GB1564349A - Light-sensitive silver halide photographic materials - Google Patents

Description

(54) LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC MATERIALS (71) We, KONISHIROKU PHOTO INDUSTRY CO. LTD., a Corporation organized and existing under the Laws of Japan, of 1-10, 3-Chome, Nihonbashi-Muro-Machi, Chuo-ku, Tokyo, Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to a novel light-sensitive silver halide photographic material. More particularly, the invention is concerned with a light-sensitive silver halide photographic material comprising a photographic couplers capable of giving an excellent neutral black dye image.

In an ordinary system of black-and-white photography, a latent image is formed in a light-sensitive silver halide photographic material by exposing said photographic material to light, the latent image thus formed is developed by means of a developer containing a common black-and-white developing agent (such agent is well known to the industry concerned, for example, as Metol, l-phenyl-3pyrazolidone, pyrogallol or hydroquinone) and metallic silver thereby formed on the exposed portion of the photographic material is utilized as a photographic image. In this black-and-white photography, the developing agent thereby oxidized is quickly removed outside of the system. Then if the thus oxidized developing agent is utilized as a material capable of forming a black dye image, there can be expected further an improvement in density or in speed.

For such purpose as mentioned above, various methods have heretofore been proposed. For instance, West German Patent Nos. 492,518 and 537,923 disclose a process for forming black dye images by carrying out color develpment by use of a mixture of such couplers as yellow, magenta and cyan, which can be used in the common color photography. In this process, however, it is difficult to obtain neutral black dye images for all density region for such reasons that these three couplers are different from one another in their rate of coupling with an oxidized color developing agent, for example, a paraphenylenediamine type color developing agent or p-aminophenol type color developing agent. Further, West German Patent No. 1,158,836 discloses a process for forming black dye images by use of 4-aminopyrazolinobenzimidazole as a developing agent, wherein the oxidation product of the developing agent is condensed with an active methylene compound. According to this process, however, it is practically difficult to obtain a substantially neutral black dye image having a sufficient density.

Furthermore, processes for forming black dye images by means of developer couplers are disclosed, for example British Patent No. 1,210,417 and U.S. Patent No. 3,615,509. The processes are intended to obtain a substantially black dye image having a sufficiently high density by developing a silver halide emulsion by use of a developing agent which has in the molecule a coupler moietv consisting of Dhenol and developing agent moiety consisting of p-aminophenol, thereby forming a polymerized dye in the exposed portion and then subjecting the polymerized dye to chelation by treatment with an alkali bath or copper chelate bath.

In these processes, however, because of the use of the so-called developer coupler, the processes according to these methods mainly involve, as a natural consequence, the so-called Kodachrome (Registered Trade Mark) type process.

Accordingly, there remain such problems as stability of the processing solution and some problems caused by the use of copper chelate, and also there remains such problems that stability of the image is not sufficient.

Still further, U.S. Patent No. 3,674,490 discloses a process for forming quinone type black dye images, according to which the silver image once obtained by the currently practiced black-and-white photographic treatment is allowed to oxidatively couple on the silver image portion with an aromatic hydroxyamino compound, utilizing hydrogen peroxide as a reaction catalyst. In this process, however, in addition to the fact that the process requires additional processing baths, it is difficult to obtain black dye images having a sufficient density under usually employed processing conditions.

The present invention provides a light-sensitive silver halide photographic material comprising a m-amino phenol compound as a coupler capable of reacting with the oxidation product of a primary aromatic amine type color developing agent to form a black dye image wherein the m-amino phenol compound has the general formula,

wherein R, and R2, which may be the same or different, each represents a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, aralkyl, aryl, or heterocyclic radical, or R, and R2, together with the nitrogen atom to which they are attached, represent a heterocyclic radical, neither R, nor R2 containing any moiety capable of development, R3 and R4,which can be the same or different, each represents a hydrogen or halogen atom or a monovalent organic radical; and X and Y, which can be the same or different, each represents a hydrogen atom, halogen atom or a monovalent organic radical, at least one of X and Y representing a hydrogen or halogen atom or a radical capable of splitting off on reaction with an oxidized primary aromatic amine color developing agent.

In the above-mentioned atomic group, R, and R2 respectively represent a hydrogen atom or a group selected from the group consisting of alkyl, alkenyl (e.g. methyl, ethyl, t-butyl, octyl, decyl, dodecyl, octadecyl, octadecenyl, terpenyl and norbornyl), substituted alkyl, substituted alkenyl (e.g. the above-mentioned alkyl or alkenyl in which at least one hydrogen atom has been substituted with such group as hydroxy, carboxyl or sulfonic acid, or the above-mentioned alkyl or alkenyl in which the skeletal carbon has been substituted with ether bond, thioether bond or the bond

and also including those in which the hydrogen atoms have been substituted with such groups as hydroxy or carboxyl, or those in which the hydrogen atoms have been substituted either directly with other alkyl, alkenyl, aryl or heterocyclic radical or through -0-,

-CONH-, -NHC, -S-, -SO2NH- or -NHSO2, for example, such group as 4-lauroylamido-phenethyl, m-pentadecylphenoxyethyl or cr-dodecylcarb- amoyl-ethyl), substituted or unsubstituted aryl and substituted or unsubstituted heterocyclic radical (e.g. 4-(2,4-di-tert-amylphenoxyacetamido)phenyl and the like), and R1 and R2 may be the same or different.

It is desirable that preferably at least one ofthe substituents has a group having a diffusion-preventing property in the photographic layer, for example, an alkyl group of 8 or more carbon atoms or an aralkyl group having alkyl of 4 or more carbon atoms. At least one of X and Y is the so-called split-off group which can readily be split on the coupling reaction with an oxidation product of a primary amine type color developing agent.

Representative examples of the m-aminophenyl type coupler used in the present invention are shown below, but the black image forming couplers usable in the invention are not limited only to those as exemplified.

(1) N-Decyl-m-aminophenyl (2) N-Dodecyl-m-aminophenyl (3) N-Octadecenyl-m-aminophenol (4) N-Octadecyl-m-aminophenol (5) 3-(p-Dodecylbenzylamino)phenol (6) 3-[4-(2,4-di-tert-Aminophenoxyacetamido)anilino]phenol (7) 3-{[α-(Hexadecyloxycarbonyl)ethyl]amino}phenol (8) N-[α-(Dodecylcarbamoyl)ethyl]-m-aminophenol (9) N-[ss-(Dodecylcarbamoyl)ethyl]-m-aminophenol (10) N-{ss-[2-Chloro-5-(2,4-di-tert-amylphenoxybutylamido)phenylcarbamoyl] ethyll-m-aminophenol (11) N-(4-Laurylamidophenethyl)-m-aminophenol (12) N-{4-[α-(2,4-di-tert-Amylphenoxy)propionamido]phenethyl}-m-amino- phenol (13) 4-Chloro-N-octadecyl-m-aminophenol (14) 4-Sulfo-N-octadecyl-m-aminophenol (15) N,N-Didodecyl-m-aminophenol (16) N-Methyl-N-octadecyl-m-aminophenol (17) N-{α-Carboxytridecyl}-m-aminophenol (18) N-{ss-[2-Sulfo-5-(N-methyl-N-octadecylamino)phenylcarbomyl]ethyl}-m aminophenol (19) 2-Benzoylamido-5-[p-(m-pentadecylphenoxy)ethylamino]phenol (20) 6-Chloro-N-octadecyl-m-aminophenol (21) 5-Ethoxy-3-hexadecyl-m-aminophenol (22) 5-Dodecyloxy-m-ethylaminophenol (23) 5-Hydroxy-3-{N-[α-hexadecyloxycarbonylethyl]amino}-phenol (24) 5-Benzoylamido-3-{α-(dodecylcarbymoyl)ethylamido}phenol (25) 2-Acetamide-3-{ a-(hexadecyloxycarbonyl)ethylamino phenol (26) 2-Benzenesulfonylamide-3-dodecylaminophenol (27) 2-Palmiticacidamido-3-N-ethylaminophenol (28) 2,5-dimethyl-3-N-octadecylaminophenol (29) 2-Hydroxy-4-chloro-5-N-octadecylaminophenol (30) 2,4,6-Trichloro-3-N-octadecylaminophenol (31) 2,4-Disulfo-5-N-hexadecylaminophenol (32) 4-Phenylthio-3-N-octadecylaminophenol (33) 6-Phenylthio-3-N-octadecylaminophenol (34) 2,4-Diphenylthio-5-{4-(2,4-di-tert-amylphenoxyacetamido)anilino}phenol (35) 2-ChloroA-phenylthio-5- ((-(dodecylcarbamoyl)ethyl1amino]phenol (36) 4-(1-Phenyltetrazolium-5-thio)-3-@ss-(m-pentadecylphenoxy)ethylamino]- phenol (37) 2-Mercapto-5-N-octadecylaminophenol (38) 4-Phenylseleno-3-N-octadecylaminophenol (39) 4-Ethoxy-3-N-octadecylaminophenol (40) 2-Chloroethoxy-5-N-octadecylaminophenol (41) 2-ChloroA-(iso-propylcarbamoylmethoxy)-5-N-octadecylaminophenol (42) 4-(iso-Propylcarbamoylmethoxy)-3-N-octadecylaminophenol (43) 2,4-Dichloro-3-methoxy-5-N-hexadecylaminophenol (44) 4-Butoxycarbonylmethoxy-3-1 [a-(hexadecyloxycarbonyl)ethyl]amino I- phenol (45) 4-(p-Carboxyphenoxy)-3-( [ac(p-dodecylphenylcarbamoyl)ethyl] amino 1- phenol (46) 4-Benzoyloxy-3-N-dodecylaminophenol (47) 4-Acetoxy-3-[(O-hexadecyloxyphenylcarbamoyl)methylamino]phenol (48) 4-Perfluoropropyl-3-[(O-hexadecyloxyphenylcarbamoyl)methylamino]- phenol (49) 2-Phenoxy-5N-octadecylaminophenol (50) 4-Benzenesulfonyloxy-3-N-octadecylaminophenol (51) 2-Chloro-4-benzenesulfonyloxy-5-N-octadecylaminophenol (52) 2-Succimido-5-N-hexadecylaminophenol (53) 4-Phthalimido-5-N-hexadecylaminophenol (54) 4-(p-Benzenesulfonylphenoxy)-3-N-octadecylaminophenol (55) 4-Phenylsulfonylamido-3-N-octadecylaminophenol (56) 4-Methanesulfonylamido-3-N-octadecylaminophenol (57) 2-Phenylsulfonylamido-4-chloro-3-N-octadecylaminophenol (58) 4-Trifluoroacetamido-3-N-dodecylaminophenol (59) 2-Amino-5-N-hexadecylaminophenol (60) 2-Anilino-5-N-octadecylaminophenol (61) 2-Ethylamino-5-N-hexadecylaminophenol (62) 4-Phenylsulfonyl-3-N-octadecylaminophenol (63) 2-Octadecylsuccimido-5-y-sulfopropylaminophenol sodium salt (64) 4-Dodecylcarbamoylmethoxy-3-N-ethylaminophenol (65) 4-Dodecylcarbamoylmethoxy-3-N-(w-sulfopropylamino)phenol sodium salt (66) 4-(p-Dodecylbenzenesulfonyloxy)-3-N-(w-sulfopropylamino)phenol sodium salt (67) 2-Chloro-4-(o-dodecylphenyl)carbamoylmethoxy-5-N-carboxymethylamino- phenol (68) 2-(m-Palmiticacidamidophenylsulfonamido)-5-(N-methoxycarbonylmethyl- amino)phenol (69) 4-[2-Chloro-{5- [(dodecyloxycarbonyl)ethoxy1c.arbonyl1phenylazo] -3-(N-};- sulfopropylamino)phenol (70) 4-Dodecylcarbamoylmethoxy-3-aminophenol (71) 4-(p-Dodecylbenzensulfonyloxy)-3-N-ethylaminophenol (72) 4-p-Methoxyphenylcarbamoyloxy-3-N-octadecylaminophenol (73) N-[/3-(Dodecylcarbamoyl)ethyll-m-aminophenol (74) N-(4-Lauroylamidophenethyl)-m-aminophenol (75) 4-Chloro-3-(N,N-di-n-octadecylamino)phenol (76) 4-{(3-Lauroylamidophenol)carbamoyloxy}-3-(N-y-sulfopropyl)aminophenol (77) 4-{(3-Lauroylamidophenyl)carbamoylmethoxyl-m-aminophenol (78) 4-(dodecylbenzensulfonyloxy)-m-aminophenol (79) 4-(Dodecylbenzensulfonylamino)-m-aminophenol (80) 4-(Dodecylcarbamoylmethoxy)-m-aminopheno (81) 4-(Dodecylcarbamoylmethoxy)-3-(N-carboxymethyl)aminophenol (82) 4-(Dodecylcarbamoylmethoxy)-3-(ethyloxycarbonylmethyl)-aminophenol Concretely illustrated below are processes for the synthesis of representative couplers of the m-aminophenol type which are used in the present invention.

