US3873324A

US3873324A - Spectrally sensitized silver halide photographic emulsion

Info

Publication number: US3873324A
Application number: US447114A
Authority: US
Inventors: Masanao Hinata; Haruo Takei; Keisuke Shiba
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1973-02-28
Filing date: 1974-02-28
Publication date: 1975-03-25
Anticipated expiration: 1992-03-25
Also published as: DE2409620A1; FR2219443A1; JPS49114419A; GB1413645A

Abstract

A silver halide emulsion spectrally sensitized with a combination of a cyanine dye of the general formula (I) as hereinafter defined and a cyanine dye of the general formula (II) as hereinafter defined and having spectral sensitivity in the wave length region ranging from 580 nm to 640 nm.

Description

nited States Patent Hinata et al.

[ Mar. 25, 1975 SPECTRALLY SENSITIZED SILVER HALIDE PHOTOGRAPHIC EMULSION Inventors: Masanao Hinata; Haruo Takei;

Keisuke Shiba, all of Kanagawa, Japan Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan Filed: Feb. 28, 1974 Appl. No.: 447,114

Foreign Application Priority Data Feb. 28, 1973 Japan 48-23987 U.S. Cl. 96/124, 96/100 Int. Cl G03c 1/14 Field of Search 96/124, 137, 100

[56] References Cited UNITED STATES PATENTS 3,666,480 5/1972 Shiba et a1. 96/124 3,672,898 6/1972 Schwan et a1 96/124 3,702,251 11/1972 Sato et al 6/124 3,799,783 3/1974 Hill et al. 96/124 Primary Examiner-J. Travis Brown Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak 13 Claims, 18 Drawing Figures SPECTRALLY SENSITIZED SILVER HALIDE A further object of the present invention is to selec- PHOTOGRAPHIC EMULSION tively find supersensitizing dyes which, when incorporated in one layer of a multi-layered light sensitive ma- BACKGROUND OF THE INVENTION terial to spectrally sensitize the layer selectively so as 1. Field of the lnvention 5 to attain the abovedescribed objects of the present in- The present invention relates to asilver halide photovention, do not diffuse into adjacent layers to cause graphic emulsion which is spectrally sensitized in a spesensitization therein. cific wave-length region by supersensitization and, A still further object of the present invention is to more particularly, it is concerned with a silver halide find sensitizing dyes which are more selective, which photographic emulsion spectrally sensitized in a wavecause less color stain after development-processing and length region of from 580 nm to 640 nm. which cause less reduction in sensitivity even upon 2. Description of the Prior Art storage after production of the light sensitive material Commonly used photographic light-sensitive materi- (spectrally sensitized by the dyes).

als are provided with a suitable spectral sensitization distribution ranging over the visible wave-length region SUMMARY OF THE INVENTION to which the human eye is sensitive. In order to impart The above-described objects can be attained as folmore Suitable Color reproducibility, more appropriate lows, i.e., by incorporating a supersensitizing combinasensitization distribution is required. Therefore, comi n of at least one carbocyanine dye represented by binations showing supersensitization comprising two th f ll wi neral formula (I);

or more sensitizing dyes are being studied and selected wherein 2, represents the atoms necessary to form a for use. benzothiazole ring, a benzoselenazole ring, a B-naph- From the standpoint of obtaining excellent color rethothiazole ring or a ,B-naphthoselenazole ring; Z repproducibility, it is not preferable to impart high sensiresents the atoms necessary to form a benzoselenazole tivity too far in the longer wave length region, e.g., ring; A represents a hydrogen atom or an alkyl group; longer than 660 nm (wave length of the sensitization R1 and R2 each represent an alkyl group or a substimaximum) or, conversely, to impart sensitivity only in tuted alkyl group, at least O Of 1 and 2 being a a too short wave length region, e.g., less than 580 nm droxyalkyl group, a carboxy-substituted alkyl group or (wave length of the sensitization maximum). a sulfo-substituted alkyl group; X, represents an acid However, in the conventional spectrally sensitizing anion group; and m represents 1 or 2 and, when the dye art. it has been difficult to selectively increase the sensif rms an in rnal alt t in -lik Structure), H1 ptivity in the wave length region ranging from 580 nm to resents l; a d at least One carbocyanine dye repre- 640 nm and the solution of this problem has been an Se ed y the general formula important subject in this art.

It is, therefore, an object of the present invention to wherein Z and Z, each represent the atoms necessary provide a novel supersensitizing combination to selecto form a halogen-substituted benzimizadole nucleus; tively increase the sensitivity in the wave length region R, and R, each represents an alkyl group or a substiranging from 580 nm to 640 nm. tuted alkyl group, at least one of R and R being a hy- Another object of the present invention is to provide droxyalkyl group, a carboxy-substituted alkyl group or a supersensitizing combination which mitigates the rea sulfo-substituted alkyl group; X, represents an acid duction in sensitivity experienced in conventional comanion; and n represents 1 or 2 and, when the dye forms binations of supersensitizing dyes. an internal salt, n represents 1.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 17 are spectrograms of photographic materials as described in the Examples and FIG. 18 showsthe per cent transmission curve of the filters used in the Examples.

DETAILED DESCRIPTION OF THE INVENTION Suitable examples of substituents which can be present on the Z, or Z containing heterocyclic nucleus are a halogen atom (e.g., chlorine, fluorine, bromine), a lower alkyl group preferably having no more than 4 carbon atoms in the carbon chain (e.g., methyl, ethyl, etc.), an alkoxy group (e.g., methoxy, ethoxy, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl, etc.), a trifluoromethyl group, a hydroxy group and a carboxy group.

