US3617294A

US3617294A - Spectrally sensitized silver halide photographic emulsion

Info

Publication number: US3617294A
Application number: US856487A
Authority: US
Inventors: Keisuke Shiba; Masanao Hinata; Akira Sato
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1968-09-09
Filing date: 1969-09-09
Publication date: 1971-11-02
Anticipated expiration: 1988-11-02
Also published as: GB1279493A; DE1944751A1; FR2017640A1

Abstract

Photographic silver halide emulsions and color photographic light-sensitive materials containing same, which emulsions comprise at least one benzimidazolocarbocyanine dye combined with at least one pseudocyanine dye containing either a benzothiazole or benzoselenazole nucleus and hydroxy-substituted at the 5position thereof. The emulsions may optionally contain, in addition a compound containing a benzimidazole nucleus. The emulsions resulting from the above combination of ingredients are green-sensitive emulsions possessing a uniformly high spectrally sensitized sensitivity over a region from 480 to 580 Mu and are not affected adversely by the presence of a color coupler in the emulsion. Further, the above combination of additives do not produce color stain upon development.

Description

United States Patent [72] lnventors Keisuke Shiba;

' Masanao Hinata; Akira Sato, all of Kanagawa, Japan [21] App1.No. 856,487 [22] Filed Sept. 9, 1969 [45] Patented Nov. 2, 1971 [73] Assignee Fuji Photo Film Co., Ltd.

Kanagawa, Japan [32] Priority Sept. 9, 1968 [33] Japan [31 43/64854 [54] SPECTRALLY SENSITIZED SILVER HALIDE PHOTOGRAPHIC EMULSION 10 Claims, No Drawings [52] US. Cl 96/124, 96/100, 260/240.6, 260/240.65, 260/2407, 260/2408 [51] Int. Cl G03c 1/28, G03c 1/40 [50] Field of Search 96/1 04, 106

[56] References Cited UNITED STATES PATENTS 2,052,754 9/1936 Dieterle et a1. 96/106 2,422,080 6/1947 Collins et a1. 96/104 2,973,264 2/1961 Nys et al 96/104 3,255,012 6/1966 Glockner et al 96/100 3,348,949 10/1967 Bannert et a1. 96/104 3,463,640 8/1969 Fickcn et al. 96/104 Primary ExaminerJohn T. Goolkasian Assistant Examiner-Robert A. Dawson Attorney- Sughrue, Rothwell, Mion, Zinn & Macpeak ABSTRACT: Photographic silver halide emulsions and color photographic light-sensitive materials containing same, which emulsions comprise at least one benzimidazolocarbocyanine dye combined with at least one pseudocyanine dye containing stabilizers present, the kind and properties Pat.

BACKGROUND OF TI-IE INVENTION Description of the Prior Art It is well known that spectral sensitizing is one of the techniques for producing silver halide photographic-emulsions. The spectral sensitivity obtained is largely influenced by the chemical structure of the sensitizing dyes used, the halogen composition of the silver halide contained in the emulsion, the crystalline system thereof, the extent of the chemical sensitization, the method of the chemical sensitization, the pAg of the emulsion, the pH thereof, the kind of binder contained in the emulsion, the kind and properties of of antifoggants properties of the wetting agents emand properties of hardening agent present, the kinds and played, and the kinds present.

Moreover, such-additives frequently act to lower the spectrally sensitized sensitivity of the emulsion. In particular, in the case of color photographic light-sensitive materials, the chemical structures of the sensitizing dyes and the manner of using them must be specifically selected so thatthe adverse influences of the colored couplers contained in the emulsions on the spectrally sensitized sensitivity are reduced as much as possible.

Further, some sensitizing dyes are known to impart higher sensitivity when they are used together with other dyes or colorless aromatic compounds having specific chemical structures, as compared with using these dyes individually. This is known as supersensitization. Combinations of compounds which provide supersensitization are required to be very rigidly selected. Thus, it is important to the spectral-sensitizing technique to find combinations of compounds which will coact to provide supersensitization.