Synthesis Example 1.

Preparation of 3-(p-dodecylbenzylamino)phenol [Exemplified compound (5)] To 25 grams of m-aminophenol heated under reflux in 200 ml of alcohol was added dropwise over a period of 3 hours a solution of 30 g of p-dodecylbenzyl chloride in 100 ml of alcohol. After completion of the addition, the refluxing was continued for an additional 3 hours, the alcohol was then distilled off, the concentrate was dissolved in 300 cc of benzene, and the solution was washed twice with 300 cc of 10% hydrochloric acid. The benzene phase was washed with water, dried over sodium sulfate, and then the benzene was distilled off, whereby an oily brown liquid was obtained. The yield was 30 g, and the boiling point was 280"C.

Synthesis Example 2.

Preparation of N-octadecyl-m-aminophenol [Exemplified compound (4)] To 25 grams of m-aminophenol heated under reflux in 200 ml of alcohol was added dropwise over a period of 3 hours a solution of 33 g of octadecyl bromide in 100 ml of alcohol. After completion of the addition, the refluxing was continued for an additional 3 hours, the alcohol was then distilled off, the concentrate was dissolved in 300 cc of ethyl acetate, and the solution was washed twice with 300 cc of 10% hydrochloric acid. The ethyl acetate phase was washed with water, dried over sodium sulfate, and then the ethyl acetate was distilled off. Recrystallization from n-hexane gave white powdery crystals. The yield was 20 g and the melting point was 66 68 C.

Synthesis Example 3.

Preparation of 3-( [rr-(hexadecyloxycarbonyl)ethyl] aminoiphenol [Exemplified compound (7)] To 25 g of m-aminophenol while heating under reflux in 200 ml of methanol was added dropwise over a period of 3 hours a solution of 37 g of hexadecyl a- bromopropionate in 100 ml of methanol. After completion of the addition, the refluxing was continued for an additional 3 hours, the methanol was then distilled off, the concentrate was dissolved in 300 cc of ethyl acetate, and the solution was washed twice with 300 cc of 10% hydrochloric acid. The ethyl acetate phase was washed with water, dried over sodium sulfate and was then concentrated. The concentrate was cooled with ice, whereby pale yellow crystals were deposited. The yield was 25 g and the melting point was 35 40 C.

Synthesis Example 4.

Preparation of N- [/3-(dodecylcarbamoyl)ethyl]-m-aminophenol [Exemplified compound (9)] (a) Preparation of N-dodecyl-p-bromoethylamide To a solution of 34 g of p-bromopropionic acid chloride in 200 ml of benzene was added 15 g of anhydrous potassium carbonate, and the mixture was heated under reflux. To the refluxing mixture was added at a time 37 g of dodecylamine, and the refluxing was continued for an additional 4 hours. After completion of the refluxing, the reaction liquid was washed with water, and the benzene phase was dried over sodium sulfate and then concentrated. The concentrate was charged with n-hexane, whereby white powdery crystals were deposited, and the crystals were recrystallized from methanol. The yield was 35 g and the melting point was 740-760C.

(b) Preparation of N-[B-(dodecylcarbamoyl)ethyl]-m-aminophenol To 25 g of aminophenol heated under reflux in 200 ml of butanol was added dropwise over a period of 3 hours a solution of 32 g of N-dodecyl-p-bromoethylamide in 100 ml of butanol. After continuing the refluxing for an additional 3 hours, the butanol phase was washed twice with 300 cc of 10% hydrochloric acid, washed thoroughly with water, and then concentrated to obtain a brown oily liquid. The oily liquid was then cooled with ice, whereby crystals were deposited. The yield was 18 g and the melting point was below 40"C.

Synthesis Example 5.

Preparation of 3-[4-(2,4-di-tert-amylphenoxyacetamido)anilino]phenol [Exemplified compound (6)] (a) Preparation of 3-(4-nitroanilino)phenol A mixture of 32.4 g (0.3 mol) of m-aminophenol and p-nitrophlorobenzene (0.15 mol) was boiled under reflux for 10 days in 400 ml of water and then poured into dilute hydrochloric acid, followed by extraction with ethyl acetate, washing 2 to 3 times with dilute hydrochloric acid and then concentrated. The deposited crystals were washed with hot benzene, cooled and then filtered. The yield was 26 g and the melting point was l580-l600C.

(b) Preparation of 3-(4-aminoanilino)phenol 20 Grams of 3-(4-nitroanilino)phenol was reduced under ordinary pressure in alcohol by the use of a palladium-carbon catalyst. After removing the catalyst by filtration, the alcohol was distilled off under reduced pressure and the residual solids were washed with benzene. The yield was 14 g, and melting point was l460-l490C.

(c) Preparation of 3-[4-(2,4-di-tert-amylphenoxyacetamido)anilino]phenol To a solution of 11 g (0.055 mol) of 3-(4-aminoanilino)phenol in glacial acetic acid was added 4.6 g of anhydrous sodium acetate. During agitation at room temperature, the mixture was charged with 17.1 g (0.055 mol) of 2,4-di-tert-amyl- phenoxyacetyl chloride at a temperature below 30"C. After continuing the agitation for an additional 30 minutes at room temperature, the mixture was poured into iced water, and the deposited crystals were filtered, followed by recrystallization with methanol. The yield was 20 g and the melting point was l500-l520C.

Synthesis Example 6.

Preparation of N-(4-lauroylamidophenethyl)-m-aminophenol [Exemplified compound (11)] (a) Preparation of 4-lauroylamidophenethyl bromide A mixture of 8 g (0.04 mol) of 4-aminophenethyl bromide, 9 g of lauroyl chloride and 5 g of dimethylaniline was boiled undeireflux for 30 minutes in 150 ml of acetonitrile. Subsequently, the acetonitrile was removed by distillation under reduced pressure, and the residue was then extracted with ethyl acetate, followed by washing with dilute hydrochloric acid. After drying over sodium sulfate, the ethyl acetate layer was concentrated under reduced pressure and the residual oily product was recrystallized from hexane. The yield was 12 g and melting point was 69" -70"C.