In the general formulae (I) and (II) which represent the sensitizing dyes to be used in the present invention, the heterocyclic ring formed by Z includes, e.g., benzothiazole, 5-chlorobenzothiazole, 5- bromobenzothiazole, S-fluorobenzothiazole 5 methylbenzothiazole, 5-methoxybenzothiazole, 5-

e.g., l-methyl-5-chlorobenzimidazole, l-methyl-5- fluorobenzimidazole, l-methyl-5,6- dichlorobenzimidazole, I-ethyl-S- chlorobenzimidazole, I-ethyl-5-fluorobenzimidazole, l-methyl-S ,o-dichlorobenzimidazole, l-ethyl5 ,6- difluorobenzimidazole. l-propyl-5- chlorobenzimidazole, l-propyl-5-fluorobenzimidazole, l-propyl-S ,o-dichlorobenzimidazole, l propyl-5 ,6- difluorobenzimidazole, l-allyl-S-chlorobenzimidazole,

l-allyl5-fluorobenzimidazole, I-allyl-5,6- dichlorobenzimidazole, l-allyl-5,6- difluorobenzimidazole, l-phenyl-S- chlorobenzimidazole, l-phenyl-5-fluoroben2imidazole, I-phenyl-5,o-dichlorobenzimidazole l-phenyl-5,6- difluorobenzimidazole ring, l-acetoxyalkyl (e.g., propyl, etc.)-5,6-dichlorobenzimidazole, l-hydroxyalkyl (e.g., ethyl, etc.)-5,6-dichlorobenzimidazole, and the like.

A represents, for example, a hydrogen atom, an alkyl group, preferably having up to 3 carbon atoms, e.g., a methyl group, and ethyl group, a propyl group, or the like.

R R R and R each represents an alkyl group such as an unsubstituted alkyl group (e.g., a methyl group, an ethyl group, a propyl group), a hydroxyalkyl group (e.g., a Z-hydroxyethyl group, a 3-hydroxypropyl group, etc.), a carboxy-substituted alkyl group (e.g., a Z-carboxyethyl group, a 3-carboxypropyl group, a 4- carboxybutyl group. etc.), a sulfo-substituted alkyl group (e.g., a 2-sulfoethyl group, a 3-sulfopropyl group. a 3-sulfobutvl group. a 2I3-sulfopropoxvlethvl group, a 2-hydroxy-3-sulfopropyl group, a 3-sulfopropoxyethoxyethyl group, etc.), an acetoxyalkyl group (e.g., acetoxyethyl, etc.), a cyanoalkyl group (e.g., cyanopropyl, etc.), a carbamoylalkyl group (e.g., B-carbomoylethyl, etc.), a morpholinocarbanylalkyl group [e.g., B-(4-morpholinocarbonyl)ethyl, etc.], an allyl group, a morpholino sulfonylalkyl group [e.g., 8-(4-morpholinosulfonyl)butyl, etc.], or the like in which the alkyl moiety has, preferably up to 8 carbon atoms.

X," and X each represents an acid anion commonly employed in cyanine dye salts, such as an iodide ion, a bromide ion, a chloride ion, a p-toluenesulfonate ion, a benzenesulfonate ion, an ethylsulfate ion, a perchlorate ion, a rhodanide ion, or the like. It is preferred that when two benzimidazole nuclei in the dye of general formula (II) are each substituted with chlorine atom(s), one of R and R is a hydroxyalkyl group, a carboxysubstituted alkyl group or a sulfo-substituted alkyl group and the other is a carbamoylalkyl group, an acetoxyalkyl group, a morpholinocarbonyl group. a cyanoalkyl group, a morpholinosulfonyl group. or an allyl group; or at least one of the nitrogen atoms at the 1- position ofthe dye of general formula (II) is substituted with an aryl group. an acetoxyalkyl group or an allyl group. Incidentally.

If: R: or RI. illustrates the above.

A chemical structural feature of the sensitizing dyes represented by the general formula (I) is that they are carbocyanine dyes wherein one or, preferably, two of the substitutents connected to the nitrogen atom or atoms in the nitrogen-containing heterocyclic nueleus or nuclei are hydroxyalkyl groups, carboxysubstituted alkyl groups or sulfo-substituted alkyl groups. These dyes show maximum sensitivity in the wave length region ranging from about 600 nm to about 670 nm. Furthermore, they have the feature that, when used in combination with the dye represented by the general formula (II), they increase the spectral sensitivity while maintaining the light sensitivity maximum at a wave length of from about 600 nm to about 630 nm.

A chemical structural feature of the sensitizing dyes represented by the general formula (II) is that they are imidazolocarbocyanines having a hydroxyalkyl group, a carboxy-substitutcd alkyl group or a suIfo-substituted alkyl group as the substituent connected to the nitrogen atom in the nitrogencontaining heterocyclic nucleus. These dyes show maximum sensitivity in the wave length region ranging from about 570 to about 585 nm and scarcely cause color stain after development processing.

The supersensitizing action by the combined use of the dyes of the present invention strongly counteracts prevention of spectral sensitization due to presence of a color coupler. For example, the desensitization, conventionally experienced in the combined use of a sensitizing dye and a coupler, is extremely small. In addition, since these dyes rarely diffuse into adjacent emulsion layers when applied to one light sensitive layer of a multi-layer light sensitive material. they never sensitize the adjacent layers (silver halide emulsion layers). The above-described effects are never adversely affected even when a color sensitizer (e.g., 2,2-cyanine, thia-2- cyanine, etc.) to increase the green-sensitivity or other color sensitizers (e.g., thiacarbocyanine, etc.) are used in combination.

The supersensitizing technique in accordance with the present invention are useful for the production of ortho-pan type light sensitive emulsions, light sensitive emulsions for mult-layer coupler in the emulsion type color films, particularly, reversal color films and negative color films, for example, as disclosed in US. Pat. Nos. 2,698.794; 2,474.293; 2,600,788; 3,311,476; 3.458.315; 3,214,437 and 3,253,924.

Specific examples of the sensitizing dyes which can be used in the present invention are illustrated below. However, the present invention is not limited to the dyes specifically described below.