Spectral sensitization for the green-sensitive region corresponding to a spectral region of high visual sensitivity is most important for the color reproduction of a color photographic light-sensitive material and the quality of the color image formed thereon. In regard to the spectral sensitization of the green-sensitive region, there is described, e.g., in US.

sensitizing action is only slightly obtained owing to the adverse influence of a color coupler present together with them. Moreover, although the method disclosed in the above U.S. patent results in a supersensitizing action, the supersensitization and the green sensitivity thus obtained are lower than those obtained by using a combination of, for example, a benzimidazolocarbocyanine dye and a benzoxazolo'carbocyanine dye (see Japanese Pat. Publication No. 4936/68 One reason for the disadvantages of the method of the above U.S. patent is considered to be a harmful inhibiting action occurring during the development process. On the other hand, the method shown in the aforesaid Japanese Pat. Publication No. 4936/68 is accompanied by the disadvantage that, although it may provide a high spectral sensitivity in the green region, contamination with dye remaining after the development procedure (hereinafter called "color stain) is large. Further, the latter method is accompanied by another disadvantage, in that the sensitivity in the region from 500 to 530 m,u., which is a portion of the shorter wave length, green region, is relatively low. 7

No. 2,701,198, a method wherein a benzimidazolonecarbocyanine dye and a pseudocyanine dye are used. However, wlieri this combination of se'nsitizers is employed in emulsions of color photographic light-sensitive materials, the spectral wherein Z, represents nonmetallic complete the benzimidazole nucleus; R represents an alkyl fopropyl, a-sulfobutyl,

2 SUMMARY OF THE INVENTION Thus, an object of the present invention is to provide a green-sensitive photographic silver halide emulsion which is not reduced in sensitivity when used in the presence ofa color coupler, which provides a uniformly high spectral sensitivity over the region from 480 to 580 mp., and which further imparts no color stain after the development procedure.

Another object of the present invention is to provide a color photographic light-sensitive material having, on a support, at least one layer of the aforesaid photographic silver halide emulsion.

The inventors have found that of this invention can be attained by incorporating in a photographic silver halide emulsion at least one of the benzimidazolocarbocyanine dyes represented by the formula the above-mentioned objects Ill Emmi a wherein 2;, represents nonmetallic atoms necessary to complete the quinoline nucleus; Y represents a sulfur atom or a selenium atomyR and R each represents an alkyl group or a substituted alkyl group, at least one of said groups R, and R being a sulfo-substituted alkyl group or a carboxy-substituted alkyl group; A represents a hydrogen atom, an alkyl group having one to four carbon atoms, or a' halogen atom; X represents an anion; and q is l or 2.

Moreover, as one embodiment of the present invention, it has been found that improved results can be obtained'by adding to the photographic silver halide emulsion, together with the aforesaid dyes, at least one of the compounds represented by the following formula atoms necessary to group or a substituted alkyl group and 2, represents a phenyl group or a substituted phenyl group.

DETAILED DESCRIPTION OF THE INVENTION As the sulfa-substituted alkyl group represented by R, or R, in formula I, there may be exemplified B-sulfoethylfiy-suly-hydroxy-l-sulfopropyl, 2-(3-sulfoprop0xy)ethyl, 2-[(3-sulfopropoxy)ethoxy]ethyl and the like. Further, as the carboxy-substituted alkyl group represented by R or R there may be exemplified B-carboxyethyl, B-carboxypropyl, 2-(2-carboxyethoxy)ethyl and the like. Moreover, as alkyl groups represented by R and R there may be exemplified methyl, ethyl, n-propyl and the like. As the substituted-alkyl group, there may be exemplified, besides the aforesaid sulfo-substituted alkyl group and the carboxy-substituted alkyl group, B-hydroxyethyl, B-acetoxyethyl and the like.

Furthermore, as the alkyl group and the substituted alkyl group represented by R, and R in formula 1, there may be exemplified methyl, ethyl, n-propyl, B-acetoxyethyl, and an alkyl group.

Z and Z of the formula represent the atoms necessary to complete the benzimidazole nucleus, as mentioned before, and the benzimidazole nucleus may be halogen, cyano, trifluoromethyl, alkyl-aminosulfonyl, or acetyl-substituted.