(b) Preparation of N-(4-lauroylamidophenethyl)-m-aminophenol A rnixture of 10 g (0.027 mol) of 4-lauroylphenethyl bromide and 6 g of m aminophenol was boiled under reflux for 3 days in alcohol.. After concentration of the alcohol, the concentrate was dissolved in ethyl acetate and the solution was washed with about 5% dilute hydrochloric acid, followed by water-washing.

Subsequently, the ethyl acetate layer was dried over sodium sulfate, concentrated under reduced pressure and the residual oily product was recrystallized from benzene. The yield was 6 g and the melting point was 111"--112"C.

Synthesis Example 7.

Preparation of 4-chloro-N-octadecyl-m-aminophenol [Exemplified compound (13)] According to the process described in Chemische Berichte, 26, 90; Chemische Berichte, 27, 195 or Beilstein, 6, (first edition), 239, 3-amino-4-chlorophenol was prepared to be used in the following synthesis: In 800 ml of alcohol, 160 g of 3-amino-4-chlorophenol was heated under reflux for 30 hours with 187 g of octadecylbromide. Thereafter, the mixture was concentrated and 1 litre of ethyl acetate was added thereto. Insoluble substance (3amino-4-chlorophenol hydrochloride) was eliminated by filtration and the ethyl acetate layer was washed three times with 1 litre of 5% hydrochloric acid and twice with 5% aqueous sodium bicarbonate solution. After being dried over sodium sulfate, the ethyl acetate layer was concentrated and the residual oil was recrystallized from 600 ml of hexane. The yield was 158 g and the melting point was 570-590C.

Synthesis Example 8.

Preparation of 2,4,6-trichloro-3-(octadecylamino)phenol [Exemplified compound (30)] To a solution of 360 g of N-octadecyl-m-aminophenol in 1 litre of chloroform were added 450 g of sulfuryl chloride at room temperature while maintaining the temperature not exceeding over 20"C. After completion of the addition, the temperature was elevated to 400C and stirring was continued for 30 minutes.

Chloroform was distilled off under reduced pressure and then extraction with 2 litres of ethyl acetate was effected. The ethyl acetate layer was washed with 5% aqueous sodium bicarbonate solution, dried over sodium sulfate and then concentrated. Recrystallization from 300 ml of hexane gave the title compound melting at 470--490C in the yield of 200 g.

Synthesis Example 9.

Preparation of 4-benzenesulfonylamido-3-(N-octadecylamino)-phenol [Exemplified compound (55)] According to the process described in Chemische Berichte, 26, 90 or Chemische Berichte, 27, 195, 3-nitro-4-aminophenol was prepared to be used in the following synthesis: (I) Preparation of l-benzenesulfonyloxy-4-benzenesulfonylamido-3-nitro- benzene To a solution of 300 g of 3-nitro-4-aminophenol in pyridine were added 870 g of benzenesulfonium chloride and the solution was stirred at 500--600C for one hour. The solution was poured into diluted hydrochloric acid/ice. The resulting crystal was washed with aqueous sodium bicarbonate solution and dried. The yield was 758 g.

(2) Preparation of 4-benzenesulfonylamido-3-nitrophenol A solution of 536 g of 1 -benzen esulfonyloxy4-b enzenesulfo nylamido-3-nitro- benzene in methanol was heated under reflux. To the solution was added a solution of 310 g of potassium hydroxide in water and the solution was heated under reflux for further one hour. The reaction solution was poured into diluted hydrochloric acid/ice and extracted with ethyl acetate. After neutralization with sodium bicarbonate, the ethyl acetate layer was washed with water, dried over sodium sulfate and distilled to remove ethyl acetate. The residue was recrystallized from benzene to afford reddish brown crystal melting at l680-l700C in the yield of 274 g.

(3) Preparation of 4-benzenesulfonylamido-3-aminophenol To a mixture of 260 g of 4-benzenesulfonylamido-3-nitrophenol, 700 cc of glacial acetic acid and 100 cc of water were added 320 g reduced iron and the mixture was stirred vigorously at 700--800C. After I hour, the mixture was poured into ice water and extracted with ethyl acetate. The extract was neutralized with sodium bicarbonate and the iron hydroxide precipitate was filtered. The ethyl acetate layer was washed with water, dried over sodium sulfate and distilled to remove ethyl acetate. The residue was recrystallized from ethyl acetate-benzene mixture to afford white powdery crystal melting at l770-l800C in the yield of 186 g.

(4) Preparation of 4-benzenesulfonylamido-3-(octadecylamino)phenol A solution of 164 g of 4-benzenesulfonylamido-3-aminophenol in ethanol was heated under reflux and 68 g of octadecyl bromide were added to the solution. The resulting solution was further heated under reflux for 50 hours. Ethanol was removed by distillation and the concentrated solution was poured into water and adjusted to pH 3--4 with hydrochloric acid. The solution was extracted with ethyl acetate and ethyl acetate was distilled off. Thereafter, the residue was recrystallized from n-hexane. The yield was 120 g and the melting point was 113"--115"C.

Synthesis Example 10.

Preparation of 4- or 6-phenylthio-3-octadecylaminophenol [Exemplified compound (32)] A solution of 370 g of N-octadecyl-m-aminophenol in 1.5 litres of carbon tetrachloride was cooled below 10"C and to this solution was added under stirring a solution of phenylsulfenylchloride which had been prepared by dissolving 110 g of phenyl mercaptan in 200 ml of carbon tetrachloride and passing therethrough chlorine gas for 15 minutes, while maintaining the temperature below 10 C.

Stirring was continued for 30 minutes and thereafter the solution was concentrated and extracted with 1 litre of ethyl acetate. The extract was washed twice with 500 cc of 5% sodium bicarbonate and dried over sodium sulfate. After removal of sodium sulfate, the ethyl acetate layer was concentrated, leaving oil which was crystallized from 1.5 litres of methanol-ethyl acetate mixed solvent (methanol:ethyl acetate = 5:1). The yield was 143 g and the melting point was 50"--51"C.

Synthesis Example 11.

According to the process described in Chemische Berichte, 49, 1401, 3-nitro-4benzoyloxyphenol was prepared and used for the syntheses of 4-(dodecylcarbamoylmethoxy)-3-aminophenol [Exemplified compound (58)] and sodium salt of 4-(dodecylcarbamoylmethoxy)-3-(y-sulfopropylamino)phenol [Exemplified compound (53)] in the manner as disclosed below.

(1) Preparation of l-benzoyloxy-3-nitro-4-(dodecylcarbamoylmethoxy)- benzene In 500 ml of DMF, 195 g of 3-nitro-4-benzoyloxyphenol were stirred with 240 g of N-dodecyl-bromoacetamide and 107 g of anhydrous potassium carbonate for 1 hour at 850--900C. The mixture was poured into 3 litres of ice water to which 100 ml of concentrated hydrochloric acid had been added. After extraction with 3 litres of ethyl acetate, the extract was washed twice with 1 litre of saturated aqueous sodium chloride solution. The ethyl acetate layer was dried over sodium sulfate and then concentrated. The residual crystal was recrystallized from 9 litres of methanol.

The yield was 452 g and the melting point was 110"--111"C.

(2) Preparation of 3-nitro-4-(dodecylcarbamoylmethoxy)phenol In 1 litre of methanol were suspended 275 g of l-benzoyloxy-3-nitro-4- (dodecylcarbamoylmethoxy)benzene and 50 g of sodium hydroxide were added to the suspension at room temperature under stirring. After stirring for 30 minutes, the reaction solution was poured into 3 litres of ice water to which 150 ml of concentrated hydrochloric acid had been added. Extraction with 3 litres of ethyl acetate was effected and the ethyl acetate layer was washed three times with 3 litres of 5% aqueous sodium bicarbonate solution, dried over sodium sulfate and concentrated. The residual crystal was washed with acetonitrile. The yield was 203 g and the melting point was 150 151 C (acetonitrile).

(3) Preparation of 3-amino-4-(dodecylcarbamoylmethoxy)phenol [Exemplified compound (70)] In an autoclave, 190 g of 3-nitro-4-(dodecylcarbamoylmethoxy)phenol were subjected to pressure reduction (50 kg/cm2) with 500 ml of alcohol and 20 g of palladium/carbon. After the palladium/carbon catalyst was removed, concentration was effected and the residual oil was crystallized from 800 ml of acetonitrile. The yield was 120 g and the melting point was 780--80"C.

(4) Preparation of sodium salt of 3-(y-sulfopropylamino)-4-(dodecylcar bamoylmethoxy)-phenol [Exemplified compound (53)] In 300 ml of alcohol, 100 g of 3-amino-4-(dodecylcarbamoylmethoxy)-phenol and 40 g of propanesultone were stirred at room temperature for 30 hours. Said alcohol was distilled off under reduced pressure and the residual oil was dissolved in 500 ml of 5% aqueous sodium bicarbonate solution. To the resulting solution was added 300 ml of saturated aqueous sodium chloride solution and the solution was allowed to stand overnight. After neutralization with hydrochloric acid, the resulting crystal was filtered. The yield was 80 g and the melting point was above 2000C with decomposition.

Synthesis Example 12.

Preparation of 4-ethoxy-3-(N-octadecylamino)-phenol [Exemplified compound (39)] Similarly to Synthesis Example 11, 3-amino-4-et

Synthesis Example 13.

