US3929486A - Silver halide photographic material containing a sensitizing and stabilizing combination of a polyalkylene oxide, a tetrazaindene and a resorcinol derivative - Google Patents

Abstract

This invention relates to a light-sensitive silver halide photographic material having a photographic layer incorporated with a polyalkylene oxide type compound, a tetrazaindene type compound and a resorcinol type compound.

Description

United States Patent 1191 Habu et a1.

[ Dec. 30, 1975 [541 SILVER HALIDE PHOTOGRAPHIC MATERIAL CONTAINING A SENSITIZING AND STABILIZING COMBINATION OF A POLYALKYLENE OXIDE, A TETRAZAINDENE AND A RESORCINOL DERIVATIVE [75] Inventors: Teiji Habu; Tomio Nakajima; Eiichi Sakamoto; Kenzi Kadokura; Kyusaku Yoshida; Katsutoshi Machida,-all of l-Iino, Japan [73] Assignee: Konishiroku Photo Industry Co.,

Ltd., Tokyo, Japan [22] Filed: May 8, 1974 [21] Appl. No.: 467,957

[30] Foreign Application Priority Data May 12, 1973 Japan 48-52094 [52] U.S. Cl 96/76 R; 96/107; 96/109 [51] Int. cl. 603C 1/28;G03C 1/34 [58] Field of Search 96/107, 109, 95, 76 R [56] References Cited UNITED STATES PATENTS 2,418,613 4/1947 Allen et al7 96/109 2,716,062 8/1955 Carroll et a1 96/109 3,236,652 2/1966 Kennard et al. 96/109 3,457,079 7/1969 Koda et al. 96/109 3,563,754 2/1971 Jones et al..... 96/109 3,671,258 6/1972 Taber 96/109 Primary Examiner-Won H. Louie, Jr. Attorney, Agent, or FirmBierman & Bierman [57] ABSTRACT This invention relates to a light-sensitive silver halide photographic material having a photographic layer incorporated with a polyalkylene oxide type compound, a tetrazaindene type compound and a resorcinol type compound. -o

4 Claims, No Drawings SILVER I-IALIDE PHOTOGRAPI-IIC MATERIAL CONTAINING A SENSITIZING AND STABILIZING COMBINATION OF A POLYALKYLENE OXIDE, A

TETRAZAINDENE AND A RESORCINOL DERIVATIVE Recently, light-sensitive silver halide photographic materials are required to have properties satisfying increasingly complex and diverse requirements. Particularly, high speed to ultra-high speed silver halide pho-' tographic materials having stable photographic properties are demanded, and, in the radiography, X-ray photographic materials high in speed and free from fog are demanded so as to obtain more informations with smaller doses of X-rays in order that the human body is less exposed to radiation.

It has heretofore been said that for increase in speed of a light-sensitive silver halide photographic material, it is quite effective to incorporate a polyalkylene oxide type compound into the photographic material, as disclosed in, for example, The Theory of the Photographic Process, Third Edition, pages 369-370 (1967). However, the amount of polyalkylene oxide type compound used in such case is restricted, and if the amount thereof exceeds a definite limit, the photographic material is greatly increased in fog. Furthermore, when the photographic material is subjected, during its preparation, to quick drying under low humidity conditions, or subjected to development under severe conditions at elevated temperatures, the increase of fog is further promoted to cause such fatal disadvantage that the photographic material is greatly deteriorated in photographic properties.

In order to prevent the said high speed silver halide photographic material from formation of fog to stabilize the photographic properties thereof, there have been made attempts to use such tetrazaindene type compounds as disclosed in, for example, Japanese Patent Publication No. 9,432/57 and US. Pat. No. 2,716,062. However, the said tetrazaindene com-' pounds are extremely weak in action of preventing the formation of fog and the degradation of photographic properties in the case where the photographic material is subjected to such severe conditions required in recent years that it is prepared through low humidity quick drying steps, stored under high temperature high humidity conditions, or processed under high temperature quick development conditions. Thus, the tetrazaindene type compounds cannot display practical effects. To cope with this, there have been desired proper antifoggants necessary to make the polyalkylene oxide type compound effectively display its action as a sensitizer. However, the actual state is such that no satisfactory antifoggants have been discovered yet.

An object of the present invention is to provide a light-sensitive silver halide photographic material sensitized with a polyalkylene oxide type compound which is high in speed and free from fog and thus is stable in photographic properties.

