[go: up one dir, main page]

US3920458A - Photographic sensitive material suitable for the silver-dyestuff bleaching method - Google Patents

Photographic sensitive material suitable for the silver-dyestuff bleaching method Download PDF

Info

Publication number
US3920458A
US3920458A US412521A US41252173A US3920458A US 3920458 A US3920458 A US 3920458A US 412521 A US412521 A US 412521A US 41252173 A US41252173 A US 41252173A US 3920458 A US3920458 A US 3920458A
Authority
US
United States
Prior art keywords
beta
group
sensitive material
naphthothiazole
naphthoselenazole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US412521A
Inventor
Keisuke Shiba
Masanao Hinata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP8453470A external-priority patent/JPS4934140B1/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Priority to US412521A priority Critical patent/US3920458A/en
Application granted granted Critical
Publication of US3920458A publication Critical patent/US3920458A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed

Definitions

  • ABSTRACT 1 A photographic sensitive material having at least one sensitive silver halide emulsion layer containing dyestuffs suitable for the silver-dyestuff bleaching method, the improvement which comprisesa combination of at least one of sensitizing dyestuffs of the following general Formula (I) and at least one of sensitizing dyestuffs of the following general Formula (11):
  • Z represents a non-metallic atomic grouping required for the completion of a naphthothiazole or naphthoselenazole ring
  • Z represents a non-metallic atomic grouping required for the completion of a naphthothiazole, benzothiazole, naphthoselenazole or benzoselenazole ring
  • R represents a member selected from the first group consistinf of a hydrogen atom, lower alkyl or aryl radical
  • R and R each represents an alkyl radical and at least one of said R and R is an alkyl radical containing a carboxyl or sulfo group
  • X represents an anion
  • n is 1 or 2
  • n 1 if an intermolecular salt is formed:
  • Z and Z which may be identical or different, each represents a non-metallic atomic grouping required for the completionof a benzothiazole or benzoselenazole ring
  • R represents a member selected from the second group consisting of a hydrogen atom, lower alkyl or aryl radical, R and R have the same meanings as R, and R and at least one of said R and R is an alkyl radical containing a carboxyl or sulfo group
  • X represents an anion
  • m is l or 2
  • m l if an intermolecular salt is formed.
  • sensitizing dyestuffs used in the sensitive material for the silver-dyestuff bleaching method must satisfy some necessary requirements.
  • sensitizing dyestuffs should not cause residual coloration afterithe photographic sensitive material is treated. Further, sensitizing dyestuffs must be adsorbed firmly onto silver halide particles lest they must be substituted by dyestuffs suitable for the silver dyestuff bleaching method; otherwise the sensitizing effect is diminished highly by thepresence of dyestuffs suitable for the silver dyestuff bleaching method. 7
  • a multi-layer material contains at least a blue sensitive emulsion layer, a green sensitive emulsion layer and a red sensitive emulsion layer. It is necessary that each color sensitization region of these. Three layers is :separated well, above all that the red sensitive'emulsion is as little green sensitive as possible. For this purpose, a red sensitive layer having a low green sensitivity and a high red sensitivity-is required. The sensitizing dyestuff used in the red sensitive emulsion should not difdoes not show these characteristics.
  • An object of this invention is to provide a combination of sensitizing dyestuffs useful to the silver halide photographic emulsion used in the silver-dyestuff bleaching method and, in particular, to provide a photographic emulsion for the red sensitive layer, which has a high sensitivity and is substantially free from the residual coloration and does not provide the red sensitivity to other layers.
  • Z represents a non-metallic atomic grouping required for the completion of a naphthothiazole or naphthoselenazole ring
  • Z represents a non-metallic atomic grouping required for the completion of naphthothiazole, benzothiazole, naphthoselenazole or benzoselenazole ring
  • R represents hydrogen atom, lower alkyl or aryl radical
  • R each represents alkyl radical such as, for example, methyl, ethyl, n-propyl, B-hydroxyethyl, ,B-acetoxyethyl and y-acetoxypropyl radical, alkyl containing carboxyl group (for example, carboxymethyl, B-carboxyethyl and 'y-carboxypropyl radical, 2-(2-carboxyethoxy)ethyl, alkyl containing sulfo group (for example, B-sulfoethyl, y-sulf
  • R represents a hydrogen atom, lower alkyl or aryl radical
  • R and R have the same meanings as R and R and at least one of R and R represents an alkyl radical containing a carboxyl or sulfo group
  • X represents an anion
  • naphthothiazole and naphthoselenazole rings which may be completed by Z and a-naphthothiazole, B-naphthothiazole, B, B-naphthothiazole, anaphthoselenazole, B-naphthoselenazole and [3,13- naphthoselenazole.
  • naphthothiazole, benzothiazole, naphthoselenezole and benzoselenazole rings which may be completed by Z are (Ii-I'lfiPI'ItI'IOthIfiZOlG, B-naphthothiazole, B,/3-naphthothiazole, benzothiazole, 5- methylbenzothiazole, 5-chlorobenzothiazole, 5- methoxybenzothiazole, 5-bromobenzothiazole, 5 ,6- dimethylbenzothiazole, S-cyanobenzothiazole, 5- phenylbenzothiazole, 5-hydroxy-6-methylbenzo- Examples of R and R; as lower alkyl and aryl radicals are methyl, ethyl, n-propyl, phenyl, p-methoxyphenyl, o-carboxyphenyl and the like.
  • X there may be mentioned chlorine, bromine, iodine, perchlorate, p-toluenesulfonic acid, ethyl sulfuric acid ion etc.