Preparation of sodium salt of 2-(octadecylsuccinimido)-5-(y-sulfopropylamino)phenol [Exemplified compound (63)] (1) Preparation of 2-octadecylsuccinimido-5-nitro-phenol In 3 litres of ethyl acetate and 50 ml of concentrated sulfuric acid were dissolved by heating 150 g of 2-amino-5-nitro-phenol and 350 g of octadecylsuccinate and the resulting solution was boiled under reflux for further 30 hours.

Thereafter, the solution was cooled up to room temperature and washed twice with 2 litres of 10% hydrochloric acid and twice with 10% sodium carbonate solution.

Then, ethyl acetated was distilled off and the residue was recrystallized from hexane to afford light yellow powdery crystal melting at 1150--1200C in the yield of 153 g.

(2) Preparation of 2-octadecylsuccinimido-5-amino-phenol In 2 litres of ethanol were suspended 150 g of 2-octadecylsuccinimido-5-nitrophenol and 7.5 g of palladium/carbon were added to the suspension, which was subjected to catalytic reduction with hydrogen gas at room temperature under normal pressure. After about 10 hours of reaction period of time, palladium/carbon was filtered off and ethanol was removed by distillation. The residue was recrystallized from benzene to give white powdery crystal melting at 850--900C in the yield of 90 g.

(3) Preparation of sodium salt of 2-(octadecylsuccinimido)-5-(y-sulfopropyl amino)-phenol In 1.5 litres of ethanol, were dissolved by heating 90 g of 2-octadecylsuccinimido-5-amino-phenol and 24 g of propanesultone and the resulting solution was boiled under reflux for 35 hours. After completion of the reflux, ethanol was distilled off and 300 ml of 5% sodium bicarbonate solution was added to the concentrated solution. The solution was filtered and 75 ml of saturated sodium chloride solution was added to the filtrate. After neutralization with hydrochloric acid, the resulting crystal was collected by filtration. The yield was 27 g and the crystal was slowly decomposed above 2000 C.

Synthesis Example 14.

Preparation of sodium salt of 4-[2-chloro-(5-[a-(dodecyloxycarbonyl)- ethoxyicarbonyli-phenyl-azo]-3-(}'-sulfopropylamino)-phenol [Exemplified compound (69)] (1) Preparation of 3-(y-sulfopropylamino)-phenol In 3 litres of ethanol were dissolved 330 g of m-amino-phenol and the resulting solution was boiled under reflux and to this solution were added 360 g of propanesultone all together. Continuation of the reflux yielded gradually white powdery crystal. After refluxing for 5 hours, the reaction solution was cooled with ice and the yielded white powdery crystal was collected by filtration and washed several times with ethanol. The yield was 146 g and the melting point was above 250"C.

(2) Preparation of sodium salt of 4-[2-chloro-!5-[a-dodecyloxycarbonyl)- ethoxy]-carbonyll-phenylazo]-3-(y-sulfopropylamino)-phenol To a solution of 204 g of 2-chloro-15-[a-(dodecyloxycarbonyl)-ethoxy]- carbonyli-aniline in 1 litre of acetone was added a mixed solution of 300 ml of concentrated hydrochloric acid and 300 ml of acetone. Further, 6 litres of a mixed solution of acetate:water = 2:1 were added to the solution, which was then cooled with ice up to 0"--5"C and further 4 litres of acetone were added thereto. To the resulting solution, a solution of 51 g of sodium nitrite in 300 ml of water was added in small portions while maintaining the reaction temperature at 00--50C. After completion of the addition, stirring was continued for 2 hours and 9 litres of a mixed solution of acetone:water = 2:1 were added to the solution and further 6 litres of acetone were added. The solution was then stirred for 1 hour, elevating the temperature to 13"C to form a diazo solution. To a solution of 1.2 g of 3-(y-sulfopropylamino)-phenol in 1.8 litres of 10% sodium carbonate solution and 2.3 litres of acetone was added dropwise the diazo solution as prepared above at 00--30C with stirring, while maintaining the reaction temperature at 00--30C over about 2 hours.

After completion of the addition, stirring was continued for further 2 hours and yellowish orange powdery crystal yielded was collected by filtration, washed several times with water and dried.

In the manner above illustrated, various couplers may be synthesized in accordance with the aforementioned synthesis processes. Of the couplers obtained in the manner mentioned above, the exemplified compounds were subjected to elementary analysis to obtain the results as shown below.

Elementary Analytical Value Exemplified Calculated Found compound (%) (%) (I) C 77.06 77.32 H 10.91 10.88 N 5.62 5.73 (2) C 77.92 77.68 H 11.26 11.09 N 5.05 5.15 (3) C 80.15 80.05 H 11.49 11.50 N 3.90 3.96 (4) C 79.71 79.66 H 11.99 14 1-1.82 N 3.87 3.92 (5) C 81.69 81.91 H 10.15 9.99 N 3.81 .3.68 (6) C 75.91 76.76 H 8.07 8.23 N 5.90 5.70 (7) C 74.03 73.97 H 10.69 10.68 N 3.45 3.56 (8) C 72.37 72.37 H 10.41 10.61 N 8.04 7.98 (9) C 72.37 72.50 H 10.41 10.70 N 8.04 8.24 Elementary Analytical Value - (continued) Exemplified Calculated Found compound (%) (%) (10) C 69.12 68.92 H 7.62 7.55 N 6.91 6.68 Cl 5.83 5.81 (11) C 76.05 76.13 H 9.33 9.48 N 6.82 6.55 (12) C 76.94 77.01 H 8.74 8.83 N 5.28 5.08 (13) C 72.78 72.92 H 10.69 10.98 N 3.54 3.31 Cl 8.95 9.20 (14) C 65.27 64.99 H 9.81 9.96 N 3.17 3.21 S 7.26 7.48 (15) C 80.83 80.85 H 12.44 12.58 N 3.14 3.26 (16) C 79.93 80.05 H 12.08 11.94 N 3.73 3.99 (17) C 71.60 71.70 H 9.92 10.01 N 4.18 4.25 (18) C ' 66.09 66.31 H 8.97 9.03 N 6.80 7.01 S 5.19 5.28 Elementary Analytical Value - (continued) Exemplified Calculated Found compound (%) (%) (19) C 77.38 77.26 H 9.02 8.98 N 5.01 4.99 (20) C 70.11 70.36 H 10.08 9.98 N 3.41 3.25 Cl 8.62 8.88 (21) C 76.31 76.63 H 11.50 11.21 N 3.71 3.75 (22) C 74.93 74.68 H 10.71 11.01 N 4.37 4.29 (23) C 71.20 71.53 H 10.30 10.51 N 3.32 3.08 (24) C 71.90 72.18 H 8.85 8.67 N 8.99 9.11 (25) C 70.07 69.79 H 10.04 9.94 N 6.06 6.43 (26) C 66.63 66.90 H 8.40 8.41 N 6.48 6.53 S 7.40 7.11 (27) C 73.78 73.50 H 10.86 11.21 N 7.17 7.30 Elementary Analytical Value - (continued) Exemplified Calculated Found compound (%) (%) (28) C 76.90 76.58 H 11.70 11.49 N 3.45 3.60 (29) C 69.94 70.02 H 10.29 10.34 N 3.40 3.11 Cl 8.60 8.35 (30) C 63.91 63.79 H 8.96 9.11 N 3.11 3.02 Cl 23.58 23.47 (31) C 53.53 53.80 H 7.98 8.19 N 2.84 2.77 S 12.97 12.73 (32) C 76.70 76.67 H 10.10 9.98 N 2.98 2.71 S 6.81 7.12 (33) C 76.70 76.82 H 10.10 9.99 N 2.98 2.99 S 6.81 6.64 (34) C 73.01 73.09 H 6.72 6.44 N 4.06 3.88 S 9.26 9.21 (35) C 65.56 65.51 H 7.96 7.92 N 5.67 5.80 Cl 14.34 14.21 Elementary Analytical Value - (continued) Exemplified Calculated Found compound (%) (%) (36) C 70.20 69.89 H 8.04 8.09 N 11.37 11.31 S 5.20 5.52 (37) C 73.21 73.50 H 11.03 10.88 N 3.56 3.80 S 8.13 8.37 (38) C 69.73 69.68 H 9.19 8.89 N 2.71 2.94 Se 15.28 (39) C 76.96 77.01 H 11.70 11.77 N 3.45 3.51 (40) C 70.98 71.40 H 10.56 10.38 N 3.18 3.16 Cl 8.06 7.89 (41) C 68.12 67.95 H 10.07 10.00 N 5.48 5.17 Cl 6.93 7.22 (42) C 73.04 72.81 H 11.01 10.85 N 5.88 5.94 (43) C 64.01 63.95 H 8.89 . 8.91 N 3.25 3.40 Cl 16.43 16.42 Elementary Analytical Value - (continued) Exemplified Calculated Found compound (%) (%) (44) C 69.48 69.41 H 9.99 10.20 N 2.61 2.94 (45) C 72.81 73.14 H 7.92 8.06 N 5.00 5.17 (46) C 77.28 77.56 H 9.85 9.75 N 2.91 2.77 (47) C 70.27 70.49 H 8.67 8.81 N 5.46 5.74 (48) C 57.64 57.92 H 6.21 6.42 N 4.20 4.01 F 19.95 20.36 (49) C 79.40 79.26 H 10.45 10.32 N 3.09 3.41 (50) C 69.65 69.59 H 9.09 9.13 N 2.71 2.75 S 6.20 6.26 (51) C 65.29 65.27 H 8.33 8.35 N 2.53 2.59 Cl 6.42 6.36 S 5.81 5.80 (52) C 72.92 72.60 H 9.34 9.51 N 6.54 6.19 Elementary Analytical Value - (continued) Exemplified Calculated Found compound (%) (%) (53) C 75.28 75.35 H 8.84 8.51 N 5.85 5.98 (54) C 72.80 73.05 H 8.66 8.60 N 2.36 2.24 S 5.40 5.28 (55) C 69.73 69.58 H 9.36 9.70 N 5.42 5.36 S 6.20 6.22 (56) C 66.04 66.29 H 10.20 10.25 N 6.16 6.47 S 7.04 7.08 (57) C 65.37 65.33 H 8.60 8.89 N 5.08 5.01 S 5.82 5;91 Cl 6.42 6.19 (58) C 61.84 61.87 H 8.04 8.31 N 7.21 7.10 F 14.67 14.50 (59) C 75.81 75.98 H 11.57 11.19 N 8.04 8.04 (60) C 79.59 79.81 H 10.69 10.59 N 6.19 6.08 Elementary Analytical Value - (continued) Exemplified Calculated Found compound (%) (%) (61) C 76.54 76.63 H 11.78 11.94 N 7.44 7.48 (62) C 71.81 71.76 H 9.44 9.54 N 2.79 2.87 S 6.39 6.50 (63) C 61.77 61.96 H 8.53 8.69 N 4.65 4.27 S 5.32 5.40 (64) C 69.80 69.80 H 10.12 10.07 N 7.40 7.44 (65) C 55.85 55.97 H 7.95 7.72 N 5.66 5.60 S 6.48 6.70 (66) C 56.13 56.62 H 6.98 6.81 N 2.42 2.37 S 11.10 11.01 (67) C 62.85 63.27 H 7.35 7.18 N 5.23 5.18 Cl 6.63 6.54 (68) C 63.13 63.40 H 8.03 8.09 N 7.12 7.45 S 5.44 5.20 Elementary Analytical Value - (continued) Exemplified Calculated Found compound (%) (%) (69) C 55.06 55.37 H 6.41 6.37 N 6.21 6.28 S 4.74 4.69 Cl 5.24 4.93 (70) C 68.54 68.36 H 9.78 9.49 N 7.99 8.31 (71) C 67.64 67.29 H 8.51 8.56 N 3.03 3.05 S 6.94 7.30 -(72) C 72.97 72.88 H 9.57 - 9.63 N 5.32 5.60 (73) C 72.37 72.61 H 10.41 10.49 N 8.04 8.08 (74) C 76.81 77.07 H 8.43 8.43 N 6.89 6.67 (75) C 77.78 77.90 H 12.12 12.34 N 2.16 2.12 Cl 5.47 5.24 (76) C 59.66 59.72 H 7.33 7.01 N 7.45 7.59 S 5.69 5.34 Elementary Analytical Value -- (continued) Exemplified Calculated Found compound (%) (%) (77) C 68.54 68.73 H 8.19 8.01 N 9.22 9.26 (78) C 66.48 66.28 H 8.14 8.25 N 3.23 3.30 S 7.39 7.51 (79) C 66.63 66.52 -H 8.39 8.12 N 6.47 6.37 S 7.42 7.25 (80) C 68.54 68.79 H 9.78 9.74 N 7.99 8.17 (81) C 64.68 64.96 H 8.88 8.57 N 6.86 6.64 (82) C 66.03 66.20 H 9.23 9.31 N 6.42 6.47 The m-aminophenol type coupler of the present invention may be incorporated into a silver halide emulsion according to procedure commonly employed heretofore in the art of so-called internal type or Koda-color (Registered Trade Mark) type color photography. For example, the present coupler is dissolved in a high boiling organic solvent having a boiling point of 175"C. or higher, such as tricresyl phosphate or dibutyl phthalate, or in a low boiling organic solvent, such as ethyl acetate or butyl propionate, which solvents may be used either singly or in the form of a solvent mixture thereof. Thereafter, the resulting solution is mixed with an aqueous gelatin solution, the mixture is emulsified by dispersion by means of a high speed rotary mixer or colloid mill, and the emulsified dispersion is then incorporated into the silver halide emulsion, or alternatively said emulsified dispersion is divided, after setting, into small portions from which the low boiling organic solvent is removed by such means as water-washing and the like, and the emulsified dispersion thus treated may be incorporated into the silver halide emulsion. Of the present couplers, those which are alkali-soluble may also be incorporated into the silver halide emulsion by means of a so-called Fissher's dispersion method. Thus, the light-sensitive silver halide photographic material of the present invention contains therein the m-aminopheno type coupler either in its emulsion layer or layer adjacent thereto, and the material may also contain at the same time 2 or more kinds of the m-aminophenol type couplers, and if necessary common yellow, magenta and cyan couplers simultaneously therewith.