Specific examples ofthe dyes represented by the general formula (l):

Se\c (HHS /Se CH C CH C 5 (I +1) N N (lm hon Br" (Hz)zOH Se\ CH3 /Se (CHm BH H0380;

S\ /Se /C=CH-C=CHC\ J@ l l (CH; s'o n (on: ,so,

/ Se\ I /Se 1 c cu c on c cn,o lil 1 4o (CHz)zCOOH tcnzizc Specific examples of the dyes represented by the general formula (II):

CzHs C2H5 N on c on on CH 11 I \\N at (CHz 2 )2( 2)a s- 13 14 Sensitizing dyes used for comparison in demonstrating lae (I) and (II) of the present invention are described the effects of the present invention are as follows: below:

Se\ /Se c on c cn' 0V on: N 1;! on,

I 6 H; BI (3H5 Se f ,Se -C=CH-C=CH-C N I l I CgHs I 2 5 1 2 s $2 5 C9. n I 11 C2.

C=CH-CH=CH-C CR. N N or. I I C2H5 5t CZHS Suitable sensitizing dyes which can be used together mbiaatiqwitha ensr rfoml Q (Dfj CH N I N I I (CHZ)SSOS ),S0 HN(CzHs)s I CH N I I (OH: ,so, 0211;

03H; S I C 1 CH C 8 CH C N N The silver halide photographic emulsions which can be used in the present invention are those produced in a conventional manner and containing silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide or mixed silver halide grains thereof, which are precipitated through a single jet method, a double jet method, or a combination of these methods followed by ripening. A preferred silver halide is silver bromoiodide or silver chlorobromoiodide and a preferred mean diameter of the grains (measured by, e.g., a projected area method or a number average method) is from 0.04 micron to 2 microns. Suitable examples of and the preparation thereof are disclosed in U.S. Pat. Nos. 3,217,157; 2,222,264; 3,320,069; 2,592,250; 3,206,313; and 3,367,778 and Belgian Pat. No. 704,255; U.S. Pat. NO. 2,996,382 and Klein and Moisar Journal of Photographic Science, volume 12, page 242 et seq., or Markvcki The Spectral Sensitization of Silver Bromide Emulsion on Different Crystallographic Faces", Journal of Photographic Science, volume 13, 1965.

To the silver halide photographic emulsion used in the invention conventionally employed chemical sensitization techniques such as gold sensitization (as described in U.S. Pat. Nos. 2,540,085; 2,597,856; 2,597,915; 2,399,083; etc.), sensitization with a Group V111 metal ion, sulfur sensitization (as described in U.S. Pat. Nos. 1,574,944; 2,278,947; 2,330,206; 2,410,689;

3,189,458; 3,415,649; etc.), reduction sensitization (as described in U.S. Pat. Nos. 2,518,698; 2,419,974; 2,983,610; etc.), or a combination of these sensitization techniques can be employed.

More specifically, the emulsion can contain a sulfur sensitizer such as allylthiocarbamide, thiourea, sodium thiosulfate or cystine; a noble metal sensitizer such as potassium chloroaurate, aurous thiosulfate, or potassium chloropalladate; a reduction sensitizer such as tin chloride, phenylhydrazine or reductone; and the like. Also, the emulsion can contain such a sensitizer as a polyoxyethylene derivative, a polyoxypropylene derivative, a quaternary ammonium group-containing derivative or the like. Furthermore, the emulsion can contain an antifogging agent such as nitrobenzimidazole or ammonium chloroplatinate, and a stabilizing agent such as 4-hydroxy-6-methyl-l,3,3a,7-tetrazaindene.

In addition, the emulsion can contain a hardener, such as formaldehyde, chrome alum, l-hydroxy-3,5- dichlorotriazine sodium salt, glyoxal, dichloroacrolein, etc., and a coating aid such as saponin, sodium alkylbenzenesulfonate, etc.

Particularly preferred examples of hardeners are aldehyde series compounds such as formaldehyde, glutaraldehyde and halocarboxyaldehydes (e.g., mucochloric acid); ketones such as diacetyl and cyclopentanedione; active halogen-containing compounds such as bis(2-ch1oethyl urea), 2-hydroxy-4,6-dichloro-l ,3,5- triazine and those compounds as disclosed in U.S. Pat.

974,723 and 1,167,207; active olefin-containing compounds such as divinylsulfone, 5-acetyl-l,3- diacryloylhexahydro-l,3,5-triazine and those compounds as disclosed in U.S. Pat. Nos. 3,635,718; 2,232,763; 3,490,911 and 3,642,486 and British Pat. No. 994,869; N-methylol compounds such N-hydroxymethylphthalimide and those compounds as disclosed in Us Pat. Nos. 2,732,316 and 2,586,168; isocyanates as disclosed in U.S. Pat. Nos. 3,103,437; aziridines as disclosed in U.S. Pat. Nos. 3,017,280 and 2,983,611; acid derivatives as disclosed in U.S. Pat. Nos. 2,725,294 and 2,725,295; carbodiimide series compounds as disclosed in U.S. Pat. No. 3,100,704; epoxy compounds as disclosed in U.S. Pat. No. 3,091,537; isooxazoleseries compounds as disclosed in U.S. Pat. Nos. 3,321,313 and 3,543,292; dioxane derivatives such as dihydroxydioxane and dichlorodioxane and inorganic hardeners such as chrom alum and zirconium sulfate, precursors of the above-described materials such as addition compounds of an alkali metal bisulfite and an aldehyde, methylol derivatives of hydrazine, and primary aliphatic nitro alcohols and those compounds as disclosed in U.S. Pat. Nos. 3,288,775; 3,017,280 and 2,983,611 and British Pat. No. 1,167,207. Any of the known surface active agents as a coating aid can be employed and sepcifically, anionic surface active agents containing acidic groups such as a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfate group, a phosphate group, etc., ampholytic surface active agents of carboxylic acid type, sulfonic acid type, sulfate type or phosphate type; nonionic surface active agents of the polyalkyleneoxide series or the polyglycerin series; and natural surface active agents such as saponin, are preferably used. Suitable such materials and the amounts thereof generally suitable for use are disclosed for example, in

U.S. Pat. Nos. 2,600,831; 3,068,101; 3,415,649; 3,617,286; 2,271,623; 2,240,472; 2,288,226; 2,739,891; 3,158,484; 3,201,253; 3,210,191; 3,294,540; 3,415,649; 3,441,413; 3,442,654; 3,475,174; 3,545,974; German OLS No. 1,942,665;

and British Pat. Nos. 1,077,317 and 1,198,450.