  • sensitizing dyestuffs to be used in this invention are known to those skilled in the art.
  • sensitizing dyestuffs provides a photographic emulsion having'a low green sensitivity and a high red sensitivity in the presence of dyestuffs suitable for the silver dyestuff bleaching method. While, in the case of a red sensitive layer.
  • sensitizing dyestuffs of the general Formula (I) used in this invention are shown as follows, but
  • the sensitizing dyestuffs are not restricted only to these examples s H- ⁇ N (C 2 )a rf (CHQ SOI OCH lI-7 c 14,
  • the sensitizing dyestuffs of the general Formula (I) and (II) are introduced together with the dyestuff suitable for the silver-dyestuff bleaching method into the photographic layer used to the method. It is convenient to add the sensitizing dyestuffs to the emulsion, which has been washed with water and is not used for coating, especially before the addition of the dyestuff suitable for the method.
  • sensitizing dyestuffs to the photographic emulsion.
  • it may be added as a solution in a solvent such as water, methanol, ethanol, methyl cellosolve, etc., to the photographic emulsion.
  • silver halide such as silver chloride, bromide, iodobromide, chlorobromide and chloroiodobromide may be used.
  • gelatine-silver halide emulsion While a conventional gelatine-silver halide emulsion is used in this invention, resinous substances or cellulose derivatives which do not effect adversely to the sensitive material, may be used instead of gelatine.
  • the photographic emulsion used in this invention may contain conventional additives such as chemical sensitizer, anti-fogging agent, stabilizer, hardener, coating assistant, plasticizer, development accelerator and air anti-fogging agent.
  • the photographic emulsion may be coated in a common manner on a suitable supporter such as glass, film of cellulose derivate, a film of synthetic resin, a laminated paper, a synthetic paper and Baryta paper.
  • a suitable supporter such as glass, film of cellulose derivate, a film of synthetic resin, a laminated paper, a synthetic paper and Baryta paper.
  • the dyestuffs which are used together with the sensitizing dyestuffs and which are suitable for the silverdyestuff bleaching method are those which are used commonly in the method. In particular, those containing phenolic hydroxyl group or sulfonic acid group are preferred. Preferred dyestuffs are described in th specification US. Pat. No. 3,157,508.
  • EXAMPLE 1 6 Single sensitizing dyestuffs and combined ones were added respectively to a silver iodobromide emulsion (iodine content: mol%) and stirred well for 20 minutes, and, after standing for a while, 19.0 g/silver halide g mol of dyestuff of the following formula were added and stirred well, both common coating assistant and hardener were added and stirred well, and the whole h 5. Hardening for 5 min,
  • tetrasodium ethylenediaminetetracetate 26 g anhydrous sodium carbonate 24 g ferric chloride l5 g anhydrous sodium sulfite 13 g crystalline sodium thiosulfate 200 g water enough to make up I 1 .IO. Washing with water for 20 min.
  • a photographic sensitive material having at least one red sensitive silver halide emulsion layer contain ing cyan azo dyestuffs suitable for the silver-dyestuff bleaching method, theimprovement which comprises a combination of at least one of sensitizing dyestuffs'of the following general Formula (I) and at least one of 2 sensitizing dyestuffs of the following general Formula (II):
  • Z represents a non-metallic atomic grouping required for the completion of a naphthothiazole or naphthoselenazole ring
  • Z represents a non-metallic atomic grouping required for the completion of a naphthothiazole, benzothiazole, naphthoselenazole or benzoselenazole ring
  • R represents a member selected from the first group consisting of a hydrogen atom, lower alkyl or aryl radical
  • R and R each represents an alkyl radical and at least one of said R and R is an alkyl radical containing a carboxyl or sulfo group
  • X represents an anion
  • n is l or 2, and n1 if an intermolecular salt is formed
  • Z and Z which may be identical or different, each represents a non-metallic atomic grouping required for the completion of a benzothiazole or benzoselenazole ring
  • R represents a member selected from the second group consisting of a hydrogen atom, lower alkyl or aryl radical, R and R having the same meanings as R, and R and at least one of said R and R is an alkyl radical containing a carboxyl or sulfo group
  • X represents an anion
  • m is 1 or 2
  • m l if an intermolecular salt is formed.
  • Formula (I) is selected from the group consisting of the following:
  • sensitizing dyestuff according to Formula ll is selected from the group consisting of the (C Hg mom lected from the fourth group consisting of methyl, ethyl, n-propyl, ,B-hydroxyethyl, B-acetoxyethyl, yacetoxypropyl, carboxymethyl, B-carboxyethyl, y-carboxypropyl, 2-(2-carboxyethoxy)ethyl, ,B-sulfoethyl, 'y-sulfopropyl, 'y-sulfobutyl, 8-sulfobutyl, 2-hydroxy-lsulfopropyl, 2-acetoxy-l-sulfopropyl, 2,(3-sulfopropoxy ethyl 3-methoxy-2-( 3-sulfopropoxy )propyl 2-(2-(3-sulfopropoxy)eth
  • Z is selected from the group consisting of a-naphthothiazole ,B-naphthothiazole, 8,8- naphthothiazole, a-naphthoselenazole, B-naphthoselenazole, and B,B-naphthoselenazole.
  • Z is selected from the group consisting of a-naphthothiazole, B-naphthothiazole, [3,8- naphthothiazole, benzothiazole, S-methylbenzothiazole, 5-chlorobenzothiazole, S-methoxybenzothiazole, 5-bromobenzothiazole, 5,6-dimethylbenzothiazole, S-cyanobenzothiazole, S-phenylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, S-hydroxybenzothiazole, 5-ethyoxy-6-methylbenzothiazole, 5- carboxybenzothiazole, a-naphthoselenazole, ,B-naphthoselenazole, B,B-naphthoselenazole, S-methylbenzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzosele

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract


wherein Z2 and Z3, which may be identical or different, each represents a non-metallic atomic grouping required for the completion of a benzothiazole or benzoselenazole ring, R3 represents a member selected from the second group consisting of a hydrogen atom, lower alkyl or aryl radical, R4 and R5 have the same meanings as R1 and R2 and at least one of said R4 and R5 is an alkyl radical containing a carboxyl or sulfo group, X represents an anion, m is 1 or 2, and m 1 if an intermolecular salt is formed.

wherein Z represents a non-metallic atomic grouping required for the completion of a naphthothiazole or naphthoselenazole ring, Z1 represents a non-metallic atomic grouping required for the completion of a naphthothiazole, benzothiazole, naphthoselenazole or benzoselenazole ring, R represents a member selected from the first group consistinf of a hydrogen atom, lower alkyl or aryl radical, R1 and R2 each represents an alkyl radical and at least one of said R1 and R2 is an alkyl radical containing a carboxyl or sulfo group, X represents an anion, n is 1 or 2, and n 1 if an intermolecular salt is formed:
D R A W I N G
A photographic sensitive material having at least one sensitive silver halide emulsion layer containing dyestuffs suitable for the silver-dyestuff bleaching method, the improvement which comprises a combination of at least one of sensitizing dyestuffs of the following general Formula (I) and at least one of sensitizing dyestuffs of the following general Formula (II):