When a light-sensitive silver halide photographic material thus prepared according to the present invention is developed by use of a common primary aromatic amine type color developing agent, the exposed silver particles on the material are reduced by means of the color developing agent to form a silver image and, on the other hand, the oxidized color developing agent couplers with the maminophenol type coupler to give a substantially black dye of indoaniline type.

Thus, the light-sensitive silver halide photographic material containing the maminophenol type coupler of the present invention is to give a substantially black dye image when subjected to such treatment as color development fixing waterwashing, which treatment is the most general treatment system in the current color photography, and any of currently used primary aromatic amine type color developing agents may be used for developing the light-sensitive silver halide photographic materials of the present invention. As particularly preferable color developing agents used in the present invention, there may be mentioned paminophenol type and p-phenylenediamine type developing agents, for example, paminophenol, N,N-diethyl-p-phenylenediamine, N-ethyl-N-w-sulfobutyl-p- phenylenediamine, 2-amino-5-diethylaminotoluene, p-amin o-N-ethyl-N-p- hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N-( -hydroxyethyl)aniline, 4 amino-3-methyl-N-ethyl-N-(p-methoxyethyl)aniline, 4-amino-3-methyl-N-ethyl-N (p-methylsulfonamidoethyl)aniline and p-aminophenols.

In the present invention, further, there may also be used such so-called Dev Dev compounds, for example, 2,2'-methylenebis(p-aminophenol), N,N'-ethylenebis(4-amino-3-methyl-N-ethylaniline) and the like.

Hydrophilic colloids advantageously usable in the preparation of lightsensitive emulsion in the light-sensitive silver halide photographic materials of the present invention, include gelatin, gelatin derivatives, colloidal albumin, agar, gum arabic, cellulose, acrylamide, imido polyacrylamide, casein, polyvinyl alcohol, polyvinyl pyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerization of protein or saturation acylated protein with a mdnomer having a vinyl group, and the like. Usable as silver halide in tke light-sensitive silver halide photographic materials used in the present invention, may be any of those which are commonly used in silver halide photographic emulsion, such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide and silver chloroiodobromide.

The silver halide emulsion used in the light-sensitive silver halide photographic materials of the present invention may be prepared according to the commonly practice method and other various processes, for example, such as disclosed in Japanese Patent Publication No. 7772/1971 or U.S. Patent Specification No.

2,592,250, that is, the emulsion may be prepared by any process such as for preparing a so-called conversion emulsion or so-called Lippman's emulsion. The silver halide emulsion thus prepared may be sensitized with chemical sensitizers, for example1 such sulfur sensitizers as allylthiocarbamide, thiourea, allylisothiocyanate and cystine, active or inert selenium sensitizers, the noble metal sensitizers including such gold compounds as potassium chloro aurate, auric trichloride, potassium auricthiocyanate, 2-aurothiabenzothiazole methylchloride and the like, such palladium compounds as ammonium chloropalladate and the like, ruthenium compounds, rhodium compounds iridium compounds, which sensitizers may be used either singly or in the form of a suitable combination thereof. The said emulsion may be subjected to reduction sensitization using a reducing agent, in addition to the chemical sensitization, and may further be stabilized with triazoles, imidazoles, azaindenes, benzothiazolium compounds, mercaptanes or mixtures thereof, and the emulsion may contain therein sensitizing compounds of thioether type, quaternary ammonium salt type or polyalkylene oxide type. Furthermore, the aforementioned silver halide emulsion may be incorporated with such wetting agents, plasticizers and film property-improving agents, for example, as glycerine, dihydroxyalkanes such as 1,5-pentadiol, esters of ethylenebisglycolic acid, bisethoxydiethyleneglycol succinate and water-dispersible particulate high molecular compounds obtained by emulsion polymerization, and also with various photographic additives, for example, such film hardeners as ethyleneimine type compounds, dioxane derivatives, dicarboxylic acid chlorides and diesters of methanesulfonic acid, such coating aids as saponin and sulfosuccinates, fluorescent whitening agents, antistatic agents and anti-staining agents.

The silver halide photographic emulsion of the present invention is sensitized in the desired light-sensitive spectrum region and hence may also be subjected to optical sensitization by means of suitable sensitizing dyes. Various sensitizing dyes may be usable for this purpose, and they may be used singly or in the form of a combination of two or more kinds.

The light-sensitive silver halide photographic material of the present invention may contain therein, if necessary, various photographic additives, in addition to the compounds previously mentioned. For instance, into a light-sensitive emulsion layer or layer adjacent thereto, there may be incorporated, for example, such compound as capable of releasing a development inhibitor at the time of development in responding to a density of an image being developed, for example such development inhibitor-releasing compounds as disclosed in the Japanese Patent Publication No. 22514/1971 or, for example, tetrazolium compounds, according to the purposes.

