoms,

R₂ is H or an alkyl group of 1 to 4 carbon atoms,

R₃ is selected from the group consisting of acylic hydrocarbon, alkyl-aryl, or aryl groups,

R₄ is H or alkyl of 1 to 3 carbon atoms,

Z represents the non-metallic atoms required to complete a 5 or 6 membered desensitizing heterocyclic nucleus, and

X is an acid anion.

2. The light-sensitive fogged direct positive silver halide emulsion of claim 1 containing a sensitizing amount of at least one dye of the formula:

##STR39## wherein;

Y is an oxygen or sulfur atom,

n is 2, 3, or 4,

R and R₁ independently represent a halogen atom,

R₂ is H or an alkyl group of 1 to 4 carbon atoms,

R₃ represents an acyclic hydrocarbon, alkyl-aryl, or aryl group,

R₄ is H or alkyl of 1 to 3 carbon atoms, and

X represents an acid anion.

3. The emulsion of claim 2 wherein R and R₁ are independently selected from the group consisting of Cl and Br and R₃ is an alkyl group of 1 to 12 carbon atoms.

4. The emulsion of claim 3 wherein R and R₁ are the same halogen and R₃ is alkyl of 1 to 4 carbon atoms.

5. The light-sensitive fogged direct positive silver halide emulsion of claim 1 containing a sensitizing amount of at least one dye of the formula:

##STR40## wherein;

m is 1 or 2,

Z represents the C, S, O, Se, or N atoms necessary to complete a 5- or 6-membered desensitizing heterocyclic nucleus,

Y is an oxygen or sulfur atom,

n is 2, 3, or 4,

R and R₁ independently represent a halogen atom,

R₂ is H or an alkyl group of 1 to 4 carbon atoms,

R₃ represents an acyclic hydrocarbon, alkyl aryl, or aryl group, and

X represents an acid anion.

12. The light-sensitive fogged direct positive silver halide emulsion of claim 1 also containing a color coupler.

13. A direct positive photographic element containing at least one layer of the light-sensitive emulsion of claim 1.

6. A light-sensitive fogged direct positive silver halide emulsion containing a sensitizing amount of 3,3'"'"'-diethyl-5,7-5'"'"',7'"'"'-tetrabromo-oxacarbocyanine perchlorate.

7. A light-sensitive fogged direct positive silver halide emulsion containing a sensitizing amount of 3,3'"'"'-dimethyl-5,7-5'"'"',7'"'"'-tetrabromo-9-ethyl-oxacarbocyanine perchlorate.

8. A light-sensitive fogged direct positive silver halide emulsion containing a sensitizing amount of 3,3'"'"'-diethyl-5,7-5'"'"',7'"'"'-tetrachloro-6,6'"'"'-dimethyloxacarbocyanine ethylsulfate.

9. A light-sensitive fogged direct positive silver halide emulsion containing a sensitizing amount of 3,3'"'"'-diethyl-5,6-5'"'"',6'"'"'-tetrachloro-thiacarbocyanine bromide.

10. A light-sensitive fogged direct positive silver halide emulsion containing a sensitizing amount of 3,3'"'"'-diethyl-5,7-5'"'"',7'"'"'-tetrachloro-thiocarbocyanine iodide.

11. A light-sensitive fogged direct positive silver halide emulsion containing a sensitizing amount of 3,3'"'"',9-triethyl-5,7-5'"'"',7'"'"'-tetrachloro-thiocarbocyanine iodide.