Description

United States Patent 1191 Shiba et al.
[ Nov. 18, 1975 PHOTOGRAPHIC SENSITIVE MATERIAL SUITABLE FOR THE SILVER-DYESTUFF BLEACHING METHOD [75] Inventors: Keisuke Shiba; Masanao Hinata,
both of Minami-ashigara, Japan [73] Assignee: Fuji Photo Film Co., Ltd., Japan [22] Filed: Nov. 2, 1973 [21] Appl. No.: 412,521
Related US. Application Data [63] Continuation of Ser. No. 184,585, Sept. 28, 1971,
abandoned.
[30] Foreign Application Priority Data Primary Examiner-J. Travis Brown Attorney, Agent, or F irmSughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT 1 A photographic sensitive material having at least one sensitive silver halide emulsion layer containing dyestuffs suitable for the silver-dyestuff bleaching method, the improvement which comprisesa combination of at least one of sensitizing dyestuffs of the following general Formula (I) and at least one of sensitizing dyestuffs of the following general Formula (11):
wherein Z represents a non-metallic atomic grouping required for the completion of a naphthothiazole or naphthoselenazole ring, Z represents a non-metallic atomic grouping required for the completion of a naphthothiazole, benzothiazole, naphthoselenazole or benzoselenazole ring, R represents a member selected from the first group consistinf of a hydrogen atom, lower alkyl or aryl radical, R and R each represents an alkyl radical and at least one of said R and R is an alkyl radical containing a carboxyl or sulfo group, X represents an anion, n is 1 or 2, and n=1 if an intermolecular salt is formed:
wherein Z and Z which may be identical or different, each represents a non-metallic atomic grouping required for the completionof a benzothiazole or benzoselenazole ring, R represents a member selected from the second group consisting of a hydrogen atom, lower alkyl or aryl radical, R and R have the same meanings as R, and R and at least one of said R and R is an alkyl radical containing a carboxyl or sulfo group, X represents an anion, m is l or 2, and m=l if an intermolecular salt is formed.
8 Claims, No Drawings PHOTOGRAPHIC SENSITIVE MATERIAL SUITABLE FOR THE SILVER-DYESTUFF BLEACHING METHOD This is a continuation, of application Ser. No. 184,585, filed Sept. 28, 1971, now abandoned.
FIELD OF THE INVENTION BACKGROUND OF THE INVENTION One of the disadvantages in the silver-dyestuff bleaching method is that the sensitive rate of the dyed photographic layer is reduced to a considerable extent, The reason therefor is that the maximum sensitive wavelength is approximately identical to the maximum absorption wavelength of dyestuff. The sensitivity rate of the sensitive layer in the silver-dyestuff bleaching method is lower than that inother color photographic methods. Accordingly, a serious problem in the silverdyestuff bleaching method is in the preparation of a layer having a sufficient sensitivity.
In the art of manufacturing a silver halide emulsion, it has been well known that the addition of sensitizing dyestuffs to the emulsion spreads the sensitive spectrum region of the emulsion resulting in an optically sensitized emulsion. The sensitizing dyestuffs used in the sensitive material for the silver-dyestuff bleaching method must satisfy some necessary requirements.
Except for the high sensitization, sensitizing dyestuffs should not cause residual coloration afterithe photographic sensitive material is treated. Further, sensitizing dyestuffs must be adsorbed firmly onto silver halide particles lest they must be substituted by dyestuffs suitable for the silver dyestuff bleaching method; otherwise the sensitizing effect is diminished highly by thepresence of dyestuffs suitable for the silver dyestuff bleaching method. 7
A multi-layer material contains at least a blue sensitive emulsion layer, a green sensitive emulsion layer and a red sensitive emulsion layer. It is necessary that each color sensitization region of these. three layers is :separated well, above all that the red sensitive'emulsion is as little green sensitive as possible. For this purpose, a red sensitive layer having a low green sensitivity and a high red sensitivity-is required. The sensitizing dyestuff used in the red sensitive emulsion should not difdoes not show these characteristics.
An object of this invention is to provide a combination of sensitizing dyestuffs useful to the silver halide photographic emulsion used in the silver-dyestuff bleaching method and, in particular, to provide a photographic emulsion for the red sensitive layer, which has a high sensitivity and is substantially free from the residual coloration and does not provide the red sensitivity to other layers. Other objects will be apparent to those skilled in the art as the description of this invention proceeds.
DESCRIPTION OF THE INVENTION Objects of this invention are accomplished by using the combination of sensitizing dyestuffs represented by the following general Formula (I) and (II):