The light-sensitive silver halide photographic material of the present invention is prepared by coating the present silver halide photographic emulsion thus incorporated with various photographic additives on a support which has been subjected to corona discharge treatment, fire flame treatment or ultraviolet irradiation treatment, or on a support through a subbing layer or intermediate layer.

Advantageously usable as supports in the present invention, are those which include, for example, baryta paper, polyethylene-coated paper, glass plate, cellulose acetate, cellulose nitrate, polystyrene terephthalate and, in addition, polyamide, polycarbonate and polystyrene films.

Preferably, the light-sensitive silver halide photographic material of the present invention is advantageously color developed according to a common color development method employed for developing a so-called internal type lightsensitive silver halide color photographic material, but a so-called incorporated type or Koda-color type color treatment process may also be applicable thereto.

As the internal type color developers usable in the present invention, there may be mentioned, as a typical example, a developer having the under-mentioned composition.

Composition of developer: Sodium carbonate monohydrate lOg Sodium sulfite 2-g Potassium bromide Ig 4-Amino-N,N-diethylaniline sulfate 6 Water to make 1 litre Adjusted pH to 11.0 According to purposes, these developers may contain therein one or more kinds of black-and-white developing agents, for example, Metol, I-phenyl-3pyrazolidone and hydroquinone.

After color development treatment using such developer as mentioned above, the developed light-sensitive silver halide photographic material of the present invention may be subjected to common photographic treatment, for example, a combination of treatments suitably selected, using a stopping solution containing an organic acid, a stop-fixing solution containing an organic acid and hypo or such fixing component as ammonium thiosulfate, a fixing solution containing such fixing component as hypo or ammonium thiosulfate, and other processing solutions as a stabilizing solution and the like, and other treatments such as water-washing and drying.

The light-sensitive silver halide photographic material of the present invention may be applicable advantageously to every black-and-white light-sensitive material including negative material for common black-and-white photography, paper for common black-and-white photography, material for X-ray photography, material for photo-lithography or material for common microfilm, and particularly may be effectively applicable to such high silver content black-and-white light-sensitive materials as those for X-ray photography and photo-lithography, wherein not only the silver content can be greatly reduced but also the speed thereof can be increased.

Further, the light-sensitive material of the present invention may advantageously applicable to such image reinforcing treatment methods, for example, as disclosed in Japanese Patent Publication No. 46419/1974, Japanese Patent Applications Nos. 70907/1974, 80321/1974 and 109213/1974, and a further drastic curtailment of silver content comes to be possible by application of such method to the present invention.

The present invention is concretely illustrated below with reference to examples, but embodiments of the invention are not limited only thereto.

Example 1.

10 Grams of the exemplified compound (9) was added to a mixture of 10 ml of dibutyl phthalate and 30 ml of ethyl acetate and allowed to completely dissolve at 40"C. in the mixture. The solution was mixed with 5 ml of a 10% aqueous solution of Alkanol B (a trade name of a product of alkylnaphthalene sulfonate produced and sold by Du Pont Co.) and 200 ml of a 5% aqueous gelatin solution, and the mixture was emulsified by dispersion by use of a colloid mill, thereby to obtain a coupler dispersion. The coupler dispersion was incorporated into 500 g of a silver iodobromide emulsion (containing 5 mol% of silver iodide) for common black-andwhite negative and the emulsion was coated on a cellulose triacetate base so that the amount of silver present in the resulting coating became about 20 mg per 100 cm2 of the coated base (sample A). For comparison, on the other hand, the same emulsion as in the sample A but not containing a dispersion of the exemplified compound (9) was coated on a cellulose triacetate base so that the amount of silver present in the resulting coating became about 40 mg per 100 cm2 of the coated base (sample B as a control).

After exposure through an optical wedge in the usual way, the samples A and B were individually developed at 200 C. for 6 minutes with a developer having the following composition.

Metol 25g Anhydrous sodium sulfite 30 g Hydroquinone 25g Sodium carbonate monohydrate 10 g Potassium bromide 0.5 g Water to make 1 litre The samples A and B thus developed were individually subjected in the usual procedure to stopping, fixing and water-washing, thereby to obtain samples A-l and B--l, respectively. On the other hand, the sample A was exposed to light and then color developed at 200 C. for 6 minutes with a developer having the following composition.

4-Amino-3-methyl-N-ethyl-N-methane sulfonamidoethylaniline 3/2 H2SO4 5 g Anhydrous sodium sulfite 25 g Sodium carbonate monohydrate 20 g I*Phenyl-3-pyrazolidone 0.5 g Water to make I litre After development, the developed sample A was subjected in the usual procedure to stopping, fixing and water-washing, thereby to obtain a sample A-2.

The sample A-2 was found to give a tone of bluish black color. The samples A--l, A-2 and B-I were individually subjected to sensitometry, thereby to obtain the results as shown in Table 1.

TABLE 1 Photographic characteristics Notes) Specific Sample speed Gamma Fog Dmax A-I 65 0.22 0.03 1.1 A-2 (Present invention) 105 0.46 0.06 2.6 B-I 100 0.43 0.05 2.7 As is clear from Table 1, it was observed that the sample A-2 according to the present invention, even though the silver content thereof, is only half that of the control sample B-l, had a maximum density (Dmax) at substantially the same level as that of the control sample B-1. The specific speed was represented by a relative speed as measured by assuming as 100 the speed of the sample B--l.

The same procedures as above were repeated but using each of the exemplified compounds (2), (4), (11) and (12) instead of the exemplified compound (9). The same results were observed equally.

Example 2.

To a low speed silver chlorobromide emulsion for contact film for photolithography was added 500 g of the coupler dispersion as prepared in Example 1 and the emulsion was coated on a cellulose triacetate base so that the amount of silver present in the resulting coating became about 20 mg/100 cm2 (sample A). For comparison, the same emulsion as used in the sample A but not containing the coupler dispersion was coated on a cellulose triacetate base so that the amount of silver present in the resulting coating became about 50 mg/100 cm2 (sample B).

Thus, the sample B had a silver content substantially identical with those of currently used products of light-sensitive graphic materials, whereas the sample A was a low silver content light-sensitive material, the silver content of which was, only 2/5 of that of the sample B.

The samples A and B were individually brought into contact with a screen negative and exposed to light by means of a printer. Therefore, the samples thus exposed were individually developed at 200C. for 2 minutes and 30 seconds with a developer having the following composition.

Metol 1.5g Anhydrous sodium sulfite 23 g Hydroquinone 6g Sodium carbonate monohydrate 41 g Potassium bromide 1.0 g Water to make I litre The samples A and B thus developed were individually fixed and waterwashed in the usual procedure to obtain samples A-I and B--l, respectively. On the other hand, the sample A which had been likewise exposed to light was subjected to color development at 200 C. for 2-minutes and 30 seconds with a developer having the following composition.

4-Amino-N,N-diethylaniline 1/2 H2SO4 8 g Sodium carbonate monohydrate 40 g I-Phenyl-3-pyrazolidone 0.3 g Anhydrous sodium sulfite 20 g Potassium bromide 1.5 g Water to make 1 litre The sample A thus developed was fixed and water-washed in the usual procedure to obtain a sample A-2. It was found as a result of comparative examination that the sample A--l, when compared with the control sample B--l, was low in dot density and the quality of dot, per se. of the sample A-l was poor.

In the case of the sample A-2 which had been prepared by subjecting the aforesaid sample A to color development in the manner above illustrated, however, because of the increased bluish black color due to color reaction, the sample A-2 was substantially equal in density of as well as in quality of the dot to the control sample B--l, though the silver content of the sample A-2 was only 2/5 of that of the control sample B--l.

Example 3.

10 Grams of the exemplified compound (4) was added to a mixture of 10 ml of tricresyl phosphate and 30 ml of ethyl acetate and allowed to completely dissolve at 50"C. in the mixture. The solution was mixed with 5 ml of a 10% aqueous solution of Alkanol B and 200 ml of a 5% aqueous gelatin solution, and the mixture was emulsified by dispersion by use of a colloid mill to obtain a coupler dispersion. The coupler dispersion was incorporated into 500 g of a silver iodobromide emulsion (containing 5 mol% of silver iodide) for X-ray, and the emulsion was coated on one side of a polyester base so that the amount of silver present in the r It was found as a result of the above treatment that the sample A formed thereon a bluish black dye image and a silver image, and had photographic characteristics, when compared with the control sample B, as shown in Table 2. In Table 2, the specific speed was represented by a relative value as measured by assuming as 100 the speed of the sample B.

TABLE 2 Photographic characteristics Specific Sample speed Gamma Fog Dmax A (present invention) 115 2.6 0.05 2.3 B (control) 100 1.2 0.03 1.1 As is clear from Table 2, it is understood that the light-sensitive silver halide photographic material according to the present invention has excellent performance as a light-sensitive material for X-ray.

Example 4.

The same samples as in Example 3 were treated in the same manner as in Example 3 using p-aminophenol as a color developing agent.

It was found as a result of the treatment that the sample A produced thereon a slightly brownish black dye image and a silver image, and had a maximum density, when compared with the control sample B, as shown in Table 3.

TABLE 3 Sample Dmax A 2.2 B 1.2 Example 5.

Into a silver chlorobromide emulsion for common black-and-white photographic printing paper was incorporated a dispersion of the exemplified compound (11). The emulsion was coated on a cellulose triacetate base in the manner as shown in Table 4, and the base was provided on the coated surface with a protective layer consisting of gelatin, a film hardener and a extender.