Another object of the invention is to provide a light-- sensitive silver halide photographic material which is free from increase in fog and stable in photographic properties even when subjected to such severe conditions as in the case where it is prepared through low humidity quick drying treatment at the time of coatingand drying of silver halide emulsion, stored in a high temperature high humidity atmosphere, or processed under high temperature quick development conditions.

The above-mentioned objects can be accomplished by incorporating, into' a-lighvsensitive silver halide photographic "material sensitized with a. polyalkylene oxide typefcompound, at least one compound selected from tetrazaindene type compounds, andat least one compound selected from resorcinol type compounds (hereinafter referred to as compound A) having the following generalformulas I and II:

General formula I:

wherein Ris, same or different, are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may haveasubstitu'ent, an aralkyl group which may have a substit'u'ent,'an alkoxy group which may have a substituent, anjacyl group 'which may have a substituent, a carboxymethyl group which may have a substituent, or agroup "COOM or 'SO M (where M is a hydrogen atom, an alkali'm etalat'om or an ammonium group); R and Rg'areindividually a group COOM or SO M; and n, and n are individually an integer of l 33 v i v 7 That is, when the .said'light-sensitive silver halide photographic material sensitized witha polyalkylene v oxide type compound is incorporated with a tetrazaindenetype compound and a compound A, the sensitizing action, possessed by the polyalkylene oxide type compound is effectively displayed tomake it possible toobtain a photographic material which is high in speed andfree from fog and can maintain stable photographic properties even under such severe conditions as, mentioned previously The polyalkylene oxide type compound used as a sensitizer for the photographic material according to the present invention includes various compounds such as, for example, polyalkylene glycols, addition polymerization products of alkylene oxides with hexitol ring dehydration compounds, and addition polymerization products of phenol-formalin resins with alkylene oxides. These polyalkylene oxide type compounds should have a molecular weight of at least 300, preferably from 500 to 8,000. Typical examples of these compounds are as follows:

(P-l) Addition polymerization product of 1 mole of ptbutylphenol with about 27 moles of ethylene oxide.

(P-2) Addition polymerization product of 1 mole of nonylphenol-formalin resin with 10 moles of ethylene oxide. 3

(P-3) Condensation product of 1 mole of lauryl alcohol with about 20 moles of ethylene oxide.

(P-4) Polyethylene glycol.

(P-S) Condensation product of 1 mole of phenol with about 20 moles of ethylene oxide.

' 3,929,486 3 4 (P-6) Addition polymerization .product of l'mole of (TU-5) n-butylmercaptan: with 10 molesf propylerifl I oxide and20 moles of ethylene oxide, (P-7;) Addition polymerization product of 1 mole of octylphenol-formalin resin with 15 ,moles'of ethyl- I, ,ene oxide. a I I i -(P-8) Additionpolymerization productof 1. mole of OH p-cresol-formalin resin with 8 moles of ethylene I oxide. J, g (P-9) Addition polymerization product of 1 mole of 10 I p-thiocresol with 30 moles of ethylene oxide. 7 The tetrazaindene type compound used in the pres ent invention includes compounds of various struc- N N tures. Particularly effective are" compounds of the fol- V lowing general formula "I. 1\I\N/ 5 /NTN r J;( \N% 11 III R2 '20 wherein R is a hydrogen atom, a carboxyl group, an l E esterified carboxyl group, a mercapto group, an alkyl I 2 group which may have substituent, an, aryl group C 2 I which may have a subst tuent, a heterocyclic group N I which may have a SuBs tituent an alkylthio group which may have a subfstituen t, an arallgylthiofgroup which may have a 'substitue nfllor an, alicyclic imp which may have a substituent; R is a hydrogen atom, a halogen atom, a carboxyl' group, an esterified carboxyl group, an amino groupwhich may have a substituerit, an aryl group which may have a substitu'ent an aralkyl group N I N which may have a substituent, an alicyclic grolip which v. 5 may have a substituent', a hete i'ocy'clic gro'up which" i N 5 may have a substituent, or a thiuronium groupwhich may have a substi tuent; and R is a hydrogen atom, a I OH hydroxyl group, a carbonyl group, an esterified c'ar: bo xyl group,'an amino group which may have'a substit uent, an alltyl'group which ma-y'have 'substituent, an 40 I alicyclic group which'may have a subs tituentfor a het- (P-"7) erocyclic group which may have asubStitiientfRQand R may form, in combination, a carbocyclic ring or a I H C heterocyclic ring. 5 Y C Typical examples of "the'tetraz aindcne coni- 5 pound used in the present invention are as follows:

, ll-8. 5 I.