wherein Z represents a non-metallic atomic grouping required for the completion of a naphthothiazole or naphthoselenazole ring, Z represents a non-metallic atomic grouping required for the completion of naphthothiazole, benzothiazole, naphthoselenazole or benzoselenazole ring, R represents hydrogen atom, lower alkyl or aryl radical, R, and R each represents alkyl radical such as, for example, methyl, ethyl, n-propyl, B-hydroxyethyl, ,B-acetoxyethyl and y-acetoxypropyl radical, alkyl containing carboxyl group (for example, carboxymethyl, B-carboxyethyl and 'y-carboxypropyl radical, 2-(2-carboxyethoxy)ethyl, alkyl containing sulfo group (for example, B-sulfoethyl, y-sulfopropyl, y-sulfobutyl, fi-sulfobutyl, Z-hydroxy-l-sulfopropyl, 2- acetoxy-l-sulfopropyl, 2-(3-sulfopropoxy)ethyl, 3- methoxy- 2-( 3-sulfoprop oxy)propyl, 2-( 2-( 3-sulfopropoxy)ethoxy)ethyl and 2-hydroxy-3-(3-sulfopropoxy)propyl radical) etc., and at least one of R and R is an alkyl radical containing carboxyl or sulfo group, X represents an anion, n is l or 2 and n =1 if an intermolecular salt is formed.
- quired for the completion of a benzothiazole or benzoselenazole ring, R represents a hydrogen atom, lower alkyl or aryl radical, R and R have the same meanings as R and R and at least one of R and R represents an alkyl radical containing a carboxyl or sulfo group, X represents an anion, m is l or 2 and m =l if an intermolecular salt is formed.
Examples of naphthothiazole and naphthoselenazole rings which may be completed by Z and a-naphthothiazole, B-naphthothiazole, B, B-naphthothiazole, anaphthoselenazole, B-naphthoselenazole and [3,13- naphthoselenazole.
Examples of naphthothiazole, benzothiazole, naphthoselenezole and benzoselenazole rings which may be completed by Z are (Ii-I'lfiPI'ItI'IOthIfiZOlG, B-naphthothiazole, B,/3-naphthothiazole, benzothiazole, 5- methylbenzothiazole, 5-chlorobenzothiazole, 5- methoxybenzothiazole, 5-bromobenzothiazole, 5 ,6- dimethylbenzothiazole, S-cyanobenzothiazole, 5- phenylbenzothiazole, 5-hydroxy-6-methylbenzo- Examples of R and R; as lower alkyl and aryl radicals are methyl, ethyl, n-propyl, phenyl, p-methoxyphenyl, o-carboxyphenyl and the like.
As examples of X, there may be mentioned chlorine, bromine, iodine, perchlorate, p-toluenesulfonic acid, ethyl sulfuric acid ion etc.
The sensitizing dyestuffs to be used in this invention are known to those skilled in the art.
The combined use of sensitizing dyestuffs according to this invention provides a photographic emulsion having'a low green sensitivity and a high red sensitivity in the presence of dyestuffs suitable for the silver dyestuff bleaching method. While, in the case of a red sensitive layer.
Examples of sensitizing dyestuffs of the general Formula (I) used in this invention are shown as follows, but
the sensitizing dyestuffs are not restricted only to these examples s H- \N (C 2 )a rf (CHQ SOI OCH lI-7 c 14,
(CH CH OMCHQ SOJ (CHQ SO I-I mula (I) to one of the Formula (II) used is not critical but an especially effective range is 9:1 1:9 by weight and may be varied according to the purpose for use.
The sensitizing dyestuffs of the general Formula (I) and (II) are introduced together with the dyestuff suitable for the silver-dyestuff bleaching method into the photographic layer used to the method. It is convenient to add the sensitizing dyestuffs to the emulsion, which has been washed with water and is not used for coating, especially before the addition of the dyestuff suitable for the method.
The process for the addition of said sensitizing dyestuffs to the photographic emulsion is well known in the field of manufacturing the emulsion. In general, it may be added as a solution in a solvent such as water, methanol, ethanol, methyl cellosolve, etc., to the photographic emulsion.
For the emulsion used in this invention, silver halide such as silver chloride, bromide, iodobromide, chlorobromide and chloroiodobromide may be used.
While a conventional gelatine-silver halide emulsion is used in this invention, resinous substances or cellulose derivatives which do not effect adversely to the sensitive material, may be used instead of gelatine.
The photographic emulsion used in this invention may contain conventional additives such as chemical sensitizer, anti-fogging agent, stabilizer, hardener, coating assistant, plasticizer, development accelerator and air anti-fogging agent.
The photographic emulsion may be coated in a common manner on a suitable supporter such as glass, film of cellulose derivate, a film of synthetic resin, a laminated paper, a synthetic paper and Baryta paper.
The dyestuffs which are used together with the sensitizing dyestuffs and which are suitable for the silverdyestuff bleaching method are those which are used commonly in the method. In particular, those containing phenolic hydroxyl group or sulfonic acid group are preferred. Preferred dyestuffs are described in th specification US. Pat. No. 3,157,508.