TABLE 4 Amount of silver Amount of coupler Sample (mg/100 cm2) (mg/100 cm2) A (control) 13 mg 0 mg B 6mg lOmg C 1.5 mg 10 mg After exposure through an optical wedge, the samples A, B and C were individually developed at 20"C. for 1 minute with a developer having the following composition.

Metol Ig Anhydrous sodium sulfite 7.5 g Hydroquinone 4g Sodium carbonate monohydrate 26.7 g Potassium bromide 0.7 g Water to make I litre The samples A, B and C thus developed were individually subjected to in the usual way to stopping, fixing and water-washing, thereby to prepare samples Nos. 1, 2 and 3. On the other hand, samples B and C which had been separately prepared were individually exposed to light through an optical wedge and then color developed at 20cC. for 1 minute with a developer having the following composition.

4-Amino-N,N-diethylaniline 1/2 H2SO4 4 g Anhydrous sodium sulfite 4 g Sodium carbonate monohydrate 25 g Potassium bromide 1.0 g Water to make 1 litre Subsequently, the thus developed samples B and C were individually subjected in the usual manner to stopping, fixing and water-washing, thereby to prepare samples Nos. 4 and 5, respectively.

Furthermore, a sample C which had been separately exposed to light through an optical wedge was developed at 200C for 1 minute with a developer prepared by adding 2.0 g/l of cobalt III hexamine chloride, followed likewise by stopping, fixing and water-washing, thereby to prepare sample No. 6.

Each of the samples thus prepared was subjected to measurement of a maximum density thereof, thereby to obtain the results as shown in Table 5.

TABLE 5 Sample No. Relative speed Dmax 1 (control 100 1.4 2 62 0.6 3 4 168 1.4 5 6 102 1.5 Thus, in the case of the sample No. 4 where the present compound was used, it is understood that the sample No. 4, the silver content of which is only about half that of the control sample, was sufficiently usable even when subjected to the usual development treatment, and that a further drastic curtailment in the silver content could be possible in the case of the sample No. 6 which was subjected to the color development effected in the presence of the cobalt hexamine chloride.

Example 6.

Samples were individually prepared by coating a polyester base on the surface with a coating material such as shown in the following Table 6.

TABLE 6 Amount of silver Amount of coupler Sample (mug/100 cm2) (mg/100 cm2) A 40 mg B 5 mug C 40 mg 10 mg D Smg 10mg On the coated surface of each sample, however, was formed a gelatin protective film containing a film hardener, an extender, etc. As the silver halide emulsion, there was used a silver iodobromide emulsion for X-ray, and in the case of each of the samples C and D, the exemplified compound (7) was protect dispersed together with tricresyl phosphate in the silver iodobromide emulsion in the same manner as in Example 1.

After exposure through an optical wedge, the sample A was developed at 20 C. for 5 minutes with the same monochromatic developer as used in Example 3, followed by common fixing and water-washing, thereby to prepare sample No. 1 (control). Also the sample B was likewise treated to prepare sample No. 2. The samples C and D were individually color developed at 200 C for 5 minutes with the same developer as used in Example 3, followed likewise by fixing and waterwashing, thereby to prepare samples Nos. 3 and 4, respectively. The developed samples C and D were individually treated further at 200 C. for 5 minutes with a developer having the following composition.

4-Amino-N,N-diethylaniline 1/2 H2SO4 7 g Anhydrous sodium sulfite 20 g Anhydrous sodium carbonate 50 g Hydroquinone 5g l-Phenyl-3-pyrazolidone 0.5 g N-Methylbenzthiazolium p-toluene sulfonate 1.0g l-Phenyl-5-mercaptotetrazole 20 20 mg Water to make 1 litre Subsequently, the thus treated samples C and D were individually subjected to common fixing and water-washing, thereby to prepare samples Nos. 5 and 6, respectively. Of the two samples thus treated, the sample D was further treated, after development, at 200 C. for 6 minutes in a hydrogen peroxide bath having the following composition, followed likewise by fixing and water-washing, thereby to prepare sample No. 7.

35% H202 25 ml Water to make 1 litre Adjusted to pH 8 by addition of IN--NaOH.

Each of the samples thus treated was subjected to measurement of fog and maximum density thereof, thereby to obtain the results as summarized in Table 7.

TABLE 7 Coating conditions Treatment conditions Results Amount of Sample silver Coupler Monochromatic Color H202 No. (mg) (mg development development treatment Fog Dmax 40 - Done - - 0.04 1.1 (control) 2 5 - Done - - - - 3 40 10 - Done - 0.04 2.2 4 5 10 - Done - - 5 40 10 - Done - 0.05 2.6 6 5 10 - Done - - - 7 5 10 - Done Done 0.07 2.9 Reviewing the results as shown in Table 7, it is understood thah by using the present compound in combination with the hydrogen peroxide reinforcement treatment, a further drastic curtailment in the silver content of light-sensitive silver halide photographic material.

Example 7.

Using a low speed silver chlorobromide emulsion for graphic purposes and an alkali dispersion of the exemplified compound (17), samples as shown in Table 8 were individually prepared.

TABLE 8 Amount of coating Silver Coupler Sample (mg/100 cm) (mg/100 cm) A (control) 40 B 20 8 C 4 8 Separately, subjected to supersonic wave dispersion was a mixture of 15 ml of a 5% aqueous solution of DES (sodium di-(ethylhexyl succinate)-sulfonate), 60 ml of a 10% aqueous gelatin solution, 200 mg of 1,3,5-triphenyl-tetrazolium chloride (hereinafter abbreviated to "T-salt") and 35 ml of water. The liquid thus dispersed was incorporated into a mixture of the aforesaid emulsion and coupler dispersion, and the resulting mixture was coated according to the manner as shown in Table 9 on a cellulose triacetate film based to prepare samples shown in said table.

TABLE 9 Amount of 1,3,5-triphenyl coating tetrazolium Silver Coupler chloride Sample (mg/100 cm2) (100 mg/100 cm2) (mg/100 cm2) D 40 2 E 20 8 2 F 4 8 2 The samples A, B, C, D, E and F were individually exposed in the usual way to light through a crossline screen and treated in the following manner. The samples A and D were individually developed at 20"C. for 2 minutes and 30 seconds with a developer having the following composition, followed by common fixing and water-washing, thereby to prepare samples Nos. 1 and 4, respectively.

Metol 1.5g Anhydrous sodium sulfite 20 g Hydroquinone 6g Sodium carbonate monohydrate 40 g Potassium bromide 1.0 g Water to make 1 litre The samples B and E were individually developed at 20"C. for 2 minutes and 30 seconds with a developer having the following composition, followed by fixing and water-washing, thereby to prepare samples Nos. 2 and 5, respectively.

4-Amino-N,N-diethylaniline 1/2 H2SO2 7 g l-Phenyl-3-pyrazolidone 0.5 g Anhydrous sodium sulfite 20 g Sodium carbonate monohydrate 40 g Potassium bromide 1.0 g Water to make 1 litre The samples C and F were individually developed in the same manner as in the case of the samples Nos. 2 and 5 with the above-mentioned developer. Thereafter, the developed samples C and F were individually treated at 20"C. for 5 minutes with a hydrogen peroxide amplification bath having the following composition, followed by fixing and water-washing, thereby to prepare samples Nos. 3 and 6, respectively.

35% H202 25 ml Water to make l litre Adjusted pH with IN NaOH to 8.

The results obtained were as summarized in Table 10.

TABLE 10 Coating conditions Treatment conditions Results Sample Monochromatic Color H2O2 No. Silver Coupler T-salt development development treatment Dmax Dot 1 40 mg - - Done - - 2.0 Bad 2 20 mg 8 mg - - Done - 2.1 Bad 3 4 mg 8 mg - - Done Done 2.6 Bad 4 40 mg - 2 mg Done - - 2.0 Good 5 20 mg 8 mg 2 mg - Done - 2.0 Good 6 4 mg 8 mg 2 mg - Done Done 2.5 Good Reviewed the results, it is understood that the samples containing T-salt gave excellent dots of good image quality even when treated with a common developer which was not a special developer for light-sensitive photolithographic material, and that when the T-salt was used in combination with the present coupler in a light-sensitive silver halide graphic material, a sufficient density and dot of good image quality could be obtained thereby even when the silver content of said material was only about half that commonly used in the material of this kind and, in addition, similar results could be obtained by use of a light-sensitive silver halide graphic material containing the T-salt and the present coupler but having a drastically curtailed silver content when the material was treated with a hydrogen peroxide reinforcement bath.

Example 8.

The exemplified compound (18) was alkali dispersed in the usual manner. The alkali dispersion was tehn incorporated into a silver iodobromide emulsion (containing 5 mol% of silver iodide) for X-ray, and the emulsion was coated in the manner as shown in Table 11 on one side of a polyester base, thereby to prepare samples.

Separately, the same emulsion as above but not containing the present coupler was likewise coated on a polyester base, thereby to prepare a sample used as a control.

TABLE 11 Amount added Silver Coupler Sample (mg/100 cm2) (mg/100 cm2) A (control) 40 B 40 13 C 7 13 The sample A was developed at 200 C. for 5 minutes with a monochromatic developer having the same composition as in the developer used in Example 3, followed by fixing and water-washing, thereby to prepare sample No. I (control).