The alkyl group or substituted alkyl group represented by R or R in formula II are as set forth above in connection with R and R,,. At least one of R and R is a substituted alkyl group having either a sulfo group or a carboxyl group as set forth above in connection with R; and R,,. Z; in formula II represents the nonmetallic atoms necessary to complete a quinoline nucleus, as mentioned above, and the quinoline nucleus may be substituted by a methyl group, an ethyl group, a hydroxyl group, an alkoxyl group or a halogen atom.

X, and X, in general formulas l and II, respectively, are an anion, such as, a bromine ion, an iodine ion, a thiocyanate ion, an alkylsulfate ion, a perchlorate ion, and a p-toluenesulfonate ion. Also, the case wherein p is l and q is 1 in these formulas represents the formation of an intramolecular salt.

R, in general formula III is the alkyl group or the substituted alkyl group as set forth in connection with groups R; and R, in general formula 1. Moreover, as the substituent for the substituted phenyl group shown by group 2,, in general formula III, there may be illustrated an alkyl group such as a methyl group, an ethyl group, or a propyl group; and alkoxyl group such as a methoxy group or an ethoxy group; and a halogen atom such as a chlorine atom or bromine atom.

The feature of the sensitizing dye represented by general formula I is that at least one of R and R is a sulfo-substituted alkyl group or a carboxy substituted alkyl group as mentioned above, which renders the dye reactive for supersensitization by the sensitizing dye represented by general formula ll as well as for supersensitization by the compound represented by general formula III.

On the other hand, the feature of the sensitizing dye represented by general formula ll is that the benzothiazole or the benzoselenazole nucleus has a hydroxyl group at the 5- position thereof and also at least one of R and R is a sulfosubstituted alkyl group or a carboxyl substituted alkyl group. Most preferably, R is a sulfo-substituted alkyl group.

Sensitizing dyes wherein the benzothiazole or the benzoselenazole nucleus has a hydroxyl group at the 6-position have the drawback that the dye has high desensitizing properties and such dyes tend to form fog upon development. Also, sensitizing dyes having a hydroxyl group on the quinoline nucleus have the disadvantage that such dyes are weak in supersensitizing properties.

Accordingly, it is important that the sensitizing dye have a hydroxyl group at the 5-position of the benzothiazole or benzoselenazole nucleus.

In general, when a pseudocyanine dye having no substituent on the nucleus is substituted by a sulfo-alkyl group at the 5- or 6-position in general formula II, the dye provides hardly any spectral sensitivity. However, when a pseudocyanine dye having a hydroxyl group or a phenyl group at the 5-position of the benzothiazole nucleus or benzoselenazole nucleus is substituted by a sulfo-alkyl group at R; or R in the general formula, the spectral sensitivity obtained is markedly increased.

Furthermore, pseudocyanine dyes having a phenyl group at the 5-position have very weak supersensitizing action to the sensitizing dye represented by general formula I and form severe fog. On the other hand, pseudocyanine dyes having a hydroxyl group at the 5-position provide a strong supersensitizing action.

Since the pseudocyanine dye represented by general formula II and used in the present invention has a sulfo-alkyl or a carboxy-alkyl group and also has a hydroxyl group at the 5- position of the benzothiazole or benzoselenazole nucleus, photographic light-sensitive material having a photographic silver halide emulsion layer containing the dye gives less color stain after development. Also, in the case of using the aforesaid pseudocyanine dye, the reduction in spectrally sensitized sensitivity caused by the use of a color coupler is considerably less. However, the use of said pseudocyanine dye is accompanied with the disadvantage that the dye is diffused into adjacent emulsion layers to spectrally sensitize said emulsion layers owing to the poor adsorption power of the dye to silver halide. On the other hand, when the pseudocyanine dye mentioned above is used together with the sensitizing dye represented by general formula I, the spectrally sensitized sensitivity obtained by supersensitization is markedly increased, the harmful reduction of sensitivity caused by the presence of a color coupler together with the pseudocyanine dye can be completely prevented, and also the formation of color stain is reduced.

When the sensitizing dye represented by general formula ll is used together with the sensitizing dye represented by general formula I, no harmful inhibiting action in development by the dyes occurs and, to the contrary, the development tends to be promoted, each of which are particular advantages of the present invention.

