US3682640A

US3682640A - Spectrally sensitized photographic materials suitable for silver dye bleaching method

Info

Publication number: US3682640A
Application number: US65713A
Authority: US
Inventors: Keisuke Shiba; Masanao Hinata; Makoto Yoshida; Shinich Imai; Akira Sato; Shigaru Watanabe
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1969-08-20
Filing date: 1970-08-20
Publication date: 1972-08-08
Anticipated expiration: 1989-08-08
Also published as: CH548049A; JPS4933785B1; DE2041200A1; GB1325487A; BE755064A; CA971817A; FR2058405A1; DE2041200B2; FR2058405B1

Abstract

A LIGHT-SENSITIVE SILVER HALIDE EMULSION CONTAINING A DYE CAPABLE OF BEING BLEACHED OUT IN THE SILVER DYE BLEACHING PROCESS AND AT LEAST ONE SENSITIZING DYE HAVING THE FOLLOWING GENERAL FORMULA I

S<(-C(=C<(-S-C(=S)-N(-R3)-CO-))-N(-R2)-CO-C(=(C(-R4)-CH)D=

C<(-Z-N(-R1)-(CH=CH)(N-1)-))-)

WHEREIN R1 IS SELECTED FROM THE GROUP CONSISTING OF AN ALKYL GROUP, A SUBSTITUTED ALKYL GROUP, AN ALLYL GROUP, AN ARALKYL GROUP, A SUBSTITUTED ARALKYL GROUP AND AN ARYL GROUP, WHEREIN R2 AND R3 EACH IS SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM, AN ALKYL GROUP, A SUBSTITUTED ALKYL GROUP, AN ALLYL GROUP, AN ARALKYL GROUP, A SUBSTITUTED ARALKYL GROUP AND AN ARYL GROUP, WHEREIN R4 IS SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM, AN ALKYL GROUP AND AN ARYL GROUP, WHEREIN Z IS A NONMETALLIC ATOM GROUP NECESSARY TO COMPLETE A 5- OR 6-MEMBERED HETEROCYCLIC RING, WHEREIN D REPRESENTS 0, 1 OR 2 AND N REPRESENTS 1 OR 2, IS DISCLOSED. THE EMULSION CAN BE SUPERSENSITIZED BY THE ADDITION OF APPROPRIATE SUPERSENSITIZING DYES.

Description

United States Patent Int. Cl. G63: 1/10 U.S. Cl. 96-99 14 Claims ABSTRACT OF THE DISCLOSURE A light-sensitive silver halide emulsion containing a dye capable of being bleached out in the silver dye bleaching process and at least one sensitizing dye having the following general Formula I wherein R is selected from the group consisting of an alkyl group, a substituted alkyl group, an allyl group, an aralkyl group, a substituted aralkyl group and an aryl group, wherein R and R each is selected from the group consisting of a hydrogen atom, an alkyl group, a substituted alkyl group, an allyl group, an aralkyl group, a substituted aralkyl group and an aryl group, wherein R is selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group, wherein Z is a nonmetallic atom group necessary to complete a 5- or 6-membered heterocyclic ring, wherein 0! represents 0, 1 or 2 and n represents 1 or 2, is disclosed. The emulsion can be supersensitized by the addition of appropriate supersensitizing dyes.

BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to the spectral sensitization of a photographic light-sensitive layer containing a dye suitable for the silver-dye bleaching method.

(2) Description of the prior art It is well known that monoor multi-colored photographic images are obtained by the silver-dye bleaching method based on breakage of the dye depending on the quantity of developed silver. In this method, an image is recorded first as a silver image on a light-sensitive layer colored uniformly with a dye using conventional exposing and developing methods. Then the dye present in this layer is decomposed in proportion to the quantity of the silver present sectionally by the silver-dye bleaching bath. Thereafter, the silver is removed to retain a dye layer having a gradation reverse to that of the original silver image. In the silver-dye bleaching method also, as is well known, the use of a multi-layer material having three or more component color layers differing in sensitivity to the spectrum regions is advantageous to obtain a multicolored photograph as in the case of the color developing method of the color forming type using a multi-layer photographic material. For example, such a multi-layer photographic material has on a support member a redsensitive layer containing a cyan dye, a green sensitive layer containing a magenta dye, a yellow filter layer capable of decreasing the intrinsic sensitivity of the layers 3,682,640 Patented Aug. 8, 1972 ice under the filter layer and a blue-sensitive layer containing a yellow dye as an uppermost layer.