When used in a color photographic light sensitive material, the silver halide emulsion used in the present invention contains a color coupler and a dispersing agent therefor.

Of the color couplers, a cyan coupler is particularly preferred. For example, the phenolic couplers as described in U.S. Pat. No. 2,698,794 and the naphtholic couplers as describedin U.S. Pat. No. 2,474,293 are particularly useful. Also, the couplers described in US. Pat. No. 2,600,788, British Pat. No. 904,852 and Japanese Patent Publication Number 603 1/65, the a-naphtholic cyan couplers and the phenolic cyan couplers described in, e.g., U.S. Pat. Nos. 3,311,476; 3,458,315; 3,214,437 and 3,253,924 can be used. For example, the couplers represented by the following structural formulae can be used, all of which are known com- Nos. 3,288,775 and 2,732,303 and British Pat. Nos. pounds.

HzC-fi NHCO Ha 1C: 5 CONH COOH COCHzCONH COOH OCH:

- CO(|ZH CONH NHCOfHCSH? C2 O COCHzCONH NHCOCHzO C5H11('G) OCHa cslhflt) Photographic emulsions spectrally sensitized with the dye combinations of the present invention can contain various colloids alone or in combination as vehicles or binding agents. Suitable hydrophilic materials include both naturally-occurring substances such as proteins, for example, gelatin, gelatin derivvtives suchas phthaloylated gelatin or malonoylated gelatin, cellulose derivatives such as hydroxyethyl cellulose or carboxy methyl cellulose, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as water soluble polyvinyl compounds, c.g., polyvinyl alcohol, poly(vinylpyrrolidone), acrylamide polymers, polystyrenesulfonic acid, or other synthetic polymeric compounds such as dispersed vinyl compounds in latex form, and particularly those which increase the dimensional stability of the photographic materials. Suitable synthetic polymers include those described, for example, in US. Pat. Nos. 3,142,568; 3,193,386; 3,062,674; 3,220,844; 3,287,289 and 3,411,911. Particularly effective are those water insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, those which have cross linking sites which facilitate hardening or curing and those having recurring sulfobetaine units as described in Canadian Pat. No. 774,054. As the matting agent which can also be present in the emulsion, there are preferably used silver halide grains of a suitable grain size; inorganic compounds such as silica, strontium barium sulfate, etc.; water-dispersable vinyl polymers such as polymethyl methacrylate, etc. Examples of plasticizers which can be present in the emulsion are waxes such as liquid paraffin, higher fatty acid esters, etc.; polyfluorinated hydrocarbons or derivatives thereof;

silicones such as polyalkylpolysiloxane, polyarylpolysiloxane, polyalkylarylpolysiloxane or the alkylene oxide adduct derivatives thereof; and the like are preferably used. I r

The finished emulsion is applied to a suitable support such as baryta paper, a resin-coated paper, a synthetic paper, a triacetate film, a polyethylene terephthalate film, a gl'ass plate or other plastic bases.

These addenda described above are used in an amount to achieve their known function and such can easily be determined by one skilled in the art.

The sensitizing dyes of the general formula (1) and (11) used in the present invention are added as a solution prepared by dissolving the dyes in water or a water-miscible organic solvent such as methanol, ethanol, t yl. qsq vst2y isli OI sl e- Each of these dyes is used in the amount usually employed in supersensitization, c.g., 5 X 10 mol to l X 10 mol, preferably 1 X 10" mol to 1 X 10' mol, per 1 mol of silver. A preferred molar ratio of the amount of the dye represented by the general formula (11) to that of the dye represented by the general formula (1) ranges from 1:10 to 10:], particularly 1:5 to 5:1 and more particularly 1:3 to 3:].

Also, the dyes to be used in the present invention can be used for spectral sensitization according to German OLS Pat No. 2,104,284 and US. Pat. No. 3,649,286.

The present invention will now be illustrated in greater detail by reference to the following examples which, however, are not intended to limit the present invention in any way. Unless otherwise indicated. all parts, percents, ratios and the like are by weight.

23 EXAMPLE 1 ameter of 0.42 p. and this emulsion contained 0.52 mol silver halide per 1 kg. 1 kg portions of this emulsion were weighed out in a pot, which was then placed in a 50C thermostatic bath to melt the emulsion. Methanol solutions of the sensitizing dyes of the present invention and sensitizing dyes for comparison were added to the emulsion portions in predetermined amounts (as shown in Table I), and mixed and stirred at 40C.

To each emulsion portion were added 10 cc of a 0.1 by weight aqueous solution of 4-hydroxy-6-methyl- I,3,3a,7-tetrazaindene, 10 cc of a 1 by weight aqueous solution of I-hydroxy-3,5-dichlorotriazole sodium salt and 10 cc of a I by weight aqueous solution of soidum dodecylbenzenesulfonate, and stirred. Each of the thus finished emulsion portions was applied to a cellulose triacetate film base in a dry thickness of 5 p. and then dried. Thus, light sensitive material samples were obtained. Each of these film samples was cut into. strips. Three of the strips were wedgewise exposed using a sensitometer containing a light source of a color temperature of 5400K light source being covered, respectively, by a blue filter (Sp-I a yellow filter. (Sc- 50) and a red filter (Sc-56) (made by the Fuji Photo 30 Film Co., Ltd.) On the other hand, one remaining strip was exposed using a grating spectrophotograph having a 2660K tungsten light source to obtain spectrograms.