CH O

CC-OH C-SCH COOH COOH

COOH

OH Q1 can be easily synthesized, according to the processes described in, for example, The Journal of Organic Chemistry, Vol. 24, pages 779-801 I959) and Vol.

25, pages 861 8660960), Japanese Patent Publication No. 9,432/57, and U.S. Pat. Nos. 2,835,581 and 2,566,659.

COOH

OH HOOC i 4o Br OH (PM 0 K (2) OH H000 t Cl I GOOH COOH

H 2) OH SO /H 2/ H O O S O C 2/ H C 2 2 rH BO H 2/ H O O S S 5 O H 0 5 6 6 H H O H o C 0 O 1 H 6 H OH COH O 0 C 9 (25) OH (24) OH H N s OH OH 5 5 4 30 N11 (25) H OH HO COOH HOOC OH 15 (26) OH OH HOOO CH2 000B HO OH Typical examples of compounds of the aforesaid general formula ll are as follows:

(27) OH (28) OH OH \OH COOH 9) OH (50) OH $05K K053 0H K058 OH The above-mentioned compounds A can be easily synthesized according to the processes described in, for example, Gazzetta Chimica ltaliana, Vol. 57, pages 793-802 (1927), Chemical Abstracts, Vol. 41, page 5495 (1947), Helvetica Chemica Acta, Vol. 43, page 644 (1960), Beilsteins Handbuch der Organischen Chemie, Vol. 6, page 987, and Vol. 11, page 304.

The said polyalkylene oxide type compound, tetrazaindene type compound and compound Aare preferably made present in the silver halide emulsion layer of a light-sensitive silver halide photographic material, but may be made present in any of protective layer, sub layer or inter layer adjacent to said silver halide emulsion layer. The compounds may be made present either in combination in one layer or independently in separate adjacent layers. At the time of incorporation into a photographic material, the compounds may be brought into the form of a solution or solutions in water or an organic solvent compatible with water such as lower alcohol or ketone, or in a mixed solvent comprising water and organic solvent, and may be added either simultaneously or separately. For example, the polyalkylene oxide type compound as a sensitizer, the tetrazaindene type compound and the compound A may be added in this order.

The time of addition of these compounds to a silver halide emulsion, for example, may be an optional stage during preparation of the emulsion, but is preferably the stage immediately before completion of the second ripening.

.The amounts of the compounds to be added to a silver halide emulsion vary depending on the kinds of the compounds and of the silver halide emulsion. Ordinarily, however, the amount of the polyalkylene oxide type compound is preferably in the range from 0.01 to 5 g., and the amount of each of the tetrazaindene'type compounds and the compound A is in the range from 0.1 to 50 g., more preferably from 0.5 to 50 g., per mole of the silver halide. The proportion of the compound A is preferably in the range from 0.1 to 10 parts by weight per part by weight of the tetrazaindene type compound.

Silver halide emulsions usable in the light-sensitive silver halide photographic materials of the present invention are black-and-white photographic emulsions, X-ray photographic emulsions, lith-type emulsions, incorporated type and Fischer type color photographic emulsions, and black-and-white and color photographic emulsions for diffusion transfer, and may contain various silver halides such as silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. Further, the silver halide emulsions may have been sensitized with noble metal sensitizers, chemical sensitizers such as sulfur or reduction sensitizers,o'r"color sensitizers, and may have been incorporated with various photographic additives used hitherto.

The thus prepared light-sensitive silver halide photographic material of the present invention is not only high in speed, free from fog and excellent in gradation, but also have photographic properties capable of withstanding such severe conditions as in the cases where it is prepared through low humidity quick drying treatment at the time of coating and drying of silver halide emulsion, stored under high temperature high humidity conditions, and processed under high temperature quick development conditions.

The present, invention is illustrated in detail below with reference to examples, but the examples do not limit the scope of the invention.