One of the disadvantages of the silver-dye bleaching method is that the light-sensitive speed of a dyed photographic layer is considerably decreased, because the maximum wavelength of the sensitivity substantially coincides with the absorption maximum wavelength of the dye. The sensitivity of the light-sensitive layer in the silver-dye bleaching method is lower than that of other color photographic methods. Therefore, one of the great disadvantages of the silver-dye bleaching method is to prepare a layer having sufiicient sensitivity.

In making silver halide emulsions, a sensitizing dye is added to the silver halide to enlarge the spectrum region of the sensitivity of the silver halide emulsion and for optical sensitization. A sensitizing dye used in the lightsensitive material for the silver-dye bleaching method must satisfy certain necessary conditions. The sensitizing dye should not have an adverse influence upon the sensitivity and stability of the emulsion, in particular, during storage. Furthermore, the sensitizing dye should not cause any coloration remaining after processing of the photographic material. Furthermore, the sensitizing dye should be adsorbed strongly on the silver halide grains so as not to be substituted by a dye suitable for the silver-dye bleaching method. Otherwise the sensitizing action is decreased by the presence of the dye suitable for the silverdye bleaching method. Many of the sensitizing dyes used hitherto in silver halide materials are not suitable for the silver-dye bleaching method.

For example, basic cyanines tend to be desorbed from silver halide grains by a dye having sulfonate group, suitable for the silver-dye bleaching method. Betaine cyanines may be used as sensitizing dyes for a photographic layer in the silver-dye bleaching method, but often retain a slight coloring therein.

It is an object of the invention to provide a sensitizing dye available for the silver halide emulsion used in the silver-dye bleaching method.

It is another object of the invention to provide a photographic material constituted of at least one light-sensitive silver halide emulsion layer optically sensitized and containing a dye suitable for the silver-dye bleaching method.

Other objects will be apparent from the following description and examples.

SUMMARY OF THE INVENTION A photographic light-sensitive layer suitable for the silver-dye bleaching method and having an extraordinarily high sensitivity is prepared by adding to a silver halide emulsion containing a dye suitable for the silver dye bleaching method, a sensitizing dye represented by the following general Formula I, as a sensitizer.

In this formula, R represents an alkyl, a substituted alkyl, an aryl, an aralkyl, or an allyl group, R and R each represents a hydrogen atom, an alkyl, a substituted alkyl, an allyl, an aralkyl, a substituted aralkyl and an aryl group, R represents a hydrogen atom, an alkyl or an aryl group, Z represents the non-metallic atoms necessary to complete a 5- or G-membe'red heterocyclic ring, d represents 0, 1 or 2 and n represents 1 or 2.

R in the general Formula I can be, for example, a methyl, an ethyl, a propyl, a ,B-hydroxyethyl, a B-acetoxyethyl, a sulfatoethyl, a carboxymethyl, a B-carboxyethyl, a y-carboxypropyl, a ,B-sulfoethyl, a 'y-sulfopropyl, a 6- sulfobutyl, a vinylmethyl, a benzyl, a p-carboxybenzyl, a p-sulfophenethyl or a phenyl group.

R and R in the general Formula I can be, for example, a methyl, an ethyl, a propyl, a fl-hydroxyethyl, a ,3- acetoxyethyl, a sulfatoethyl, a carboxymethyl, a ,B-carboxyethyl, a 'y-carboxypropyl, a fl-sulfoethyl, a -sulfopropyl, a a-sulfobutyl, a vinylmethyl, a benzyl, a phenyl, a p-carboxybenzyl, and a p-sulfophenethyl group.

R in the general Formula I can be, for example, a hydrogen atom, a methyl, an ethyl or a phenyl group.