20 Water to make The thus exposed strips were development-processed at 20C for 2 minutes using a developer (D-I9) having the following composition followed by stopping, fixing and washing. Thus, strips having given black-and-white images were obtained. The density of these images was measured using a S-type densitometer (made by Fuji Photo Film Co., Ltd.). Thus, the blue filter sensitivity (S yellow filter sensitivity (5,), red filter sensitivity (S and fog were obtained. The standard point of the optical density to determine the sensitivity was fog Composition of the Developer (D-I9):

Water Metol 2 Sodium Sulfite (anhydrous) 90 Hydroquinone 8 Sodium Carbonate (monohydrate) 2. Potassium Bromide 5 The results obtained are shown in Table I as the relative values.

Run Nos. 3, 4, 9 and 12 were conducted for comparison.

The spectral transmission curves of filter Sp-I, filter Sc-SO and filter 80-56 are shown in FIG. 18. The spectrograms obtained are shown in FIGS. 1 to 10. From the values given in Table I and from the spectrograms. it can be seen thatthe effects of the combination of dyes of the present invention showing a supersensitizing action are excellent.

TABLE I Dye and Amount D e and Amount Dye and Amount No. Uscd X 10 me! sad X 10 mol Used X 10'' mol Sy* S,,* S,,* Fog spectrogram I (I A) I 160 88 94 0.07 FIG. 1 1

2 280 I64 86 0.07 4 360 230 80 0.07 (11 B) I 127 75 94 0.07 2 I80 I00 86 0.09 4 I98 107 75 0.10 FIG. I 2 (l-A) I (II-B) 4 420 270 88 010 FIG. 1-3 2 4 420 285 80 0.10 2 (6) I 75 98 0.07

2 I14 100 90 0.08 FIG. 2 4 (I -A) I (II-B) 4 (6) 2 570 370 92 0.10 FIG. 2-5 3 (I) I I24 53 86 0.07

2 I 73 78 0.07 FIG. 3 6 4 200 86 70 0.07 (I) I (II B) 4 328 I96 78 0.09

2 4 338 206 73 0.10 FIG. 3 7 4 (3 I 56 25 80 0.07 2 I10 46 0.09 4 I17 49 68 0.11 FIG.4-8 (I-A) l (3) v4 280 I60 7 0.10

2 j 4 280 I69 67 0.10 FIG. 4 9 5 (I E) I 100 I00 88 0.07 FIG. 5 10 2 I68 146 70 0.07 4 250 230 60 0.07 (I-E) I (II-B) 4 400 250 92 0.10 FIG.5-I1

2 4 420 272 84 0.10 6 (I-E) 1 (11 B) 4 (6) 2 505 358 92 0.10 7 (7) 0.5 100 0.07 FIG. 6 12 1 118 96 0.07 (1-E) I (II-B) 4 (7) 0.5 480 330 96 0.10 FIG.6- I3 8 (4) 4 I8 100 0.07 FIG. 7 I4 8 20 92 0.08 (I-E) I (II-B) 4 (4) 4 472 250 92 0.10 FIG.7-15 9 (2) I 22 I2 62 0.07

2 24 23 50 0.10 FIG. 8 l6 4 27 25 45 0.13 (2) I (II B) 4 I46 88 55 0.09

2 4 146 91 46 0.10 FIG.8-17

tion was added to a mixture, prepared by adding as an aqueous solution 2.5 g of dodecylbenzenesulfonic acid to 1 kg of a 10 by weight gelatin, stirred at a high speed and subjected to ultrasonic wave stirring to emulsify. Thus, an emulsion was obtained.

1 kg portions of the silver bromoiodide emulsion prepared according to the method of Example 1 were weighed out in a pot. which was then placed in a 50C thermostatic bath to melt the emulsions. Methanol so-' lutions of the sensitizing dyes of the present invention and the sensitizing dyes for comparison were added to the emulsion portions in predetermined amounts (as shown in Table 2), mixed and stirred at 40C, and then left for IS minutes. To each emulsion portion were added 250 g of the above-described emulsion, l cc of a 0.1 by weight aqueous solution of 4-hydroxy-6- methyl-l,3,3a,7-tetrazaindene, 10 cc of a l by weight aqueous solution of l-hydroxy-3,5- dichlorotriazine sodium salt and 10 cc of a 1 by fonate, and stirred.

Each of the thus finished emulsion portions was applied to a cellulose triacetate film base in a dry thickness of p. followed by drying. Thus, light sensitive material samples were obtained.

Each of these film samples was cut into strips. One of the strips was wedgewise exposed through a red filter Sc-56 using a sensitometer containing a light source of a color temperature of 5400K.

This was development-processed at 24C for minutes in a developer having the following composition followed by washing. hardening, washing and second reversal exposure.

'45 weight aqueous solution of sodium dodecylbenzenesul- TABLE l-Continued Dye and Amount Dye and Amount Dye and Amount No Used X l0 mol Used X 10" mol Used X 10" mol S\-* S,,* S,,* Fog spectrogram l mo 92 92 0.07 FIG. 9 l8 2 I42 I30 0.08 10 (ll E) l 140 86 98 0.07 2 198 I 10 90 0.08 4 230 88 008 FIG. 9 19 (l F) 0.5 (ll E) 4 395 350 92 0.08

1 4 405 358 92 0.08 FIG. 9 20 11 (I A) I (ll E1 4 432 280 96 0.08 FIG. l0 21 2 4 128 80 40 0.10 FIG. 10 22 100 0.07

* Relative value EXAMPLE 2 Composition of the Developer:

N-Methyl-p-aminophenol 4.5 g 20 Hydroquinone 4.5 g 80 grams of a cyamne coupler, l-hydroxy-4- Sodium Sultite (anhydrous) 50 g maleimidO-Z-naphthamide, was completely dissolved in gg tgg g gg if g a mixed solution of [00 cc of tricresyl phosphate and Potassium Thiocyanate 2 g 50 cc of ethyl acetate. Furthermore, 2 g of sorbitan Wate'm make I I monolaurate was dissolved therein. The resulting solu- 25 The strip was then color development-processed at 24C for 15 minutes in a color developer having the following composition followed by washing, bleaching, washing, fixing and washing. Thus, a color positive image was obtained.