The sensitivity in the spectrally sensitive region of from 500 to 530 mu obtained by the use of the combination of the sensitizing dye represented by general formula I and the sensitizing dye represented by general formula ll is higher than the sensitivity in that region obtained by the method disclosed in Japanese Pat. Publication No. 4936/68 mentioned above but, strictly speaking, is still not as great as desired. This difficulty can be overcome by further adding at least one compound represented by general formula III.

The sensitizing dyes and, if necessary, the compound used in the present invention, may be dissolved in a water-miscible organic solvent such as methanol, ethanol, alkalified ethanol, acidified methanol, acetone, or pyridine and they may be added to a photographic emulsion either as a mixture or separately. The amount of the additive is varied according to the kind of the silver halide emulsion to be employed but is preferably from 1Xl0'6 mole to 1X 104 mole per g. of the silver halide emulsion. The order of addition of these additives and the proportions may be varied according to the intended purpose.

In general, the ratio of the cyanine dye represented by general formula II to the cyanine dye represented by the general formula I may be from one-tenth to 10, the ratio of the cyanine dye represented by the general formula Ill to the cyanine dye represented by the general formula I may be from one-tenth to 10. As the photographic silver halide emulsion used in the present invention, there may be mentioned silver chloride emulsion, silver chlorobromide emulsion, silver bromide emulsion, silver iodobromide emulsion and the like. The photographic emulsion of this invention may further contain, aside from the sensitizing dyes of the present invention and, if necessary, the compound of general formula lll, such additives as a stabilizer, an antifoggant, a hardening agent, a wetting agent, a plasticizer, and the like. In particular, in the case of preparing a coupler incorporated type of color photographic light-sensitive material, a magenta coupler may be incorporated in the silver halide emulsion containing the aforesaid additives.

The photographic silver halide emulsion of this invention, prepared by the above-mentioned procedures, may be applied to a suitable support such as a cellulose derivative film, a baryta-coated paper, a glass plate, a polyethylene terephthalate film and the like.

Examples of the sensitizing dyes and the compound of formula 111 used in the present invention are shown below, although the invention is not limited only to those shown.

sensitizing dyes represented by general formula I (IA) (lhHs (E2115 C=CHCH=CH-C F 0 F N ((511928 OaNa MS a (1B) $3H5 (llzHs N N 01- -o1 C=CH-CH=CHC I 01 t SO NHC;H

CrHs QSS 3 (IO) 532E: $2H5 O=CHOH=OHC C1 -Ol (CH2)4COOH (01104000151 (ID) (12115 $H5 i v Cl -C1 C=CH--CH=OHC C1 -c1 N I (CH2CH2O)2(CH2)3SO3 (C 2 2 )2( 2)aS 3 N(C2H6)a Sensitizing dyes represented by general formula II:

IIA H3C S CH: \fi/ CH=C\ OH $2115 if] 93 3- (IIB) 01 s CH=C fi l I OH CH3 I? CHzC 00 HO 2 f CH=C m N/ OH CgHs 1? II D) i /se 011:0 i ID- 02 1? N lgHs IIE w a s l K \N CH= I 4 M a f MM Oa 2 i)a Compound represented by general formula III: 7

(IIIA) C2115 The sensitizing dyes represented by general formula I may be prepared by the methods described in, for instance, the specifications of U.S. Pat. No. 2,912,329 and Belgian Fat. Ni; 697,245.

Typical examples of preparing the sensitizing dyes represented by general formula II are briefly shown below.

1. Preparation of dye (II A):

To a mixture of ml. of ethanol and 6 ml. of triethyl amine were added 1 g. of l-ethyl-2-ethylmercapto-6-methylquinolinium p-toluenesulfonate and l g. of anhydro S-hydroxy-2,5-dimethyl-3-(y-sulfopropyl)benzothiazolium hydroxide and the mixture was refluxed by heating for 1 hour to cause the reaction. The crystals thus precipitated were filtered, washed with water, and recrystallized from a mixed solvent of methanol and chloroform to provide crystals of the dye (II A) having a melting point higher than 300 C. and a MaOH max.

of 506 my" Dyes (II B), (II C), (II D), and (ll E) can be also prepared by the above method.

2. the compounds represented by general formula 111 can be prepared by the following manner.