Suitable examples of the heterocyclic ring containing Z in the general Formula I are thiazoles, such as thiazole and thiazoles having a methyl or aphenyl group in the ring; benzothiazoles, such as benbothiazole and benzothiazoles having nucleus substituents such as a halogen atom, alkyl, alkoxy and phenyl groups in the benzene ring; naphthothiazoles, such as a-naphthothiazole, B-naphthothiazole, tetrahydronaphthothiazole and napht-hothiazoles having nucleus substituents such as an alkoxy group in any of the benzene rings; oxazoles, such as oxazole and oxazoles having substituents such as alkyl and phenyl groups in the ring; benzoxazoles, such as benzoxazole and benzoxazoles having nucleus substituents such as a halogen atom, methyl, ethyl, ethoxy, hydroxy and phenyl groups in the benzene ring; naphthoxazoles such as a-naphthoxazole and fl-naphthoxazole; selenazoles, such as 4-methylselenazole and 4-phenylselenazole; benzoselenazoles, such as 5- chlorobenzoselenazole, S-methylbenzoselenalole, S-methoxybenzoselenazole and S-hydroxybenzoselenazole; naphthoselenazoles, such as a-naphthoselenazole and ti-naphthoselenazole; thiazolines, such as thiazoline and 4-methylthiazoline; 2-quinolines, such as 2-quinoline and Z-quinolines having nucleus substituents (exclusive of the 2-position) such as a halogen atom, methyl, methoxy and hydroxyl groups in any of the benzene rings; 4-quinolines, such as 4-quinoline and 4-quinolines having nucleus substituents (exclusive of the 4-position) such as methyl and methoxy groups in any of the benzene rings; benzimidazoles, such as 1,3-diethylbenzimidazole, 1,3-diethyl-5- chlorobenzimidazole and 1,3-diethyl-5,6-dichlorobenzimidazole; 3,3-dialkylindolenines, such as 3,3'-dimethylindolenine, 3,3',5-triethylind0lenine and 3,3',7-trimethy1- indolenine; Z-pyridines, such as 2-pyridine and Z-pyridines having nucleus substituents (exclusive of the 2-position) such as methyl group, and 4-pyridines, such as 4-pyridine.

The sensitizing dye represented by the general Formula I is a dye having four hetero radicals wherein two ketomethylene radicals are directly bonded. The sensitizing dye can sensitize a silver halide emulsion strongly in coexistence with the dye used in the silver-dye bleaching method. 'Since the dye gives a more excellent sensitivity even in the case of a small quantity of the dye added per g-mole of the silver halide in comparison with conventional basic cyanine dyes, any photographic layer containing the dye substantially is freed from any color remaining after processing.

The sensitizing dye represented by the general Formula I can favorably sensitize an emulsion used in the silverdye bleaching method, containing a dye suitable for the silver-dye bleaching method, without any aid, but the supersensitization thereof by a compound represented by the following general Formula II or III is preferred.

II N N m-f |-NHA-NHW 1-111 Y N N Y I I R. I

In 'Formula 11, Y represents =CH- or =N, R R R and R each represents a hydrogen atom, a hydroxyl group, an alkoxy! group, an aryloxyl group, a substituted aryloxyl group such as phenoxyl, o-toloxyl or p-sulfophenoxyl group, a halogen atom such as a chlorine or a bromine atom, a heterocyclic nucleus such as morpholinyl or pipcridyl, an alkylthio group such as a methylthio or an ethylthio group, a heterocyclic thio group such as a benzothiazylthio group, an arylthio group such as a phenylthio or a tolylthio group, an amino group, an alkylamino group or a substituted alkylamino group such as a methylamino, an ethylamino, a propylamino, a dimethylamino, a diethylamino, a dodecylamino, a cyclohexylamino, a B hydroxyethylamino, a di 13 hydroxyethylamino or a p sulfoethylamino group, an arylamino group or a substituted arylamino group such as an anilino, an o-sulfoanilino, a m-sulfoanilino, a p-sulfoanilino, an oanisilamino, a m anisilamino, a p anisilamino, an o-toluidino, a m-toluidino, a p-toluidino, an o-carboxyanilino, a m-carboxyanilino, a p-carboxyanilino, a hydroxyanilino, a naphthylamino or a sulfonaphthyla'mino group, a heterocyclicamino group such as a 2-benzothiazoleamino or a Z-pyridylamino group, or an aryl group such as a phenyl group, and A represents A or A in the following, wherein A is:

wherein A is:

in particular, at least one of R R R and R representing a substituent containing a -SO M group when A is A2- In Formula III, R represents an acylamino group such as an acetamide, a sulfobenzamide, a 4-methoxy-3-sulfobenzamide, a Z-ethoxybenzamide, a 2,4 diethoxybenzamide, a p-toluylamino, a 4-methyl-Z-methoxybenzamide, a l-naphthylamino, a 2-naphthylamino, a 2,4-dimethoxybenzamide, a 2-phenylbenzamide, or a Z-thienylbenzamide group, or a sulfo group, R represents an acylamino group such as defined for R R represents a hydrogen atom or a sulfo group and the general Formula III has at least one sulfo group.