EXAMPLE 1 6 Single sensitizing dyestuffs and combined ones were added respectively to a silver iodobromide emulsion (iodine content: mol%) and stirred well for 20 minutes, and, after standing for a while, 19.0 g/silver halide g mol of dyestuff of the following formula were added and stirred well, both common coating assistant and hardener were added and stirred well, and the whole h 5. Hardening for 5 min,
The ratio of sensitizing dyestuff of the general Forwas coated on a cellulose triacetate basefThe treatment was carried out according to the following formulation. The results are shown in the Table l.
1. Development for 5 min.
p-methylaminophenol hydrochloride l hydroquinone I 1 3 anhydrous sodium sulfite potassium bromide I anhydrous sodium carbonate water enough to make up I Washing with water for 5 min. Fixing for 5 min.
crystalline sodium thiosulfate potassium metabisulfite waterenough to make up I l 4. Washing with water for 5min.
30% aq. solution of formaldehyde anhydrous sodium carbonate 2 g water enough to make up I 6, Washing with water for 5 min. 7. Bleaching the dyestuff for l0 min.
thiourea 28 g potassium bromide 18 g Z-amino-3-hydroxyphenazine 3 g conc. hydrochloric acid 200 ml water enough to make up l l 8, Washing with water for 5 min. 9, Bleaching-fixing for l0 min.
tetrasodium ethylenediaminetetracetate 26 g anhydrous sodium carbonate 24 g ferric chloride l5 g anhydrous sodium sulfite 13 g crystalline sodium thiosulfate 200 g water enough to make up I 1 .IO. Washing with water for 20 min.
The structural formula of dyestuff used was as follows:
What is claimed is: v
1. In a photographic sensitive material having at least one red sensitive silver halide emulsion layer contain ing cyan azo dyestuffs suitable for the silver-dyestuff bleaching method, theimprovement which comprises a combination of at least one of sensitizing dyestuffs'of the following general Formula (I) and at least one of 2 sensitizing dyestuffs of the following general Formula (II):
R, r 1 c=ci-| c=cii "c r 1 R;1(X
wherein Z represents a non-metallic atomic grouping required for the completion of a naphthothiazole or naphthoselenazole ring, Z represents a non-metallic atomic grouping required for the completion of a naphthothiazole, benzothiazole, naphthoselenazole or benzoselenazole ring, R represents a member selected from the first group consisting of a hydrogen atom, lower alkyl or aryl radical, R and R each represents an alkyl radical and at least one of said R and R is an alkyl radical containing a carboxyl or sulfo group, X represents an anion, n is l or 2, and n1 if an intermolecular salt is formed;
I Z a Z3 wherein Z and Z which may be identical or different, each represents a non-metallic atomic grouping required for the completion of a benzothiazole or benzoselenazole ring, R represents a member selected from the second group consisting of a hydrogen atom, lower alkyl or aryl radical, R and R having the same meanings as R, and R and at least one of said R and R is an alkyl radical containing a carboxyl or sulfo group, X represents an anion, m is 1 or 2, and m=l if an intermolecular salt is formed.
2. The photographic sensitive material according to claim 1 wherein the sensitizing dyestuff according to.
Formula (I) is selected from the group consisting of the following:
3. The photographic sensitive material according to claim 1 wherein the sensitizing dyestuff according to Formula ll is selected from the group consisting of the (C Hg mom lected from the fourth group consisting of methyl, ethyl, n-propyl, ,B-hydroxyethyl, B-acetoxyethyl, yacetoxypropyl, carboxymethyl, B-carboxyethyl, y-carboxypropyl, 2-(2-carboxyethoxy)ethyl, ,B-sulfoethyl, 'y-sulfopropyl, 'y-sulfobutyl, 8-sulfobutyl, 2-hydroxy-lsulfopropyl, 2-acetoxy-l-sulfopropyl, 2,(3-sulfopropoxy ethyl 3-methoxy-2-( 3-sulfopropoxy )propyl 2-(2-(3-sulfopropoxy)eth0xy)ethyl and 2-hydroxy-3- (3 '-sulfop ropoxy )propyl.
6. The photographic sensitive material according to claim 1 wherein said X is selected from the fifth group consisting of chlorine, bromine, iodine, perchlorate, p-toluenesulfonic acid, and ethyl sulfuric acid.
7. The photographic sensitive material according to claim 1 wherein said Z is selected from the group consisting of a-naphthothiazole ,B-naphthothiazole, 8,8- naphthothiazole, a-naphthoselenazole, B-naphthoselenazole, and B,B-naphthoselenazole.
8. The photographic sensitive material according to claim 1 wherein said Z is selected from the group consisting of a-naphthothiazole, B-naphthothiazole, [3,8- naphthothiazole, benzothiazole, S-methylbenzothiazole, 5-chlorobenzothiazole, S-methoxybenzothiazole, 5-bromobenzothiazole, 5,6-dimethylbenzothiazole, S-cyanobenzothiazole, S-phenylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, S-hydroxybenzothiazole, 5-ethyoxy-6-methylbenzothiazole, 5- carboxybenzothiazole, a-naphthoselenazole, ,B-naphthoselenazole, B,B-naphthoselenazole, S-methylbenzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, S-phenylbenzoselenazole, 5,6-dimethylbenzolselenazole, S-hydroxybenzoselenazole.