2. Preparation of compound (III A):

In 70 ml. of acetone was suspended 4.7 g. of 2-(5-anilinovinyl)-5,6-dichloro-l,3-diethylbenzimidazolium iodide and to the suspension was added dropwise a solution of 2 g. of sodium hydroxide in 25 ml. of water with stirring at room temperature. After 20 minutes, a large amount of water was added to the solution prepared. The crystals thus precipitated were filtered, washed with water, and recrystallized from ligroin to provide 1.2 g. of crystals ofcompound (III A) having a melting point of 151 C. and

MeOH max.

of 384 mu.

Other compounds, e.g., (Ill B) and (III C) can be prepared by the above procedure.

The following examples further illustrate the present invention.

EXAMPLE i In abeaker was melted 100 g. of a conventionally prepared gelatino silver iodobrornide emulsion (Agl 6.0 mole percent) and, after adding to the emulsion a methanol solution of the sensitizing dye or methanol solutions of the sensitizing dyes,

drying to provide a green-sensitive photographic silver halide EXAMPLE 2' In a beaker was melted 100 g. of a conventionally prepared gelatino silver iodobromide emulsion (Agl 4.0 mole percent) and, after adding to the emulsion a methanol solution of the light Sensitive material' 5 sensitizin d e or methanol solutions of the sensitizin d es The film was cut into strips and the same strip was exposed g y g y o 1 shown in table 2, the system was st1rred for 15 m1nutes at 35 to yellow llght through Fu 1 Filter 012 (a yellow filter made by FM Photo Film co usin an ti 3] Wed 6 d C. Then 20 ml. of a 5 percent alkalme solut1on of a magenta subbcted t M g g l g i z g coupler having the following structure was added to the emulo a w e 1 opmen an en lo sion with stirring and the system was neutralized by the addito provide a black and white negative image.

non of c1tr1c ac1d. By measurlng the denslty of the black and wh1te negative image thus obtained, the relative green sensitivity was then ob- 0 tained. CH & f

0n the other hand, an unexposed sample strip obtained as 1 2 above was subjected to a spectral exposure by means of a l reflection type grating spectroscope and then subjected to H O -C=N black and white development. By measuring the density of the image, a distribution curve of spectral sensitization was ob- A h d i ag nt wa added to the emulsion and thereafter tamed. the emulsion was immediately applied to a film support fol- These results are shown in table 1 together with the sensitizlo ed by drying to provide a green-sensitive color photoing dyes and the amounts thereof employed. The black and graphic light-sensitive material. white development was conducted for 10 minutes at 20 C. in The light-sensitive film was cut into strips and the sample the developer having the following composition. strip was subjected to a yellow exposure by means of a sensitometer. The sample thus exposed was subjected to a color Black and white developer development for 10 minutes at 20 C. in a color developer,

containing as a color developing agent at N,N'-diethylamin0- Nmemybpmminopheml Km 4 8. p-aminoaniline derivative, having the following composition; m w odlum ilfifig ham H H '7 so a- Hydroquinone 5 I- Color developer Sodium Carbon!" (m hy rm) 8- N,N-diethylamino-p-aminoanillne 2.0 5. Potassium bromide 5 g. (u-ate Potassium thiocyannte l g. Sodium gulf": 2 8' F flfl iodide 1 801W) 5 Sodium carbonate (monohydrate) 50.0 g. make L000 (PH 10120-1) hlydroxylemine hydrochloride [.5 g. Potassium bromide l.() g.

Water to make 1,000 ml. TABLE 1 (pH 10.11101 (B) (c) (D) (E) The sample was then subjected to first fixing, bleaching and second fixing to provide a magenta image. By measuring the 1. 40 density of the magenta image using a green light, a relative Mole, 1 1111. 70 0.08 563 green sensitivity was obtained. The results are shown in table 2 1111. 79 0.10 553 2' (llA) lxIO'J mole, 2 1111. 100 0.15 5558 T BLE 2 4 1111. 126 0.20 5512 21111. 41111. 159 015 550-560 (A) (B) (C) (D) (IB) 4x10" 11) 4x10" mole, 1 1111. 40 0.13 564 mole, 1 1111. 71 0.019 580 2 1111. 56 0.17 564 2 1111. 100 0.10 585 41111. 48 0.19 565 41111. 110 0.12 5113 113 11111. (lIA) 1x10" 50 2 1111. 11c 1 10" mole, 4 ml. I52 0.22 560 mole. 2 ml. 158 0.l2 578 2 1111. 4 1111. 152 0.22 550 2 1111. 4 1111. 195 0.13 576 21111. Sml. 188 0.14 540-570 2 1111. 66 0.011 550 l 28 o N 57 4 1111. 71 0.13 562 mo e, I rn 8 l. 98 .I