The sensitizing dye represented by the general Formula I is used more advantageously through supersensitization with a novolak type condensate of a polyhydroxybenzene and formaldehyde where the term polyhydroxybenzene is intended to encompass a substituted benzene having from 1 to 3 hydroxyl groups on the benzene nu cleus. The novolak type condensate of the polyhydroxybenzene and formaldehyde will hereinafter be referred to as the formalin condensate.

The polyhydroxybenzene is represented by the following general Formulae (W21, W13, IVc, IVd,

(Iva 011 ,.1 (IVb) 011 ,.2

ORrz S02E11 (1V0) (Oin ([V(]) 011 in which R and R each represents OH, OM, R141 NHg, NHRpg, -(R14)2, and NHNHR R represents an alkyl group of from 1 to 8 carbon atoms, an aryl group or an aralkyl group, M represents an alkali metal or an alkaline earth metal, X represents OH or a halogen atom, X represents a halogen atom, and n n n and 12* each represents 1, 2 or 3 except that n and n are equal to 3 at the same time.

The sensitizing dye of the invention, represented by the general Formula I is described in British Pats. Nos. 487,051 and 489,335, and in US. Pat. No. 2,504,615.

Some of the compounds represented by the general Formula II are described, for example, in U.S. Pats. 2,171,- 427; 2,660,578 and 2,595,030. A method of synthesis of the formalin condensate is illustrated as follows.

The condensate of the polyhydroxybenzene can be synthesized according to the conventional synthesis method for phenol-formaldehyde resins of the novolak type [for example, as described in W. R. Sorenson, T. W. Campbell, Preparative Methods of Polymer Chemistry, John Wiley and Sons, Inc. (1961)]. The poly-substituted hydroxybenzene is dispersed in Water, heated after concentrated hydrochloric acid and 37% formalin are added and held at 100 C. for 30 minutes to 1 hour with agitation. Then, if necessary, hydrochloric acid is further added and the heating with agitation is continued. After the reaction, the reaction product is removed into cold water and the resultant precipitate can be purified. As an example, 415 parts of phydroxybenzoic acid is dispersed in 1,000 parts of water with vigorous agitation, to which 25 parts of a 35% or more concentrated hydrochloric acid and 245 parts of 37% formalin are added. Then, the reaction mixture is heated at 100 C. with agitation and held as is for 30 minutes, to which parts of concentrated hydrochloric acid is added additionally followed by reaction for 30 minutes. At this point, 20 parts of concentrated hydrochloric acid is further added thereto and the stirring is continued until the reaction solution becomes cloudy. After about 1 hour and 30 minutes, the stirring is stopped and the mixture is removed into 3,000 parts of cold water with stirring. The resulting precipitate is filtered, redissolved in 1,000 parts of methanol without drying, and then reprecipitated with water. The product is obtained by filtering and dried. Other condensates can be obtained readily using other polyhydroxybenzenes in place of the p-hydroxybenzoic acid used in the above-described method. The condensation unit (degree of polymerization) of the condensate obtained by the above-described method is from 2 to 10 as in the usual novolak resins.

For the purpose of the invention, condensates having a polymerization degree of from 2 to 10, preferably hav ing a polymerization degree of from 2 to 5 and a molecular weight of from 300 to 800 are suitable.

Examples of the sensitizing dyes used in the invention are given as follows without limiting the invention.

H erably is added to an emulsion before coating, washed 01H (11H; with water, before a dye suitable for the silver dye bleaching method is added. h The method of adding a sensitizing dye to a p oto- C=CH' CH=CHCH 5 graphic emulsion is well known in making photographic N 5 5 emulsions. Generally, it is added to a photographic emul- J sion in the form of a solution in water or an organic 2H! solvent such as methanol or ethanol.

As the emulsion of the invention silver halides such as silver chloride, silver bromide, silver iodobromide, silver chlorobrornide or silver chloroiodobromide can be used. The usual gelatino-silver halide emulsion is used in the invention, but cellulose derivatives and resinous s 1 1 materials which do not afiect the light-sensitive materials can be used in place of gelatin.