Claims (8)

1. IN A PHOTOGRAPHIC SENSITIVE MATERIAL HAVING AT LEAST ONE RED SENSITIVE SILVER HALIDE EMULSION LAYER CONTAINING CYAN AZO DYESTUFFS SUITABLE FOR THE SILVER-DYESTUFF BLEACHING METHOD, THE IMPROVEMENT WHICH COMPRISES A COMBINATION OF AT LEAST ONE OF SENSITIZING DYESTUFFS OF THE FOLLOWING GENERAL FORMULA (1) AND AT LEAST ONE SENSITIZING DYESTUFFS OF THE FOLLOWING GENERAL FORMULA (II):
2. The photographic sensitive material according to claim 1 wherein the sensitizing dyestuff according to Formula (I) is selected from the group consisting of the following:
3. The photographic sensitive material according to claim 1 wherein the sensitizing dyestuff according to Formula II is selected from the group consisting of the following:
4. The photographic sensitive material according to claim 1 wherein said first and second group members are selected from the third group consisting of methyl, ethyl, n-propyl, phenyl, p-methoxyphenyl, and O - carboxyphenyl.
5. The photographic sensitive material according to claim 1 wherein said R1, R2, R3 and R4 radicals are selected from the fourth group consisting of methyl, ethyl, n-propyl, Beta -hydroxyethyl, Beta -acetoxyethyl, gamma -acetoxypropyl, carboxymethyl, Beta -carboxyethyl, gamma -carboxypropyl, 2-(2-carboxyethoxy)ethyl, Beta -sulfoethyl, gamma -sulfopropyl, gamma -sulfobutyl, delta -sulfobutyl, 2-hydroxy-1-sulfopropyl, 2-acetoxy-1-sulfopropyl, 2,(3-sulfopropoxy)ethyl, 3-methoxy-2-(3-sulfopropoxy)propyl, 2-(2-(3-sulfopropoxy)ethoxy)ethyl and 2-hydroxy-3-(3''-sulfopropoxy)propyl.
6. The photographic sensitive material according to claim 1 wherein said X is selected from the fifth group consisting of chlorine, bromine, iodine, perchlorate, p-toluenesulfonic acid, and ethyl sulfuric acid.
7. The photographic sensitive material according to claim 1 wherein said Z is selected from the group consisting of Alpha -naphthothiazole Beta -naphthothiazole, Beta , Beta -naphthothiazole, Alpha -naphthoselenazole, Beta -naphthoselenazole, and Beta , Beta -naphthoselenazole.
8. The photographic sensitive material according to claim 1 wherein said Z1 is selected from the group consisting of Alpha -naphthothiazole, Beta -naphthothiazole, Beta , Beta -naphthothiazole, benzotHiazole, 5-methylbenzothiazole, 5-chlorobenzothiazole, 5-methoxybenzothiazole, 5-bromobenzothiazole, 5,6-dimethylbenzothiazole, 5-cyanobenzothiazole, 5-phenylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, 5-hydroxybenzothiazole, 5-ethyoxy-6-methylbenzothiazole, 5-carboxybenzothiazole, Alpha -naphthoselenazole, Beta -naphthoselenazole, Beta , Beta -naphthoselenazole, 5-methylbenzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-phenylbenzoselenazole, 5,6-dimethylbenzolselenazole, 5-hydroxybenzoselenazole.
US412521A 1970-09-28 1973-11-02 Photographic sensitive material suitable for the silver-dyestuff bleaching method Expired - Lifetime US3920458A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US412521A US3920458A (en) 1970-09-28 1973-11-02 Photographic sensitive material suitable for the silver-dyestuff bleaching method

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP8453470A JPS4934140B1 (en) 1970-09-28 1970-09-28
US18458571A 1971-09-28 1971-09-28
US412521A US3920458A (en) 1970-09-28 1973-11-02 Photographic sensitive material suitable for the silver-dyestuff bleaching method

Publications (1)