21111. 20 0.16 570 m o a 562 4 1111. 14 0.16 571 21111. 1112 1x10" 1o 4 10 11a 1 10'= 2 ml. Ml 0.16 550470 mole. 2 ml. mole, 2 ml. 42 0,10 5 0 2 1111. 4 1111. I60 0.17 550470 2 1111. 4 1111. I66 0.11 550-5so 2 1111. 80 0.13 570 2 1111. s 1111. 200 013 545-500 4 1111. 100 0.17 570 60 2 1111. 79 0.011 550 a 1111. 89 0.21 570 4 1111. 109 0.09 550 s 1111. 129 0.10 550 (lD)4x10" (llA) 1x10" Note: A) In order, the kind of the sens1t1z1n d e re resented mole, 2 1111. mole, 2 1111. 200 0.22 550473 g Y P by general formula I, the concentrauon of the dye, and the ad- 2 ml. (HA) 4 1111. 250 0.25 550 578 dition amount thereof; (B) In order, the kind ofthe sensitizing 2 $3? gas 223' dye represented by general formula II, the concentration of 4 166 562 the dye, and the addition amount thereof; (C) Relative se s 1111. 1711 0.32 562 sitivity; (D) Fog; and (E) Maximum sensitized wave length in mp" From the above results, it was clear that by the combination Note: (A), (B), (C), (D), and (F) have the same meanings of the two kinds of the sensitizing dyes represented by general as those in table 1. formulas I and II, respectively, a high supersensitization was The above procedure was followed except for the addition obtained without increasing the formation of fog to any harmof a compound represented by the general formula III. The

ful extent.

results are shown below:

TABLE 3 (A) (B) (D) (E) (F) (IB) 4X10- mole: (IIC) 1X10- mole:

2ml 4m1 200 0.16 562 2ml 4m1 (IIIA) 1X10- mole, 21111.. 235 0.15 560 (HA) 1X10- rnole:

Note: (A) In order, the sensitizing dye represented by general formula I, concentration of the dye, and addition amount thereof; (B) in order, the sensitizing dye represented by general formula II, the concentration of the dye, and the addition amount thereof; (C) In order, the compound represented by general formula III, the concentration of the dye, and the addition amount thereof; (D) Relative sensitivity; (E) Fog; and (F) The maximum sensitization wave length in mp.

What is claimed is:

1. A photographic silver halide emulsion comprising at least one cyanine dye represented by general formula] wherein Z and Z are each nonmetallic atoms necessary to complete the benzimidazole nucleus; R and R are each selected from the group consisting of an alkyl group, a substituted alkyl group and an allyl group; R and R. are each selected from the group consisting of an alkyl group and a substituted alkyl group, at least one of said groups R and R being eTtlTfi6ih the group coHsTst'iiig" '6? a sulTo-su'b'stimted alkyl group and a carboxy-substituted alkyl group; X, is an anion, and p is l or 2 and at least one cyanine dye represented by general formula 11 Fri-2+ (X?) 1-1 is wherein 2 represents nonmetallic atoms necessary to complete a quinoline nucleus; Y is selected from the group consisting of a sulfur atom and a selenium atom; R and R are each selected from the group consisting of an alkyl group and a substituted alkyl group, at least one of said groups R, and R being selected from the group consisting of a sulfo-substituted alkyl group and a carboxy-substituted alkyl group; A is selected from the group consisting of a hydrogen atom, an alkyl group having one to four carbon atoms and a halogen atom; X is an anion and q is 1 or 2.

. (IIIB) 1X10 mole, 21111.. 282 0.15 540-560 2. The photographic silver halide emulsion of claim 1 wherein said benzimidazolenucleus in general formula I is substituted by at least one member selected from the group consisting of a halogen atom, a cyano group, a trichloromethyl group, an alkylaminosulfonyl group and an acetyl group.