G=CH CH=OH CH=(} c= 3 The photographic emulsion used in the invention can contain conventional additives such as chemical sensi- N tizers, fog inhibitors, stabilizers, hardeners, coating aids, t plasticizers, development accelerators and air fog inhibitors.

' The photographic emulsion can be coated onto a suit- I-11 able support such as glass, cellulose derivative films, syn- S R O thetic resin films, laminated papers or synthetic papers ZHS in conventional manner.

C=CH CH=CH CH=A7 5 The dye suitable for the silver dye bleaching method and used in combination with the sensitizing dye repres s sented by the general Formula I is a dye used conven- I tionally in the silver-dye bleaching method, preferably containing a phenolic hydroxyl group or a sulfonate group.

Suitable dyes are described in Japanese Patent Publications 10,280/61, 9,587/64, and 25,768/64; U.S. Pats. The sensitizing dye represented by the general Formula 3,264,109, 3,454,402, 3,178,291, 3,385,706, 3,455,695, I is added to a photographic layer used in the silver-dye 3,259,498, 3,244,525, 3,304,181, 3,322,543, 3,210,190, bleaching method wth a dye suitable for the silver-dye 3,454,401, 3,211,554 and 3,223,527. Suitable examples bleaching method. In particular, the sensitizing dye prefare as follows;

COIIIH (')H (|JOCH (1)131 N=N N=N 8 HzC H 0 8 S 0 H H Oas NH; H03 S o 0 O S 0:11 NH:

MMQMa nEt m-@-t1msn=t{ 0H HOG B035 3 01H I J Q Hons- S H 50H a 3 Q-CO-NH 0H H5020 with R being a benzoyl, a 4-acetylaminobenzoyl or a 4 benzoylaminobenzyl group. 50

The following examples are given in order to illustrate Q-C OHN OR the invention further without limiting the scope thereof. 1 l

EXAMPLE 1 9.68 g.-mol/g.-mol silver halide of a sensitizing dye was added to a silver chlorobromide emulsion (Br mol percent, CI mol percent) and stirred adequately for 20 minutes. 24.2 g./g.-mol silver halide of a dye represented by the following structural formula was added thereto, stirred adequately and coated onto a cellulose 60 triacetate base. The coated photographic layer was exposed through a step wedge of a blue light (Latten Filter No. 47B) and a red light (Fuji Filter N0. 7), developed and fixed. The development was carried out using the composition of Table 1 at 20 C. for 2 minutes.

The results are shown in Table 2 wherein a larger value means a higher sensitivity.

55 RO S- I-a (for comparison) TABLE 1 N-methyl-p-aminophenol sulfate 3.1 fin-cfimczkc Sodium sulfite 45 Hydroquinone 12 Sodium carbonate (anhydrous) 67.5 Potassium bromide 1.9 N Water to 1000 ml. 4

STRUCTURAL FORMULA OF DYE USED STRUCTURAY FORMULA OF COMPARISON SENSITIZING DYE USED 1 I 1 2 I-b (for comparison) (I) Development minutes G. p-Methylaminophenol 1 8 Cam 8 Hydroquinone 3 Sodium sulfite (anhydrous) 13 C=CH 5 Potassium bromide 1 I Sodium carbonate (anhydrous) 26 N Water to 1000 ml. (CH1)ISO3H(CIH5)IN (2) Water washing-5 minutes (3) Fixing5 minutes G. Crystalline sodium thiosulfate 200 (CHmSO Potassium metabisulfite 20 Water to 1000 ml. TABLE 2 (4) Water washing-5 minutes Re ative sensitivity g) (5) Hardening5 minutes Red Blue 30% aqueous solution of formaldehyde ml 100 sensitizing dye sensitivity sensitivity Sodium bicarbonate .g 2