Composition of Color Developer:

p-Amino-Nethyl-N-/3-mcthanesullonamidoethyl-m-toluidine Sulfate Water to make the total l l The density of the thus obtained strips was measured using an S-type densitometer (made by Fuji Photo Film Co. Ltd.) to obtain the relative sensitivity and cyan color fog. The standard point of the optical density to determine the sensitivity was fog 0.5. The results obtained are shown in Table 2.-

Run Nos. 3, 4, 7 and 8 were conducted for comparison.

On the other hand, the one remaining strip was exposed using a grating spectrophotograph having a 2660K tungsten light source to obtain spcctrograms. The thus obtained spectrograms are shown in FIGS. 11 to 17.

From the values given in Table 2 and from the spectrograms obtained, it can be seen that the effects of the combination of dyes of the present invention having supersensitizing action are excellent and are affected by the coupler with difficulty as compared with the comparative dyes.

TABLE 2 Relativc Dvc and Amount Dye and Amount D c and Amount Scnsi- C an Nu. Used X I mol Used X mol sud X I0 mol tivity F og spectrogram l (l A) 0.07

I 98 0.07 FIG. ll 23 2 I80 007 (II B) l 70 0.07 2 95 0.07 4 I03 0.08 FIG. ll 24 (I-A) I (II-B) 4 I86 0.08 FIG. ll -25 2 92 007 FIG. 12 26 (I-A) l (II-B) 4 (6) 2 268 0.08 FIG. 12 27 3 I) I 33 0.07

2 45 007 FIG. I3 4 28 4 52 0.07 (I) l (ll-B) 4 I55 0.08

2 4 I60 0.08 FIG. I3 29 4 (3) I 38 0.07 2 80 0.08 4 85 (H0 FIG. l4 30 (I-A) l (3) 4 I50 0.]0

2 4 I50 0.l0 FIG. l4-3l 5 (l-E) I I00 007 FIG. 15-32 2 I40 0.07 (I-E) I (II-B) 4 I80 0.08 FlG.l5-33 2 4 200 0.08 6 (l-E) l (II-B) 4 (6) 2 250 0.08 7 (2) I 2 0.07

2 3 0.07 FIG. I6 34 4 5 0.07 (2) I (II-B) 4 ll4 0.08

2 4 I25 0.08 FIG. I6 35 8 (3) I (3) 4 80 0.09

2 4 70 0.09 FIG. l7 36 The combination of sensitizing dyes of the present invention having sensitizing action is useful for spectrally sensitizing a silver halide emulsion using for a red-sensitive layer in color light sensitive materials such as a color negative light sensitive material and a color reversal light sensitive material; a silver halide emulsion for use in a plate-making light sensitive material; and a silver halide emulsion for use in a light sensitive material for microsecond exposure, particularly, a CRT sensitive material, a light sensitive material for holography and a light sensitive material for use in a facsimile system.

In the case of using as a color light sensitive material, it is preferable to provide a magenta or red outer filter above or adjacent to the red-sensitive silver halide emulsion layer obtained by the present invention so as to impart the effect of actually reducing the greensensitivity in contrast to the red-sensitivity. In order to form such filter layer. the dyes described in Japanese Pat. Nos. 18459/66, 350/68, l3l68/68, 22069/64. 98474/7], 42668/71. 42667/71, US. Pat. Nos. 3,440,05]; 3,468,883; 3,294,539; 3,379,533; 3,352,680; 3,389,994; 3,384,487; 3,423,207; 3,493,375; 3,486,897; 3,481,927; 3,497,502;

3,573,289; 3,560,214; 3,615,432; 3,282,699; British Pat. No. 506,385, etc. can be used. In particular, those dyes which selectively absorb light of wave lengths shorter than 570 mm are useful. In addition, the methods described in German OLS No. 2,008,882, US. Pat. Nos. 3,425,834; 3,282,699, Belgian Pat. Nos. 682,413; 685,292; 703,939; 627,308, Japanese Pat. Nos. 21766/68, 13498/68, 15896/70, 10254/68, etc. can be employed. These are also employable for preventing iradiation of halation,

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

What is claimed is:

1. A silver halide photographic emulsion containing a supersensitizing combination of at least one sensitizing dye represented by the following general formula wherein Z, represents the atoms necessary to form a benzothiazole ring, a benzoselenazole ring, a B-naphthothiazole ring or a ,B-naphthoselenazole ring; Z represents the atoms necessary to form a benzoselenazole ring; A represents a hydrogen atom or an alkyl group; R and R each represents an alkyl group, at least one of R and R being a hydroxyalkyl group, a carboxysubstituted alkyl group or a sulfo-substituted alkyl group; X, represents an acid anion group; and m represents l or 2 and, when the dye forms an intramolecular salt, In represents 1; and at least one sensitizing dye represented by the general formula (II) R and R, each represents an alkyl group, at least one of R and R, being a hydroxyalkyl group, a carboxysubstituted alkyl group or a sulfosubstituted alkyl group; X: represents an acid anion: and n represents 1 or 2 and, when the dye forms an intramolecular salt. n represents l.