EXAMPLE 1 Immediately before completion of second ripening, a high speed negative silver iodobromide emulsion containing 1.5 mole% of silver iodide was incorporated with 0.2 g., per mole of the silver halide, of the compound (P-l) as a polyalkylene oxide type sensitizer, in the form of an aqueous solution, and then with 0.3 g., per mole of the silver halide, of the compound (T-l After completion of second ripening, the emulsion was equally divided into 9 portions. One of the thus formed 9 emulsions was taken up, incorporated with a coating aid and a hardener, coated on a cellulose triacetate film base to dry thickness of 10 g., and then dried to prepare a control sample (Sample No. 1). Each of the remaining 8 emulsions was additionally incorporated with LC g. or 3.0 g., per mole of the silver halide, of the com pound A shown in Table l, and then treated in the same manner as in the case of the control sample tc 'prepare 8 kinds of samples (Sample Nos. 2, 3, 4, 5, 6

ally exposed, according to the method'reg'illa't'ed in JIS 'Anhy'drous sodium sulfit e 70 g'. Hydroquinone 4 10 g. Anhydrous boric acid 1 g. So'dium carbonate, monohydrate 20 g. l-Phe'nyl-3-pyrazolidone l 0.35 g. Sodium hydroxide ..5 g. S-Methylbenzotriazole 0.05 g. 'Potassium bromide g. Glutaraldehyde bisulfite 15 g. Glacial acetic acid 8 g.

One

Water to make thus processed samples and control samplewere subjected to sensitometry, to measure the photographic properties thereof. The results obtained were as set forth in Table 1.. In Table I, the speed is a relative value calculated by assuming as 100 the speed of the control sample (the same shall apply hereinafter).

Tablel 1 Sample Kind and amount of Photographic No. compound A v propemes" (g/mole silver halide) Speed Fog Gamma l I ;None -100 '2 023 "1.1 2 Compound (1) 1.0 120 0.15v 1.2; '3 Compound 3.0 130 0.10 1.2 4 -Compound (3) 1.0 125 0.12 1.1 5 Compound 3.0 1 15 0.09 1 15 6 Compound (4) 1.0 105 g 0.15 1.15 7 Compound 3.0 110 0510- 1.20 8 Compound (29). 1.0 120 =0.l0- 1.15 9 Compound 3.0 0.09 1

As isclear from Table 1, it is understood that even EXAMPLE 2 A silver iodobromide X-ray photographic emulsionv containing 2 mole% of silver iodide was subjected to second ripening by addition of a gold sensitizer, and then. incorporated witha hardener, a coating aid and the compound (T-2). Subsequently, the emulsion was equally divided into 9 portions. One of the thus formed.

9 emulsions was, taken up, and coated on a polyethyleneterephthalate film base to a dry thickness of 10 p. to

12 No. 10). Each of the remaining 8 emulsions was incorporated with 1.5 g. or 3.0 g., per mole of the silver halide, of the compound A shown in Table 2, and then treated in the same manner as in the case of the control sample to prepare 8 kinds of samples (Sample Nos. 1 1, 12,13,14,l5, 16,17 and 18).

The thus prepared samples and control sample were individually exposed for 0.5 second to X-rays at a voltage of 60 KV and a peak current of 200 mA, through a fluorescent medical X-ray screen having a medium sensitivity (KYOKKO. FS. having a fluorescence spectrum maximum of 4250 A; produced by Dainihon Paint Co., Ltd.) and through an aluminum optical wedge having a step difference of V 2. Subsequently, the samples and control sample were subjected to the same development and treatment as in Example 1 to measure the photographic properties thereof. The results obtained were as set forth in Table 2.

As is clear from Table 2, it is understood'that even when quickly dried-under high temperature high humidity conditions, a light-sensitive silver halide X-ray photographic material containing a polyalkylene oxide type compound in the protective layer can give a clear form a silver halide emulsion layer. On the thus formed layer, a 3% aqueous gelatin solution incorporated with 0.1 g., pergram of gelatin, of the compound .(P-2) as a polyalkylene oxide type sensitizer was coated to form a protective layer. The film having. the thus protected silver halide emulsion layer was quickly dried in 10. minutes in an atmosphere kept at C.-and a relative humidity of to prepare a control sample (Sample X-ray image high in sensitivity and free from fog, so far as. the photographic material has been. incorporated ith a tetrazaindene type compound and a compound EXAMPLE 3 Immediately before completion of second ripening, the same silver iodobromide emulsionas in Example 2 was incorporated with 0.2 g., per. mole of the silver halide, of the compound (P-3) as a polyalkylene oxide type sensitizer, and then with 0.3 g. per mole of the silver ha1ide,-of the compound (T-4). After completion of second ripening, the emulsion was equally divided into 6 portions. One of the thus formed 6 emulsions was taken up,- coated on a cellulose triacetate film base, and then dried..to prepare a control sample (Sample No. 1.9). Each-of the remaining 5 emulsions was incorporated with a compound A shown in Table 3, and then treated in the samemanner as in the case of the control sample to prepareS kinds of samples (Sample Nos. 20, 21, 22, 23 and 24).