1. 14 M2 Water to 1000 ml. 1.04 0.50 (6) Water washing-5 minutes {13 3 :2 (7) Dye bleaching-15 minutes 1.10 0. s2 Thiourea g 28 k g; 81;, Potassium bromide g 18 0.80 0.55 2-amino-3-hydroxyphenazine -mg 3 Concentrated hydrochloric acid ..ml 200 XQM L Water to 1000 ml. E 2 (8) Water washing5 minutes A sensitizing dye or a sensitizing dye and super-sensi- (9) Bleaching fixing l() minutes 3 tizer were added to a silver iodobromide emulsion (iodine Tetrasodium ethylenediaminetetmacetate 25 7.0 mol percent) and stirred adequately for 20 minutes. Anhydrous sodium carbonate 24 Then, 19.0 g./g.-niol silver halide of a dye represented F rric hl rid 15 by the following structural formula was added thereto, Sodium sulfite (anhydrous) 13 stirred adequately, mixed with an ordinary coating aid Sodium thiosulfite (crystalline) 200 and hardener and coated onto a baryta paper. Water to 800 ml.

The results obtained are shown in Table 3. (10) Water washing-20 minutes Structural Formula of Dye Used e e F -Q N=NN=N 1 1B:

H035 S 03H H O3H- S 0311 Structural Formula of Supersensitizer Used N N HNj fiHN-CH=CH-ONHI INK I 03m NaOaS S O Na S O Na l Mg./g.-mo1 silver halide.

What is claimed is:

1. A light-sensitive silver halide emulsion containing an azo dye capable of being bleached out in the silver dye bleaching process and at least one sensitizing dye having the following general Formula I wherein R is selected from the group consisting of an alkyl group, a hydroxyalkyl group, an acetoxyalkyl group, a sulfatoalkyl group, a carboxyalkyl group, a vinylalkyl group, a carboxyaralkyl group, a sulfoaralkyl group, a sulfoalkyl group, an aralkyl group, and an aryl group, wherein R and R each is selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group, an acetoxyalkyl group, a sulfatoalkyl group, a carboxyaralkyl group, an allyl group, carboxyalkyl group, sulfoalkyl group, an aralkyl group, a sulfoaralkyl group, and an aryl group, wherein R is selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group, wherein Z is a nonmetallic atom group necessary to complete a 5- or 6- membered heterocyclic ring ordinarily employed in cyanine dyes, wherein d represents 0, 1 or 2 and n represents 1 or 2.

2. The light-sensitive silver halide emulsion as claimed in claim 1, wherein R R and R are selected from the group consisting of methyl, ethyl, propyl, B-hydroxyethyl, fl-acetovyethyl, sulfatoethyl, carboxymethyl, p-carboxyethyl, 'y-carboxypropyl, fi-sulfoethyl, 'y-sulfopropyl, 6- sulfobutyl, vinylmethyl, benzyl, phenethyl, p-carboxybenzyl, p-sulfophenethyl and phenyl groups; and the heterocyclic ring containing Z is selected from the group consisting of the thiazoles, benzothiazoles, naphthothiazoles, oxazoles, benzoxazoles, naphthothiazoles, selenazoles, benzoselenazoles, naphthoselenazoles, thiazolines, Z-quinolines, 4-quinolines, benzimidazoles, 3,3'-dialkyl indolenines, Z-pyridines and 4-pyridines.

3. A supersensitized photographic emulsion wherein the light-sensitive silver halide emulsion of claim 1 contains additionally at least one compound having the following Formula II.

wherein Y is selected from the group consisting of =CH and =N, wherein R R R and R each is selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryloxyl group,

phenoxyl group, a toloxyl group, a sulfophenoxyl group, a halogen atom, a heterocyclic nucleus, an :alkylthio group, a heterocyclicthio group, an arylthio group, an amino group, an alkylamino group, a sulfoarylamino group, a carboxyaryl amino group, an arylamino group, a hydroxy arylamino group, an anisilamino group, a toluidino group, an anilino group, a heterocyclic amino group and an aryl group, and wherein A is selected from the group consisting of A and A wherein A is selected from the group consisting of l l I $0 M M035 $0 M I l and $0 M $0 M wherein A is selected from the group consisting of and and wherein at least one of R R R and R contains a substituent containing a SO M group when A is A 4. The supersensitized photographic emulsion as claimed in claim 3, wherein said toloxyl group is an otoloxyl and said sulfophenoxyl group is a p-sulfophenoxyl group, wherein the heterocyclic nucleus is selected from the group consisting of a morpholinyl and a piperidyl group; wherein the heterocyclicthio group is a benzothiazylthio group; wherein said hydroxy arylamino group is selected from the group consisting of a fi-hydroxyethylamino, and a di-fl-hydroxyethylamino, and said alkylamino is a ,B-sulfoethylamino group; wherein said sulfoarylamino group is selected from the group consisting of a o-sulfoaniliuo, a m-sulfoanilino, and a p-sulfoanilino group, said anisilamino is selected from the group consisting of an o-anisilamino a m-anisilamino, and a panisilamino group, said toluidino is selected from the group consisting of an o-toluidino, a rn-toluidino, and a p-toluidino group, said anilino group is selected from the group consisting of an o-carboxyanilino, a m-carboxyanilino, a p-carboxyanilino, and a hydroxyanilino group, said aryl group is selected from the group consisting of a naphthylamino and a sulfonaphthylamino group; and wherein the heterocyclicamino group is selected from the group consisting of a 2-benzothiazoleamino and a 2-pyridylamino group.