3. The photographic silver halide emulsion of claim 1 wherein said quinoline nucleus in general formula II is substituted by at least one member selected from the group consisting of a methyl group, an ethyl group, a hydroxyl group, an alkoxyl group and a halogen atom.

4. The photographic silver halide emulsion of claim 1 wherein said sulfo-substituted alkyl group represented by R; or R in general formula] and R or R in general formula II is selected from the group consisting of a [3 -sulfoethyl group, a 'ysulfopropyl group, a 'y-sulfobutyl group, a o-sulfobutyl group, a 2-hydroxy-l-sulfopropyl group, a 2-(3-sulfopropoxy)ethyl group, and a 2-[2-(3-sulfopropoxy)ethoxylethyl group.

5. The photographic silver halide emulsion of claim 1 wherein said carboxy-substituted alkyl group represented by R or R in general formula land R and R in general formula II is selected from the group consisting of a B-carboxyethyl group, an a-carboxypropyl group and a 2-(2-carb0xy-ethoxy)ethyl group.

6. The photographic silver halide emulsion of claim 1 wherein said silver halide emulsion containing said cyanine dyes is a green-sensitive silver halide emulsion containing a magenta coupler for color photographic light-sensitive materi- 7. A color photographic light-sensitive material comprising a support and at least one layer of a photographic silver halide emulsion as set forth in claim 1.

8. A photographic silver halide emulsion as set forth in claim 1 further comprising at least one compound represented by general formula III I h (III) wherein 2., represents nonmetallic atoms necessary to complete a benzimidazole nucleus; Z is selected from the group consisting of a phenyl group and a substituted phenyl group; and R is selected from the group consisting of an alkyl group and a substituted alkyl group.

9. The photographic silver halide emulsion of claim 8 wherein said silver halide emulsion is a green sensitive silver halide emulsion containing a magenta coupler for color photographic light-sensitive material.

10. A color photographic light-sensitive material comprising a support and at least one layer ofa silver halide emulsion as set forth in claim 8.

Claims

2. The photographic silver halide emulsion of claim 1 wherein said benzimidazolenucleus in general formula I is substituted by at least one member selected from the group consisting of a halogen atom, a cyano group, a trichloromethyl group, an alkylaminosulfonyl group and an acetyl group.
3. The photographic silver halide emulsion of claim 1 wherein said quinoline nucleus in general formula II is substituted by at least one member selected from the group consisting of a methyl group, an ethyl group, a hydroxyl group, an alkoxyl group and a halogen atom.
4. The photographic silver halide emulsion of claim 1 wherein said sulfo-substituted alkyl group represented by R3 or R4 in general formula I and R5 or R6 in general formula II is selected from the group consisting of a Beta -sulfoethyl group, a gamma -sulfopropyl group, a gamma -sulfobutyl group, a delta -sulfobutyl group, a 2-hydroxy-1-sulfopropyl group, a 2-(3-sulfopropoxy)ethyl group, and a 2-(2-(3-sulfopropoxy)ethoxy)ethyl group.
5. The photographic silver halide emulsion of claim 1 wherein said carboxy-substituted alkyl group represented by R3 or R4 in general formula I and R5 and R6 in general formula II is selected from the group consisting of a Beta -carboxyethyl group, an Alpha -carboxypropyl group and a 2-(2-carboxy-ethoxy)ethyl group.
6. The photographic silver halide emulsion of claim 1 wherein said silver halide emulsion containing said cyanine dyes is a green-sensitive silver halide emulsion containing a magenta coupler for color photographic light-sensitive material.
7. A color photographic light-sensitive material comprising a support and at least one layer of a photographic silver halide emulsion as set forth in claim 1.
8. A photographic silver halide emulsion as set forth in claim 1 further comprising at least one compound represented by general formula III
9. The photographic silver halide emulsion of claim 8 wherein said silver halide emulsion is a green sensitive silver halide emulsion containing a magenta coupler for color photographic light-sensitive material.
10. A color photographic light-sensitive material comprising a support and at least one layer of a silver halide emulsion as set forth in claim 8.