The thus prepared samples and-'control'sample were subjected to the same development and sensitometry as in Example 1 to measure the photographic properties Table 3 Sample Kind and amount of Photographic properties (storage test) No. compound A Stored for 3 days Stored for 3 days (g/mole silver halide) at 20C. RH 60% at 50C. RH 80% Speed Fog Speed Fog 1 amma amma v 19 None 100 0.25 1.15 87 0.37 1.10 20 Compound (25) 2.75 105 0.20 1.18 100 0.22 1.17 21 Compound (26) 2.75 115 0.18 1.20 115 0.19. 1.20 22 Compound (18) 3.0 128 0.15 1.19 130 0.15 1.20v 23 Compound (23) 3.0 132 0.12 1.21 130 0.13 1.19 24 Compound (14) 2.7 122 0.14 1.20

As is clear from Table 3, it is understood that even when stored for a long period under high temperature high humidity conditions, a high speed silver halide photographic material sensitized with a polyalkylene oxide type compound can maintain high speed and fog-free photographic properties, so far as the photographic material has been further incorporated with a tetrazaindene type compound and a compound A.

EXAMPLE 4 A silver iodobromide emulsion containing 5 mole% of silver iodide was incorporated with 0.4 g., per mole of the silver halide, of the tetrazaindene compound (T-6). A portion of the silver halide emulsion was taken up, coated on a cellulose triacetate film base, and then dried to prepare a control sample (Sample No. 25). The remaining silver halide emulsion was equally divided into 5 portions. Each of the thus formed 5 emulsions was incorporated with 0.1 g., per mole "of'zthe silver halide, of such polyalkylene oxide type compound as shown in Table 4. A portion of each of said 5 emulsions was taken up, coatedon'a cellulose triacetate film base, and then dried to prepare 5 kinds of control samples (Sample Nos. 26, 29, 32, 35 and 38). Finally, each of the said 5 emulsions was equally "divided into 2 portions, and each of the resulting l0 emulsions was incorporated with 3.0 g., per mole of the silver halide, of such compound A as shown in Table 4,

and then treated in the same manner as in the case of the control sample to prepare 10 kinds of samples (Sample Nos. 27, 28, 30, 31, 33, 34, 36, 37, 39 and 40).

The thus prepared 6 kinds of control samples and 10 kinds of samples were subjected to the same development and sensitometry as in Example 1 to measure the photographic properties thereof. The results obtained were as set forth in Table 4.

25 0.14 26 Compound (P-4) 0.28 27 Compound (24) 0.3 140 0.12 28 "(29) 155 0.14 29 Compound (P-S) 110 0.24 30 Compound (24) 140 0.13 31 "(29) 135 0.14 32 Compound (P-6) 0.26 33 Compound (24) 160 0.15 34 Compound (P-6) Compound (29) 0.3 170 0.16 35 Compound (P-7) 123 0.27 36 Compound (24) 160 0.10 37 (29) 150 0.12 38 Compound (P-8) 118 0.24 39 Compound (24) 145 0.13 40 "(29) 160 0.14

As is clear from Table 4, -it is understood that even a light-sensitive silver halide photographic material sensitized with any of such typical polyalkylene oxide type compounds as shown in Table 4 can maintain high speed and fog-free photographic properties, so far as the photographic material has been incorporated with a tetrazaindene type compound and a compound A.