5. The supersensitized photographic emulsion wherein the light-sensitive silver halide emulsion of claim 1,

3,682,640 16 contains additionally at least one of compound having densation unit of from 2 to 5 and a molecular weight of the following general Formula III from- 300 to 800.

10. The light-sensitive silver halide emulsion as claimed in claim 1, wherein the dye capable of being bleached out in the silver dye bleaching process is Q-oonn on 011.0 OH

I I wherein R is selected from the group consisting of an N=NN=N acylarnino group and a sulfo group, wherein R is an 10 I acylamino group and wherein R is selected from the 11 3s a H; 3 group consisting of a hydrogen atom and a sulfo group; and wherein said compound has at least one sulfo group. 11. The light-sensitive silver halide emulsion as 6. The supersensitized photographic emulsion as claimed in claim 1, wherein the dye capable of being claimed in claim 5, wherein the acylamino group is 15 bleached out in the silver dye bleaching process is Q-OOHN OH OH i HCOQ selected from the group consisting of an acetamide, a 12. The light-sensitive silver halide emulsion as sulfobenzarnide, a 4-rnethoxy-3-sulfobenzamide, a 2- claimed in claim 1, wherein the dye capable of being ethoxybenzarnide, a 2,4-diethoxybenzamide, a p-toluylbleached out in the silver dye bleaching process is amino, a Z-naphthylamino, a 2,4-dimethoxybenzamide, a C0NH 0H HsC-O 0H 2-phenylbenzamide and a 2-thienylbenzamide group. I I I 7. The supersensitized photographic emulsion wherein N=N- N=N the light-sensitive silver halide emulsion of claim 1, con- L tains additionally a condensate of a polyhydroxybenzene 038- 803K a having from 1 to 3 hydroxyl groups on the benzene amino, a 4-methyl-2-1nethoxybenzamide, a l-naphthylnucleus and formaldehyde. H03

Thc supefsensitiled Photographic emulsion as 13. The light-sensitive silver halide emulsion as claimed in claim 7, wherein the condensate is a novolak l i d i lai 1, wherein the dye capable of being yp condensate of formaldehyde a d a p y y ybleached out in the silver dye bleaching process is benzene selected from the group consisting of compounds having the following general formula: OH H304) OH (0B).. 1 (0H). (0H 0H I l I I Q Q and Q H038 SOzH I Hogs X2 CH3 0-CHa V 0R1: 8 zRu i) n (Iva) (IVb) (IVc) (IVd) 14. A photographic light'sensitive element comprising wherein R and R each is selected from the group a supPort thereon. least layer cqntainlng the lightconsisting of NH2, sensitive silver hahde emulsion as claimed in claim 1. '-'N(R14)g, and 'NHNHR14, wherein R14 is selected from the group consisting of an alkyl group References Cited having from 1 to 8 carbon atoms, an aryl group and UNITED STATES PATENTS an aral'kyl group, wherein M i selected from the group 2,652,330 9/1953 Carroll 96 123 consisting of an alkali metal and an alkaline earth metal, 3,401,404 9/1968 Seidel et ah wherein X is selected from the group consisting of 3,565,630 2/1971 Millikan et a1 OH and a halogen atom, wherein X: is a halogen atom, wherein n n n and n each represents 1, 2, 3 except J TRAVIS BROWN, P i E i that n and n are equal to 3 simultaneously.

9. The supersensitized photographic emulsion as US. Cl. X.R. claimed in claim 8, wherein the condensate has a con- 96-123