2. The silver halide photographic emulsion as described in claim 1, wherein in the general formula (I) Z, forms a ,B-naphthothiazole ring, a B-naphthoselenazole ring or a benzothiazole or benzoselenazole ring which is unsubstituted or substituted with a methyl group, an ethyl group, a methoxy group, a phenyl group 30 l -allyl--fluo robenzimidazole. l -allyl 5 .odichlorobenzimidazole. l-allyl-5.odifluorobenzimidazole, l-phcnyl-5lchlorobenzimidazole. l-phenyl-S-fluorobenzimitlazolc. l-phenyI-5.6-dichlorobenzimidazole. l phcnyl-5 ,(1- difluorobenzimidazole ring; wherein said alkyl group for A is a methyl group, an ethyl group. or a propyl group; wherein said R, to R, each is a methyl group. an ethyl group. a-propyl group, a Z-hydroxyethyl group. a

3'hydroxypropyl group, a Z-carboxyethyl group. a

or a chlorine atom at the 5-position; Z forms a benzol5 selenazole ring which is unsubstituted or substituted with a methyl group, an ethyl group, a methoxy group, a phenyl group or a chloride atom at the 5-position; R, and R each is a sulfosubstituted alkyl group, a carboxy-substituted alkyl group or a hydroxyalkyl group; and A is a methyl group.

3. The silver halide photographic emulsion as described in claim 1, wherein at least one of R, and R is a sulfosubstituted alkyl group and at least one of R and R, is a sulfosubstituted alkyl group.

4. The silver halide photographic emulsion as described in claim 1, wherein in the general formula (II) Z and 2, form benzimidazole rings substituted with chlorine atoms or fluorine atoms at the 5, 6, 5 and 6 positions.

5. The silver halide photographic emulsion as described in claim 1, wherein R,, R R and R, are sulfosubstituted alkyl groups.

6. A color light sensitive material comprising a support having thereon the silver halide photographic emulsion as described in claim I.

7. The silver halide photographic emulsion as described in claim 1, wherein said alkyl group for R, R, is an unsubstituted alkyl group, a hydroxyalkyl group, a carboxy-substituted alkyl group, a sulfo-substituted alkyl group, an acetoxyalkyl group, a cyanoalkyl group, a carbamoylalkyl group, a morpholinocarbonyl group, an allyl group or a morpholinosulfonylalkyl group.

8. The silver halide photographic emulsion as described in claim 1, wherein Z, is a benzothiazole, 5- chlorobenzothiazole, S-bromobenzothiazole, 5- fluorobenzothiazole, SI-methylbenzothiazole, 51- methoxybenzothiazole, S-methylcarbonylbenzothiazole, S-methoxycarbonylbenzothiazole, S-carboxybenzothiazole, S-hydroxybenzothiazole, 5- trifluoromethylbenzothiazole, 5-cyanobenzothiazole, 5,-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dichlorobenzothiazole, ,B-naphthothiazole, benzoselenazole, 5-chlorobenzoselenazole, 5- bromoselenazole, 5-methylbenzoselenazole, 51- methoxybenzoselenazole or ,B-naphthoselenazole ring; wherein Z is a benzoselenazole, 5- chlorobenzoselenazole, S-bromobenzoselenazole, 5- methylbenzoselenazole or S-methoxybenzoselenazole ring; wherein Z, and Z, each is a l-methyl-S- chlorobenzimidazole, l-methyl-5-fluorobenzimidazole,

l-methyl5 ,o-dichlorobenzimidazole, l-ethyl-5- chlorobenzimidazole, l-ethyl-5-fluorobenzimidazole, l-methyl-S ,6-dichlorobenzimidazole, l-ethyl-5 ,6- difluorobenzimidazole, l-propyl-S- chlorobenzimidazole, l-propyl-5-fluorobenzimidazole, l-propyl-5 ,-dichlorobenzimidazole, l-propyl-5 ,6- difluorobenzimidazole, l-allyl-5-chlorobenzimidazole,

3carboxypropyl group, a 4-carboxybutyl group, a 2- sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 2-[3-sulfopropoxy1ethyl group, a 2-hydroxy3- sulfopropyl group, a 3-sulfopropoxyethoxyethyl group, an acetoxyethyl group, a cyanopropyl group, a fi-carbamoylethyl group, a ,8-(4-morpholinocarbonyl)ethyl group, or a 6-(4-morpholinosulfonyl)butyl group.

9. The silver halide photographic emulsion as described in claim 1, including a cyan coupler.

10. The silver halide photographic emulsion as described in claim 1, wherein the supersensitizing com bination contains anhydro-5,5,9-trimethyl-3,3-di(3- sulfopropyl)selenacarbocyanine hydroxide and anhydro-5,5 ,6,6-tetrachlorol ,1 -diethyl-3 ,3 'di( 3- sulfopropoxyethoxyethyl)benzimidazolocarbocyanine hydroxide mono sodium salt.

11. The silver halide photographic emulsion as described in claim 1, wherein the supersensitizing combination contains anhydro-5,5,9-trimethyl-3,3-di(3- sulfopropyl)selenacarbocyanine hydroxide and anhydro-5,5 ,6,6-tetrachlorol ,l ,3-triethyl-3 3- sulfopropyl)benzimidazolocarbocyanine hydroxide.

12. The silver halide photographic emulsion as described in claim 1, wherein the supersensitizing combination contains anhydro-S,5,9-trimethyl3,3"di(3- sulfopropyl)sclenacarbocyanine hydroxide and anhydro-3-(2-carbamoylethyl )-5,5',6,6'-tetrachloro l l diethyl-3'-sulfopropyl benzimidazolocarbocyaninc hydroxide.