Publication Number Publication Date
US3920458A true US3920458A (en) 1975-11-18

Family

ID=27304577

Family Applications (1)

Application Number Title Priority Date Filing Date
US412521A Expired - Lifetime US3920458A (en) 1970-09-28 1973-11-02 Photographic sensitive material suitable for the silver-dyestuff bleaching method

Country Status (1)

Country Link
US (1) US3920458A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4042400A (en) * 1975-01-14 1977-08-16 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material
EP0472004A1 (en) * 1990-08-16 1992-02-26 Eastman Kodak Company Sensitizing dye combination for photographic materials

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3157507A (en) * 1958-12-04 1964-11-17 Ciba Ltd Optical sensitization of photographic materials suitable for the silver-dyebleachingprocess
US3615581A (en) * 1967-05-22 1971-10-26 Agfa Gevaert Ag Photographic material for the silver dye bleach process
US3617293A (en) * 1967-07-26 1971-11-02 Fuji Photo Film Co Ltd Photographic supersensitized silver halide emulsions
US3635716A (en) * 1968-08-26 1972-01-18 Ciba Geigy Ag Photographic material for the silver dye bleaching process
US3682640A (en) * 1969-08-20 1972-08-08 Fuji Photo Film Co Ltd Spectrally sensitized photographic materials suitable for silver dye bleaching method
US3793031A (en) * 1970-12-30 1974-02-19 Fuji Photo Film Co Ltd Color photographic light-sensitive materials for diffusion transfer process

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3157507A (en) * 1958-12-04 1964-11-17 Ciba Ltd Optical sensitization of photographic materials suitable for the silver-dyebleachingprocess
US3615581A (en) * 1967-05-22 1971-10-26 Agfa Gevaert Ag Photographic material for the silver dye bleach process
US3617293A (en) * 1967-07-26 1971-11-02 Fuji Photo Film Co Ltd Photographic supersensitized silver halide emulsions
US3635716A (en) * 1968-08-26 1972-01-18 Ciba Geigy Ag Photographic material for the silver dye bleaching process
US3682640A (en) * 1969-08-20 1972-08-08 Fuji Photo Film Co Ltd Spectrally sensitized photographic materials suitable for silver dye bleaching method
US3793031A (en) * 1970-12-30 1974-02-19 Fuji Photo Film Co Ltd Color photographic light-sensitive materials for diffusion transfer process

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4042400A (en) * 1975-01-14 1977-08-16 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material
EP0472004A1 (en) * 1990-08-16 1992-02-26 Eastman Kodak Company Sensitizing dye combination for photographic materials
US5597687A (en) * 1990-08-16 1997-01-28 Eastman Kodak Company Sensitizing dye combination for photographic materials

Similar Documents

Publication Publication Date Title
US6387610B1 (en) Silver halide photographic emulsion and silver halide photographic material containing said silver halide photographic emulsion
US3615632A (en) Supersensitized photographic silver halide light-sensitive elements
US3988155A (en) Silver halide photographic emulsion
US4152163A (en) Silver halide photographic emulsion containing cyanine and hemicyanine sensitizing dyes
US4046572A (en) Silver halide photographic light sensitive material
US4581329A (en) Silver halide photographic light-sensitive material
JPS5852576B2 (en) silver halide photographic emulsion
US3580724A (en) Light-sensitive supersensitized silver halide color photographic emulsions
US3945832A (en) Fogged, direct-positive silver halide emulsion containing desensitizers and a dimethine optical sensitizing dye
US3920458A (en) Photographic sensitive material suitable for the silver-dyestuff bleaching method
US4040841A (en) Silver halide photographic emulsion
US3615610A (en) Silver halide direct positive emulsions spectrally sensitized with a combination of a desensitizing dye with a 2-phenylindole methine dye
US3986878A (en) Silver halide photographic emulsion
US3907575A (en) Spectrally sensitized silver halide photographic emulsion
EP0439356A1 (en) Spectrally sensitized silver halide photographic material
US3994733A (en) Silver halide photographic emulsion
JPS6289952A (en) Photographic silver halide emulsion
US3967967A (en) Spectrally sensitized silver halide photographic emulsion
US3985563A (en) Silver halide photographic emulsion
US2159038A (en) Photographic emulsion
JP2544603B2 (en) Silver halide color photographic material
US2226158A (en) Photographic emulsion
US4493889A (en) Silver halide photographic light-sensitive materials
JPS63167348A (en) Photographic silver halide emulsion
JPS5851256B2 (en) Spectrally sensitized silver halide photographic emulsion and its manufacturing method