The sample B was color developed at 200 C. for 5 minutes with the same color developer containing the 4-amino-N,N-diethylaniline as in Example 3, followed by fixing and water-washing, thereby to prepare sample No. 2.

After color development as in the case of the sample B, the sample C was treated at 200C for 5 minutes with a hydrogen peroxide reinforcement bath having the same composition as in the bath used in Example 7, thereby to prepare sample No. 3.

The results obtained were as summarized in Table 12.

TABLE 12 Photographic characteristics Sample No. Fog Dmax 1 0.03 1.2 2 0.04 2.3 3 0.05 2.5 As is clear from Table 12, it is understood that the expected object could be accomplished even by use of the alkali dispersion type coupler according to the present invention and, the amount of silver contained in the present sample could be curtailed to about half the amount commonly required when the sample was intended to be subjected to the common color development and the amount of silver could be drastically curtailed when the present sample was intended to be treated further with the hydrogen peroxide amplification bath.

Example 9.

A high speed silver iodobromide photographic emulsion was prepared by subjecting, after the first ripening, a silver iodobromide emulsion to chemical sensitization with a sulfur sensitizer, a gold sensitizer and the like, followed by stabilization using tetrazaindenes and other stabilizers.

Separately, the exemplified compounds (4), (13), (44) and (50) were individually protect-dispersed, according to the same procedure as in Example 3, in a dibutyl phthalate/ethyl acetate mixture to prepare coupler dispersions. Each of the coupler dispersions thus prepared was incorporated into the aforesaid silver iodobromide photographic emulsion and the resulting emulsion was coated on a polyester base. Subsequently, a gelatin protective layer containing a spreading agent and a hardener was formed on the emulsion-coated polyester base. In the manner mentioned above, there were prepared samples of light-sensitive silver halide photopgraphic materials containing their respective ingredients as shown below.

Amount of Amount of Amount of Amount of dibutyl compound silver gelatin phthalated added added used added Sample (mg/dm2) (mg/dm2) (mg/dm2) (mg/dm2) A - 39.2 26.2 B (1)19.0 43.2 28.1 10.1 C (1)18.1 21.5 27.5 9.2 D (8)19.8 19.2 25.8 10.0 E (32)21.8 18.1 24.7 9.8 F (38)27.2 23.6 28.4 9.1 The samples thus prepared were individually exposed to light through an optical wedge in the usual manner. The sample A was subjected to development with the black-and-white developer described in Example 3 in the similar manner to prepare a sample 1. The samples B, C, D, E and F were individnally subjected to color development at 200 C. for 3 minutes with a color developer having the following composition.

4-Amino-N,N-diethylaniline sulfate 6 g Sodium carbonate monohydrate 10 g Potassium bromide I .0 g Sodium sulfite 10 g 5-Nitrobenzimidazole 150 mg Distilled water to make I litre Adjusted pH with sodium hydroxide to 11.0 The samples B-F thus color-developed were then subjected to stropping, fixing and water-washing to prepare samples 2--6, respectively. Each othe samples 26 had a slightly bluish black image thereon. The samples 16 thus developed were individually subjected to sensitometry to obtain the results as shown below.

Sample Fog Dmax Gamma 1 (control) 0.05 1.3 1.1 2 0.06 2.8 2.6 3 0.04 1.4 1.3 4 0.07 2.9 2.7 5 0.06 2.4 2.3 As is clear from the foregoing, it is understood that even the samples containing the exemplified compound (4) form thereon a very good black image and, on the other hand, in the samples containing such active point-substituted type couplers as the exemplified compounds (13), (44) and (50) the silver content thereof may be reduced by about one-half, as compared with the sample containing the active point-unsubstituted type coupler, and said silver content may be reduced by about one-fourth, as compared with the control sample containing only silver without any coupler as aforesaid.

Example 10.

On a polyethylene terephthalate base were successively formed the following layers according to the procedure as described in Example 3.

(I) Layer containing high speed silver iodobromide emulsion for X-ray, which layer contains 19 mg/dm2 of gelatin, 25 mg/dm2 of silver and 16 mg/dm2 of the exemplified compound (13).

(2) Gelatin protective layer, containing 11 mg/dm2 of gelatin.

The sample thus prepared was exposed to light through an optical wedge and the exposed sample was then developed at 20"C. for 3 minutes with the same color developer as in Example 9. The sample thus developed was then subjected in the usual manner to stopping and fixing, followed by water-washing, whereby a negative film sample having formed thereon a bluish black dye image was obtained.

The negative film sample was then subjected to sensitometry to obtain the results showing fog of 0.08 and Dmax of 2.2.

As is clear from the foregoing, it is understood that the silver content of the negative film sample prepared by this example may be reduced by one-third or less, as compared with the prior art films for X-ray.

Example 11.

A green-sensitive silver iodobromide emulsion for X-ray, into which the exemplified compound (30) had been incorporated, was coated according to the procedure of Example 3 on a polyethylene terephthalate base to obtain a sample containing: (1) 23 mg/dm2 of gelatin, 21 mg/dm2 of silver, and 15 mg/dm2 of the exemplified compound (30), and (2) gelatin protective layer containing 10 mg/dm2 of gelatin.

The sample thus obtained was exposed to X-ray at a distance of 1 m, 70 KV peak and 100 MA through an aluminum wedge using a sensitizing paper of GTH Ortho type produced by Tokyo Shibaura Elect. Co., Ltd.

The thus exposed sample was color-developed at 20"C. for 3 minutes with the developer of Example 9, and the developed sample was subjected to fixing and water-washing, followed by drying. The image formed on the developed sample consisted of a black dye image, and the sample was subjected to sensitometry to obtain the results showing fog of 0.05, Dmax of 2.9 and gamma of 2.6.

From the foregoing, it is understood that the present sample, even when used as an ortho type film for X-ray, forms a desired image without deteriorating image quality and the silver content thereof can be reduced to one-fourth of that required in the presently used films for X-ray.

Example 12.

A light-sensitive element was prepared by coating on a polyethylene terephthalate base a light-sensitive layer containing a chemically sensitized silver iodobromide emulsion containing 19 mg/dm2 of gelatin, 30 mg/dm2 of silver and 18 mg/dm2 of the exemplified compound (5).

Separately, an image-receiving element was prepared by forming the following layers successively in the under-mentioned order.

(I) pH-Reducing layer containing 100 mg/dm2 of poly(methylvinyl ether/maleic anhydride).

(2) Gelatin intermediate layer, containing 3 mg/dm2 of gelatin.

(3) Dye image-receiving layer containing 100 mg/dm2 of copoly[styrene-N benzyl-N,N-dimethyl-N-(3-maleimidopropyl)ammonium chloride].

The light-sensitive element was exposed to light through an optical wedge.

Thereafter, a processing composition as mentioned below was passed so as to spread in a sandwitch form between the exposed light-sensitive element and the image-receiving element placed one upon the other through a pair of rollers facing to each other.

Composition of the processing composition: B enzyl alcohol 10.0 ml Sodium hydroxide 25.0 g Aniline sulfate 30.0 g 5-Nitrobenzimidazole 0.05 g Hydroxyethylcellulose 30.0 g Piperidinohexosereductone 0.2 g Distilled water to make 1 litre The light-sensitive and image-receiving elements thus treated were left to stand at about 20bC for 80 seconds and the two elements were then peeled off from each other. The image-receiving element was then acidified with a 2% aqueous acetic acid solution and washed with water. The image-receiving element had thereon a transferred bluish black dye negative image corresponding to the image wise exposure. The results of sensitometry showed Dmax of 1.92 and Dmin of 0.24.

Claims (7)

WHAT WE CLAIM IS:

1. A light-sensitive silver halide photographic material comprising a m-amino phenol compound as a coupler capable of reacting with the oxidation product of a primary aromatic amine type color developing agent to form a black dye image wherein the m-amino phenol compound-has the general formula,

wherein R, and R2,which may be the same or different, each represents a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, aralkyl, aryl, or heterocyclic radical, or R, and R2, together with the nitrogen atom to which they are attached, represent a heterocyclic radical, neither R, or R2 containing any moiety capable of development, R3 and R4, which can be the same or different, each represents a hydrogen or halogen atom or a monovalent organic radical; and X and Y, which can be the same or different, each represents a hydrogen atom, halogen atom or a monovalent organic radical, at least one of X and Y representing a hydrogen or halogen atom or a radical capable of splitting off on reaction with an oxidized primary aromatic amine color developing agent.

2. A photographic material as claimed in Claim I wherein the primary aromatic amine color developing agent is of the p-phenylenediamine type.

3. A photographic material as claimed in Claim 1 or 2 wherein R, and R,. which can be the same or different, each represents, an alkyl, alkenyl, aryl or heterocyclic radical substituted by one or more hydroxy, carboxyl, sulfonic acid, alkyl, alkenyl, aryl, heterocyclic, -0-,

-CONH-, -NHCO-, -S-, -SO2NH-, or -NH-SO2 groups, or in which skeletal carbon has been substituted by ether, thioether or

groups.

4. A photographic material as claimed in any of the preceding claims wherein at least one substituent has diffusion-preventing properties.

5. A photographic material as claimed in Claim 4 wherein the substituent having diffusion-preventing properties is an alkyl group having 8 or more carbon atoms or an aralkyl group having alkyl with 4 or more carbon atoms.

6. A photographic material as claimed in Claim 1, wherein the phenol compound is one of the compounds (1) to (82) hereinbefore set forth.

7. A photographic material as claimed in Claim 1 substantially as hereinbefore described with reference to any of Examples 1 to 12.