13. A silver halide photographic emulsion containing a supersensitizing combination of at least one sensitizing dye represented by the following general formula wherein Z, represents the atoms necessary to form a benzothiazole ring, a benzoselenazole ring, a ,B-naphthothiazole ring or a B-naphthoselenazole ring; Z represents the atoms necessary to form a benzoselenazole ring; A represents a hydrogen atom or an alkyl group; R, and R each represents an alkyl group, at least one of R, and R being a hydroxyalkyl group; a carboxysubstituted alkyl group or a sulfo-substituted alkyl group; X represents an acid anion group; and m represents l or 2 and, when the dye forms an intramolecular salt, In represents 1; and at least one sensitizing dye represented by the general formula (ll)

Claims

1. A SILVER HALIDE PHOTOGRAPHIC EMULSION CONTAINING A SUPER SENSITIZING COMBINATION OF AT LEAST ONE SENSITIZING DYE REPRESENTED BY THE FOLLOWING GENERAL FORMULA (1)

2. The silver halide photographic emulsion as described in claim 1, wherein in the general formula (I) Z1 forms a Beta -naphthothiazole ring, a Beta -naphthoselenazoLe ring or a benzothiazole or benzoselenazole ring which is unsubstituted or substituted with a methyl group, an ethyl group, a methoxy group, a phenyl group or a chlorine atom at the 5-position; Z2 forms a benzoselenazole ring which is unsubstituted or substituted with a methyl group, an ethyl group, a methoxy group, a phenyl group or a chloride atom at the 5-position; R1 and R2 each is a sulfosubstituted alkyl group, a carboxy-substituted alkyl group or a hydroxyalkyl group; and A is a methyl group.

3. The silver halide photographic emulsion as described in claim 1, wherein at least one of R1 and R2 is a sulfosubstituted alkyl group and at least one of R3 and R4 is a sulfosubstituted alkyl group.

4. The silver halide photographic emulsion as described in claim 1, wherein in the general formula (II) Z3 and z4 form benzimidazole rings substituted with chlorine atoms or fluorine atoms at the 5, 6, 5'' and 6'' positions.

5. The silver halide photographic emulsion as described in claim 1, wherein R1, R2, R3 and R4 are sulfo-substituted alkyl groups.

6. A color light sensitive material comprising a support having thereon the silver halide photographic emulsion as described in claim 1.

7. The silver halide photographic emulsion as described in claim 1, wherein said alkyl group for R1 - R4 is an unsubstituted alkyl group, a hydroxyalkyl group, a carboxy-substituted alkyl group, a sulfo-substituted alkyl group, an acetoxyalkyl group, a cyanoalkyl group, a carbamoylalkyl group, a morpholinocarbonyl group, an allyl group or a morpholinosulfonylalkyl group.

8. The silver halide photographic emulsion as described in claim 1, wherein Z1 is a benzothiazole, 5-chlorobenzothiazole, 5-bromobenzothiazole, 5-fluorobenzothiazole, 51-methylbenzothiazole, 51-methoxybenzothiazole, 5-methylcarbonylbenzothiazole, 5-methoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-hydroxybenzothiazole, 5-trifluoromethylbenzothiazole, 5-cyanobenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dichlorobenzothiazole, Beta -naphthothiazole, benzoselenazole, 5-chlorobenzoselenazole, 5-bromoselenazole, 5-methylbenzoselenazole, 51-methoxybenzoselenazole or Beta -naphthoselenazole ring; wherein Z2 is a benzoselenazole, 5-chlorobenzoselenazole, 5-bromobenzoselenazole, 5-methylbenzoselenazole or 5-methoxybenzoselenazole ring; wherein Z3 and Z4 each is a 1-methyl-5-chlorobenzimidazole, 1-methyl-5-fluorobenzimidazole, 1-methyl-5,6-dichlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-methyl-5, 6-dichlorobenzimidazole, 1-ethyl-5,6-difluorobenzimidazole, 1-propyl-5-chlorobenzimidazole, 1-propyl-5-fluorobenzimidazole, 1-propyl-5,6-dichlorobenzimidazole, 1-propyl-5,6-difluorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-allyl-5-fluorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5,6-difluorobenzimidazole, 1-phenyl-51-chlorobenzimidazole, 1-phenyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-phenyl-5,6-difluorobenzimidazole ring; wherein said alkyl group for A is a methyl group, an ethyl group, or a propyl group; wherein said R1 to R4 each is a methyl group, an ethyl group, a propyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-carboxyethyl group, a 3-carboxypropyl group, a 4-carboxybutyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 2-(3-sulfopropoxy)ethyl groUp, a 2-hydroxy-3-sulfopropyl group, a 3-sulfopropoxyethoxyethyl group, an acetoxyethyl group, a cyanopropyl group, a Beta -carbamoylethyl group, a Beta -(4-morpholinocarbonyl)ethyl group, or a delta -(4-morpholinosulfonyl)butyl group.

10. The silver halide photographic emulsion as described in claim 1, wherein the supersensitizing combination contains anhydro-5,5'',9-trimethyl-3,3''-di(3-sulfopropyl)selenacarbocyanine hydroxide and anhydro-5,5'',6,6''-tetrachloro-1,1''-diethyl-3,3''-di(3 -sulfopropoxyethoxyethyl)benzimidazolocarbocyanine hydroxide mono sodium salt.

11. The silver halide photographic emulsion as described in claim 1, wherein the supersensitizing combination contains anhydro-5,5'',9-trimethyl-3,3''-di(3-sulfopropyl)selenacarbocyanine hydroxide and anhydro-5,5'',6,6''-tetrachloro-1,1'',3-triethyl-3''-(3 -sulfopropyl)benzimidazolocarbocyanine hydroxide.

12. The silver halide photographic emulsion as described in claim 1, wherein the supersensitizing combination contains anhydro-5,5'',9-trimethyl-3,3''-di(3-sulfopropyl)selenacarbocyanine hydroxide and anhydro-3-(2-carbamoylethyl)-5,5'',6,6''-tetrachloro1,1''-diethyl-3'' -sulfopropyl benzimidazolocarbocyanine hydroxide.

13. A silver halide photographic emulsion containing a supersensitizing combination of at least one sensitizing dye represented by the following general formula (I)