EXAMPLE 5 A blue-sensitive silver halide color photographic emulsion containing 5 mole% of silver iodide was subjected to second ripening, and then incorporated with, per mole of the silver halide, 0.1 g. of the compound (P- 7) as a polyalkylene oxide type sensitizer, 0.3 g. of the compound (T-l2), and then 70 g. of 4-dodecylbenzoyl-2-methoxyacetanilide as ayellow coupler. Subsequently, the emulsion was equally divided into. 7 portions. One of the thus formed 7 emulsions was taken up, coated on a cellulose triacetate film base, and then dried to prepare a control sample (Sample No; 41). Each of the remaining 6 emulsions was incorporated with such compound A as shown in Table;5, and then treated in the same-manner as in the case of the control sample to prepare samples (Samplew Nos. 42, 43, 44", 45, 46 and 47). 1

The thus prepared samples and control sample were individually developed at 24C. for 5 minutes by use of a developer of the following composition:

Benzyl alcohol Anhydrous sodium sulfite N-Ethyl-N-B-methylsulfonamidoethyl- 3-methyl-4-aminoaniline sulfate Sodium carbonate, monohyclrate Sodium bromide Water to make Photographic properties of the samples and control samples were as set forth in Table .Table 5 Sample Kind and amount'of Photographic No. compound A i properties (g/mole silver halide) Speed Fog Gamma 41 'r I 100 0.21 0.71 42 Com- (9) 2.75 120 0.14 0.77

pound As is clear from Table 5, it is understood that a lightsensitive silver halide color photographic material sensitized with a polyalkylene oxide type compound and containing a coupler can also give a brilliant color image high in speed and fog-free, so far as the photographic material has been incorporated with a tetrazaindene type compound and a compound A.

wherein the R 's are individually hydrogen, halogen, alkyl, aralkyl, alkoxy, acyl, carboxymethyl or a group- COOM or SO M, M is hydrogen, an alkali metal or ammonium R, and R are individually group COOM or SO M; and n, and n, are individually l to 3.

2. light-sensitive silver halide photographic material according to claim 1 wherein said tetrazaindene compounds are represented by the following general formula:

R N N Y R N\N 2 wherein R, is hydrogen, carboxyl, esterified carboxyl, mercapto, alkyl, aryl, heterocyclic, alkylthio, aralkylthio, or alicyclic; R is hydrogen, halogen, carboxyl, esterified carboxyl, amino, aryl, aralkyl, alicyclic, heterocylic, or thiuronium; and R is hydrogen, hydroxyl, carboxyl, esterified carboxyl, amino, alkyl, alicyclic, heterocyclic, or R, and R can cooperatively form a carbocycl icor hetero ring.

3. A light-sensitive silver halide photographic material according to claim 1 wherein the weight ratio of the amount of the compound represented by the general formula I or II to the amount of the tetrazaindene compound is from 0.1-l to 10-1. v

4. A light-sensitive silver halide photographic materila according to claim 1 wherein the compound of the general formula I or II is selected from the following compounds:

(1 on .(2) on (a) H 4) on @0005 on on coon 0H (6) r on coon OH H000, ,OHLH COOK CODE (7) 0H (8) on moo-on 3000 OH cn o 0H coon C H 'CH 4 9 l 2 0H OH coon m;

(11) on (12) on I on CH5 on (13) OH (14) on c1 9510003 HOOC I 03 0H on coon m Br

nooc on 5 nooca c -oH coon

Claims (4)

1. A LIGHT-SEMSITIVE SILVER HALIDE PHOTOGRAPHIC MATERIAL WHICH COMPRISES A LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER AND AN ADJACENT LAYER THEREOF, AT LEAST ONE OF WHICH CONTAINS 0.01 TO 5 G, PER MOLE OF SILVER HALIDE, OF AT LEAST ONE COMPOUND SELECTED FROM POLYALKYLENE OXIDE COMPOUNDS; 0.1 TO 50G, PER MOLE OF SILVER HALIDE, OF AT LEAST ONE COMPOUND SELECTED FROM TETRAZAINDENE COMPOUNDS; AND 0.1 TO 50G, PER MOLE OF SILVER HALIDE, OF AT LEAST ONE COMPOUND REPRESENTED BY THE GENERAL FORMULA I OR II,

2. A light-sensitive silver halide photographic material according to claim 1 wherein said tetrazaindene compounds are represented by the following general formula:

3. A light-sensitive silver halide photographic material according to claim 1 wherein the weight ratio of the amount of the compound represented by the general formula I or II to the amount of the tetrazaindene compound is from 0.1 - 1 to 10 - 1.

4. A light-sensitive silver halide photographic materila according to claim 1 wherein the compound of the general formula I or II is selected from the following compounds: