US3922170A

US3922170A - Spectrally sensitized silver halide photographic emulsion

Info

Publication number: US3922170A
Application number: US381137A
Authority: US
Inventors: Keisuke Shiba; Akira Sato
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1972-07-20
Filing date: 1973-07-20
Publication date: 1975-11-25
Anticipated expiration: 1992-11-25
Also published as: JPS4932634A; JPS5544368B2; GB1434798A; DE2337042A1; FR2193991B1; FR2193991A1

Abstract

A silver halide photographic emulsion which is spectrally sensitized so that it has a maximum sensitivity wave length within the region of 580 nm - 640 nm, characterized by containing in a super sensitizing amount the combination of at least one carbocyanine dye represented by the general formula (I) and at least one of the dyes selected from the group consisting of dyes represented by the general formula (II) and (III):

WHEREIN Z1 represents the grouping necessary for the formation of Beta -naphthothiazole or Beta -naphthoselenazole ring, Z2 represents the grouping necessary for the formation of benzoxazole ring, A1 represents a hydrogen atom, an alkyl radical or an aryl radical, R1 and R2 each represents an alkyl radical, at least one of which represents a hydroxyalkyl radical, a carboxyalkyl radical or alkyl radical having a sulfo group, X1 represents an acid anion group, and l is 1, or 2 the dye forming an intramolecular salt when l is 1:

WHEREIN Z3 and Z4 each represents the grouping necessary for the formation of a benzothiazole, benzoselenazole, Beta naphthothiazole or Beta -naphthoselenazole ring, A2 represents a hydrogen atom, an alkyl radical having less than three carbon atoms or an aryl radical, R3 and R4 each represents an alkyl radical, at least one of which represents a hydroxyalkyl radical, a carboxyalkyl radical or an alkyl radical having a sulfo group, X2 represents an acid anion group, and m is 1 or 2, the dye forming an intramolecular salt when m is 1.

WHEREIN Z5 represents the grouping necessary for the formation of a benzoxazole orbenzimidazole ring, Z6 represents the grouping necessary for the formation of a benzothiazole, benzoselenazole or Beta -naphthothiazole ring, A3 represents a hydrogen atom, an alkyl radical having less than three carbon atoms or an aryl radical, R5 and R6 each represents an alkyl radical, at least one of which represents a hydroxyalkyl radical, a carboxyalkyl radical or an alkyl radical having a sulfo group, X3 represents an acid anion group, and n is 1, the dye forming an intramolecular salt when n is 1.

Description

United States Patent 1 1 Shiba ct a1.

1 1 Nov. 25. 1975 1 1 SPECTRALLY SENSITIZED SlLVER HALIDE PHOTOGRAPH": EMULSION (751 Inventors: Keisuke Shiba; Akira Sato. both of Kanagawa.]apan Fuji Photo Film Co.. Ltd.. Minami-ashigara. Japan [22 Filed: July 20. 1973 21 Appl. No: 381,137

[731 Assignee:

Primary Examiner1 Travis Brown Attorney, Agent. or Firm-Sughrue. Rothwell. Mion, Zinn & Macpeak [57] ABSTRACT A silver halide photographic emulsion which is spectrally sensitized so that it has a maximum sensitivity wave length within the region of 580 nm 640 nm. characterized by containing in a super sensitizing amount the combination of at least one carbocyanine dye represented by the general formula (1) and at least one of the dyes selected from the group consisting of dyes represented by the general formula (11) and (111):

wherein Z, represents the grouping necessary for the formation of B-naphthothiazole or B-naphthoselenazole ring. Z represents the grouping necessary for the formation of henzoxazole ring. A represents a hydrogen atom. an alkyl radical or an aryl radical. R and R each represents an alkyl radical. at least one o1 which represents a hydroxyalkyl radical. a carbosyalkyl radical or alkyl radical having a sull'o group X. represents an acid anion group. and l is l. or Z the dye forming an intramolecular salt when l is l:

wherein Z and Z each represents the grouping necessary for the formation of a benzothiazole. benzosclen azole, B-naphthothiazole or B-naphthoselenazolc ring. A; represents a hydrogen atom. an alkyl radical having less than three carbon atoms or an aryl radical. R and R each represents an alkyl radical. at least one oi which represents a hydroxyalkyl radical. a carbosyal kyl radical or an alkyl radical having a sulto group. X;- represents an acid anion group. and m is l or Z. the dye forming an intramolccular salt when m is l wherein Z represents the grouping necessary for the formation of a benzoxazole orbenzimidazole ring. Z represents the grouping necessary for the formation of a benzothiazole, benzoselenazole or B-naphthothiazole ring, A represents a hydrogen atom. an alkyl radical having less than three carbon atoms or an aryl radical. R and R each represents an alkyl radical. at least one of which represents a hydroxyalkyl radical. a carboxyalkyl radical or an alkyl radical having a sulfo group. X, represents an acid anion group. and n is l. the dye forming an intramolecular salt when n is 1.

(Xi n 9 Claims. 17 Drawing Figures US. Patent Nov. 25, 1975 Sheet 1 of 3 3,922,170

m fix 9 8 H04 0X 5 fill WAVELENGTH [mp] U.S. Patent Nov. 25, 1975 Sheet2of3 3,922,170

FIG 9 FIG. IO

FIG. II

FIG. l2

FIG. l3

FIG. I4

FIG. I5

WAVELENGTH (my) SP-I HO I6 WAVELENGTH (nm FIG. I?

WAVELENGTH nm SPECTRALLY SENSITIZEI) SILVER HALIDE PHOTOGRAPI-IIC EMULSION BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion in which a specific wave length range is highly spectrally sensitized by a supersensitization, more especially, the present invention relates to a sliver halide photographic emulsion in which the wave length range from 580 nm to 640 nm is spectrally sensitized,

2. Description of the Prior Art An appropriate spectral sensitivity distribution over the visible wave length range to which human eyes are sensitive is given to conventional photographic sensitive materials. An appropriate spectral sensitivity distribution is required for suitable color reproduction. Usua ally, a combination of two or more sensitizing dyes is selected, the combination having a supersensitization effect.

To obtain excellent color reproduction, it is not preferred to have high sensitivity at too long a wave length, eg a wave length longer than 660 nm (the wave length at the maximum sensitization) or to have high sensitivity only at too short a wave length region, e.g., shorter than 580 nm (the wave length at the maximum sensiti zation). It is difficult to selectively increase sensitivity within the wave length region from 580 nm to 640 nm, and the solution to this problem is an important matter in this technical field.

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a new supersensitization technique to selectively increase the sensitivity within the wave length region from about 580 nm to 640 nm.

Another object of the present invention is to diminish the color residue which typically remains after development.

Moreover, a further object of the present invention is to provide a sensitizing dye that does not diffuse into and sensitize adjacent sensitive layers when a layer ofa multi layer sensitive material is selectively spectrally sensitized.

The above objects are attained as follows:

To a photographic emulsion there is added the combination of at least one carbocyanine dye of general formula (I) and at least one dye selected from the group consisting of dyes of general formula (II) and dyes of general formula (III), in an amount sufficient to provide a supersensitization:

wherein Z represents the grouping necessary for the formation of a B-naphthothiazole or B-naphthoselenazole ring, Z represents the grouping necessary for the formation of a benzoxazole ring, A, represents hydrogen atom, an alkyl group, (e.g., an unsubstituted alkyl group having up to 4 carbon atoms or a monoaralkyl group wherein the alkyl moiety has up to 2 4 carbon atoms) or monoaryl (ie. unsubstituted or sub stituted monoaryl) radical, R and R each represents an alkyl (i.e. an unsubstituted alkyl group preferably having up to 8 carbon atoms and a substituted alkyl group wherein the alkyl moiety preferably has up to 4 carbon atoms) radical, at least one of which is hydroxyalkyl, carboxyalkyl or an alkyl radical having a sulfo group, X is an acid anion group, and I is l or 2, being 0 1 when the dye forms an intramolecular salt (similar to a betaine structure wherein Z;, and Z, each represents the grouping necessary for the formation of a benzothiazole, benzoselenazole, B-naphthothiazole or B-naphthoselenuzole ring. A represents a hydrogen atom. an alkyl radical having less than three carbon atoms or a monoaryl radical (i.e., unsubstituted or substituted monoaryl R and R each represents an alkyl (ie an unsubstituted alkyl group preferably having up to 8 carbon atoms and a substituted alkyl group wherein the alkyl moiety preferably has up to 4 carbon atoms) radical. at least one of which is a hydroxyalkyl, carboxyalkyl or alkyl radical having a sulfo group, X-{ is an acid anion group. and m is 1 or 2, being l when the dye forms an intramolecular salt (similar to a betaine structure).

wherein Z represents the grouping necessary for the formation of a benzoxazole or benzimidazole ring, Z represents the grouping necessary for the formation of a benzothiazole, benzoselenazole or B-naphthothiazole ring, A represents a hydrogen atom, an alkyl group (e.g. an unsubstituted alkyl group having up to 4 carbon atoms and a monoaralkyl group wherein the alkyl moiety has up to 4 carbon atoms) or a monoaryl (i.e. unsubstituted or substituted monoaryl) radical. R and R each represents an alkyl (ie. an unsubstituted alkyl group preferably having up to 8 carbon atoms and a substituted alkyl group wherein the alkyl moiety prefer ably has up to 4 carbon atoms) radical, at least one of which is hydroxyalkyl, carboxyalkyl or an alkyl radical having a sulfo group, X represents an acid anion group, and n is l or 2, being I when the dye forms an intramolecular salt (similar to a betaine structure) BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS FIGS. 1 15 are characteristic curves of dyes employed as described in the Examples given hereafter.

FIG. 16 is the spectral transmittance curve of an SP- l-filter and FIG. I7 shows the spectral transmittance of filters SC-SO & SC56.

Atom 1. bawimm- AMWJ, 1 mun-Mr gmup Ivy 1! 1: E mp 11 HUTNAHQ w imlu MU gn/Jp m 511mm minim! Mun/Wm;

mini. Lh uinn F 3 hulk MI mm hum Arr Uwumnni} Hand m gyunwn .iyL xiii wig and the Ii'm Whiiu WIN! mmwgun u Mammy lwwwc' 3w mud mm W mud m :a

\ flllDl Control Sensitizing Dyes:

(R) s c H o C-CH-C -CHC i Br e C H i l 5 O G-CH=C-CH==C\ l N/ N I c -CH==GCH==C i Cl l The silver halide photographic emulsion used in this a conventional manner, for example, gold sensitized invention can be manufactured by any common man- (US. Pat. Nos. 2,540,085, 2,597,856, 2,597,9l5, ner. e.g., precipitated by the single or double jet 2,399,083, etc), Group VIII metal ion sensitized, sul

method or a combination thereof, and contains aged fur sensitized (US. Pat. Nos. l,574,944. 2,278,947, silver chloride, bromide, iodide or mixed silver halide 55 2,440,206, 2,l40.689, 3,189,458, 3,415,649, etc), re-

particles. The preferred silver halides are silver iododuCIiOn sensitized N 2. l bromide (A preferred halogen composition by mole 7r 2,419,974. 2,983,6[0 etc.) or sensitized by a combinaof iodine is no greater than l0 mol "/c, for example, tion of the methods mentioned above. from 2 to 7 mol "1? iodine.) or chloroidobromide (A The photographic emulsion according to this inven preferred halogen composition by mo] 92 ofiodine is no 60 tion may contain as a chemical sensitizer a sulfur sensigreater than 5 mol /2. for example, from 2 to 3 m 7 tizer such as allyl thiocarbamide, thiourea,sodium thioiodine. The bromine or chlorine composition is up sulfate and cysteine; a noble metal sensitizer such as tional. The average diameter of the silver halide partipotassium chloroaurate, aurous thiosulfate and potascles is not limited but preferably is 0.04 2 (arithmetisium chloropalladate; a reducing sensitizer such as tin cal mean determined by, for example, the proje t d chloridephenyl hydrazine and reductone,and the like. area method). It may contain other sensitizers such as polyoxyethyl- The silver halide photographic emulsion used in this fine COmPOUIIdS h H5 "1056 diSClOSed i HI- N invention can be physically and chemically sensitized in 2,716,062, polyoxypropylene compounds and compounds having quaternary ammomium group such as those disclosed in U.S. Pat. Nos. 2,271,623; 2,334,864; 2,288,226 and the like. Further, the photographic emulsion may contain anti-fogging agents such as nitrobenzimidazole and ammonium chloroplatinate and stabilizers such as 4-hydroxy-6-methyl-l ,3,3a,7-tetrazaindene. The photographic emulsion may also contain hardening agents such as formaldehyde. chrome alum, l-hydroxy-3,S-dichlorotriazine soda, glyoxal and dichloroacrolein; and coating assistants such as saponin and sodium alkylbenzene sulfonates.

When the silver halide emulsion used in this invention is used for a color light-sensitive material, it may contain color couplers and dispersing agents therefor. Among the color couplers, especially cyan coupler are present. For example, couplers of the phenol series as described in U.S. Pat. No. 2,698,794 or couplers of the naphthol series are described in U.S. Pat. No. 2,474,293 are especially useful.

The silver halide photographic emulsion used in this invention can be based upon protective colloids other than gelatin, for example, gelatin derivatives such as phthalated or malonated gelatin; cellulose derivatives such as hydroxyethyl or carboxymethyl cellulose; soluble starches such as dextrin; hydrophilic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacryiamide and polystyrene sulfonic acid; plasticizers for dimensional stability; latex polymers and matting agents. The generally used ratio by weight of silver halide to the binder is from about 1:4 to 4:1.

The finished emulsion is coated on any suitable support, for example, baryta paper, resin-coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, glass plate and other plastic bases.

The sensitizing dyes used in this invention can be added to the emulsion as a solution in water or a watermiscible organic solvent such as methanol, ethanol, methyl cellosolve, pyridine and the like.

The amount of the dyes added is as is commonly used for the supersensitization, e.g. about 55 X l X 10 mol of dye per mol of silver, and the ratio of the dye or dyes of general formula (11) and/or (III) to the dye or dyes of the general formula (I) is preferably about 1:100-121 (mol ratio). It is especially preferred that the amount of dye or dyes of general formula (1) be larger than that of the dye of general formula (11) (mol ratio).

The dyes used in this invention can be used for spectral sensitization according to the method described in German Laid Open Specification 2,104,283 and in U.S. Pat. No. 3,649,286.

Specific examples according to this invention are described below, but this invention is not restricted only to the examples. Unless otherwise indicated all parts and percents are by weight.

EXAMPLE 1 Silver halide particles were precipitated in a gelatin binder by the double jet method, physically aged in a common manner, subjected to desalting treatment and chemically aged with 4 ml of an aqueous solution con taining hypo and having a concentration of l by weight and 10 ml ofan aqueous solution containing potassium chloroaurate and having a concentration of 1 71 by weight so that a silver iodobromide (iodine content: 6 mol7r) emulsion was manufactured. The emulsion contained 0.6 mol of silver halide/kg of emulsion. The grain size of the silver halide formed was 0.8a. One kg of emulsion was placed in a crucible and dissolved in a constant temperature bath at 50C.

A given amount of each sensitizing dye of this inven tion, which was used for the comparison with the sensitizing dyes according to this invention was added to the resulting emulsion as a metlianolic solution and stirred at 40C. On the other hand, a given amount of each dye for comparison was added to the resulting emulsion in the same way as described above. 10 cc of an aqueous 0:1 wt.% solution of 4-hydroxy-6-methyl-l,3,3a,7-tetrazaindene, 10 cc of a l wtfi? aqueous solution of lhydroxy-3,S-dichlorotriazine soda and 10 cc of a l wt.% aqueous solution of sodium dodecyl benzene sulfonate were added thereto and the system stirred.

The resulting finished emulsion was coated on a cellulose triacetate film base to a dried film thickness of 5 microns, and dried to yield a sample of a sensitive ma terial.

The film sample was cut into strips. One strip was ex posed with an optical wedge to a light source provided with a blue filter (SP 1 a yellow filter (SC-50 and a red filter (SC-56) (all by Fuji Photo Film Co., Ltd.) using a sensitometer having a 5,400K color tempera ture light source. The remaining strips were exposed to obtain spectrograms using a diffraction grating spectrograph having a 2,666K tungsten light source.

The exposed strips were developed with a liquid developer having the following composition at 20C for 2 minutes, stopped, fixed and washed with water to yield strips having a black-and-white image. The densities of these strips were determined by an S-type densitometer (Fuji Photo Film Co., Ltd.) to measure the blue filter sensitivity (Sb), the yellow filter sensitivity (Sy), the red filter sensitivity (Sr) and fog. The base value of optical density for determining sensitivity was (fog 0.20).

Composition of Liquid Developer:

Water 500 cc Metol Anhydrous Sodium Sulfite 9 Hydroquinone Sodium Carbonate Monohydrate 5 Potassium Bromide Water (to make) The results obtained are shown as relative values in Table l.

Runs

12 and 13 were carried out for comparison.

The spectral transmittance curve of the SP-l filter is shown in FIG. 16 and those of the SC-SO and SC56 filters in FIG. 17. The resulting spectrograms are shown in FIG. 145.

From the values in Table l and the spectrograms, it can be seen that the combinations of dyes having a supersensitizing effect according to this invention have an excellent effect.

Table l Amount of Amount of S) Sr Sb No dye usedIKg dye used/Kg (Relative IRcIatlu: IRclativc Fug Spcctrugram Ll'llulslult emulsion \uluc) value) \aluc) x H) mull l lll "mull l I IA) I 005 2 I55 96 96 0.07 4 I00 I00 85 0.08 FIG. I Curve 1 III A) I 32 40 I00 0.06 2 38 50 I00 006 FIG. I Z 4 71 65 I00 0.0K IIA) 4 III A) l I I26 85 0.08

4 2 II. I51 III ().II FIG. I 3 4 4 I00 H2 76 0.II 2 III C) I 32 85 0.06

2 32 79 85 0.06 FIG 2 4 IIA) 4 (IIC) l I05 IIO 96 0.09

4 2 I05 H2 96 0.10 FIG. 2 5 3 III E) 2 B5 85 85 0.08

4 I I40 76 009 FIG. 3 6 IIA) 4 lIIE) 2 I56 I56 89 (H0 4 4 I56 I78 78 0.I0 FIG. 3 7 (II F) I 43 40 86 007 FIG. 4 8 4 1m 4 (II F) 0.5 I00 I19 94 um 4 I I00 I26 94 0.08 FIG. 4 9 5 (III A) I 63 67 80 0.08

2 II2 H4 85 0.08 FIG. 5 I0 (IA) 4 (IIIA) I II7 II7 76 0.10

4 2 I58 I66 63 0.1) FIG.5 II 6 III I) 2 56 63 I00 0.07

4 76 80 I00 0.07 FIGv 6 I2 (IA) 4 (III) 2 I40 I58 88 0.08 FIG.6 l3

4 4 I58 I78 85 0.08 7 (1B) 2 I4l H2 96 0.06

4 I60 I32 91 0.07 FIG. 7 Curve l4 8 I60 I28 60 0.07 A (II G) I I00 I25 I00 006 2 I25 I32 I00 006 FIG. 7 l5 (IB) 4 (ll G) I 232 200 96 0.07

4 2 232 224 92 007 FIG. 7 I6 Ii (III B] I 63 25 I05 006 2 I00 I00 0.06 FIG. 8 I7 IIB) 4 (III B) I 234 200 93 0.06

4 2 250 200 93 0.07 FIG. 8 I8 9 (IC) 2 I4I I26 87 0.07

4 I48 I50 77 0.08 FIG. 9 I9 8 I48 I53 66 0.08 (III C) I I26 II7 96 0.06 2 I50 I25 80 007 FIG. 9 20 (IC) 4 (IIIC) I 2l4 I58 89 0.08

4 2 250 I58 85 0.08 FIG. 9 2| I0 IIG) '2 I52 I50 87 0.08

4 I52 I52 80 0.08 FIG. I0 22 (II E) I 83 79 96 0.06 2 I00 I00 96 0.07 FIG. I0 23 (IG) 4 I 234 200 96 0.07

4 2 234 224 93 0.08 FIG. I0 24 II (IE) 2 I09 76 85 0.08

4 I10 96 76 0.08 FIG. II 25 III B) I 66 62 I00 0.08 2 80 78 88 009 FIG. II 26 (IE) 4 (III!) I I00 I42 50 012 FIG. II 27' 4 2 III I66 35 0.12

' Value too low to be measured The combinations of sensitizing dyes having a supersensitization effect according to this invention are useful for the spectral sensitization of silver halide emulsions in the red sensitive layer of color sensitive material such as color negative and reversal sensitive materials, the spectral sensitization of silver halide emulsions used for black-and-white sensitive materials, the spectral sensitization of silver halides used as a printing plate sensitive material and the spectral sensitization of 50 cording to this invention in order to render practically the green sensitivity less than the red sensitivity obtained by this invention. For the formation of such filter layer, dyes are used are described in Japanese Patent Publications Nos. 18459/66, 3504/68. I3l68/68 and 22069164; Japanese Pat. applications Nos. 98474/71, 42668/7] and 42667]? I and US. Pat. Nos. 3,440,051,

3,573,289, 3,560,214, 3,615,432 and 3,282,699; Brit- I ish Pat. No. 506.385 etc. Especially, dyes which absorb selectively the short wave region less than 570 nm are useful. The methods are used, which are described in the German Laid-Open Specification No. 2,008,882; U.S. Pat. 3,425,834 and 3,282,699; Belgian Pat. Nos. 682,4 I 3, 685,292, 703,939 and 627,308; Japanese Pat. Publication Nos. 2l766/68, 13498/68, 15896760 and 10254/68 etc. These may be used for the prevention of irradiation and halation.

Practicularly preferred embodiments according to this invention are as follows:

1. A compound of the formula (I) wherein the heterocyclic ring formed by the group 2, is the B-naphthothiazole ring, the heterocyclic ring formed by the group Z is a benzoxazole ring, which is substituted at the 5-position by a chlorine atom, a trifluoromethyl, methyl or phenyl radical and A, is an ethyl radical.

2. A compound of the formula (ll) wherein A is a methyl or ethyl radical, R and R, each is a methyl, ethyl, propyl, ally], carboxyalkyl or sulfoalkyl radical.

3. A compound of the formula (III) wherein A is a hydrogen atom, a methyl or ethyl radical, R and R each is a methyl, ethyl, propyl, allyl, carboxyalkyl or sulfoalkyl radical. A color sensitive material comprising an emulsion containing a cyan coupler, characterized by containing in a supersensitizing amount the combination of at least one carbocyanine dye represented by general formula (I) and at least one dye selected from the group consisting of dyes represented by general formula (II) and (11]).

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:

l. A silver halide photographic emulsion which is spectrally sensitized so that it has a maximum sensitiv ity wave length within the region of 580 nm 640 nm, characterized by containing in a supersensitizing amount the combination of:

at least one carbocyanine dye represented by general formula (I) and at least one dye represented by general formula (III):

wherein Z, represents the grouping necessary for the formation of B-naphthothiazole or B-naphthoselenazole ring, Z, represents the grouping necessary for the formation of benzoxazole ring, A, represents a hydrogen atom, an alkyl radical, or an aryl radical, R, and R each represents an alkyl radical, at least one of which represents a hydroxyalkyl radical, a carboxyalkyl radical or alkyl radical having a sulfo group,

x, represents an acid anion group, and 1 is l or 2, the dye forming an intramolecular salt when I is l:

wherein Z represents the grouping necessary for the formation of a benzoxazole or benzimidazole ring, 2,, represents the grouping necessary for the formation of a benzothiazole, benzosclenazole or B-naphthothiazole ring, when 2,, is a benzimidazole ring and 2,, represents the grouping necessary for the formation of a bcnzothi azole or benzoselenazole ring when Z is a benzoxazole ring, A, represents a hydrogen atom. an alkyl radical having less than three carbon atoms or an aryl radical. R and R each represents an alkyl radical, at least one of which represents a hydroxyalkyl radical. a carboxyalkyl radical or an alkyl radical having a sulfo group, X represents an acid anion group, and n is l, the dye forming an mtramolecular salt when n is l,

2. The silver halide photographic emulsion of claim 1, wherein the hetero ring firmed by Z Z and Z,- is substituted with at least one substituent. said substituent being selected from the group consisting of an alkyl group, a halogen atom, a monoaryl group, an alkoxy group, a hydroxy group, an alkoxy carbonyl group, a cyano group, an amino group, an aminocarbonyl group, a monoaryloxy group and an acyl group.

3. The silver halide photographic emulsion of claim 1, wherein Z is a benzoxazole. S-methyl benzoxazole, 5,6-dimethyl benzoxazole, Schlorobenzoxazole. 5- chloro-o-methyl benzoxazole, S-bromobenzoxazole. S-phenyl benzoxazole, S-tolyl benzoxazole. S-methoxy benzoxazole, S-hydroxy benzoxazole, S-methoxycarbonyl benzoxazole, S-ethoxycarbonyl benzoxazole, S-trifluoromethyl benzoxazole. S-cyanobenzoxazole, 5- aminobenzoxazole, 5-phenoxybenzoxazole. or S-acetyl benzoxazole ring; wherein A,, and A each is a hydrogen atom, a methyl, ethyl. propyl. phenethyl or phenyl radical; wherein R,, R R and R each is a methyl. ethyl, propyl, allyl, 2-carboxyethyl. 4-carboxybutyl, 3- carboxypropyl, Z-methoxyethyl, 3-sulfopropyl, 3-sulfobutyl,2-(3-sulfopropoxy)ethyl, 2-hydroxy-3-sulfo' propyl, 3-sulfopropoxyethoxyethyl, Z-bromoethyl. or p-sulfophenethyl;

Z is a ring as described for Z or 5-chlorobenzimidazole, 5,-dichlorobenzimidazole. S-trifluoromethylbenzimidazole, S-methoxycarbonyl benzimidazole or 5-cyano-6-chlorobenzimidazole ring; and X,, and X each represents an iodine, bromine, chlorine, p-toluene sulfonic acid, benzene sulfonic acid, ethyl sulfate, perchlorate, or rhodan ions.

4. The silver halide photographic emulsion of claim I, wherein said dye of the general formula (I) is Se CH l l c P- N/ (2H5 llllC) (lllDl 5. The silver halide photographic emulsion of claim 1, wherein said dyes of the general formula (I), and (III) are present at a level of from about 5 X to l X 10 mol of dye per mol of silver and wherein the molar ratio of the amount of dye of the general formula (ll) and (III) to the amount of dye of the general formula (l) is about l:100 to lzl.

6. The silver halide photographic emulsion of claim 1, wherein Z is a ,B-naphthothiazole ring Z is a benz oxazole ring which is substituted at the 5-position with a chlorine atom. a trifluoromethyl group, a methyl group or a phenyl group and A is an ethyl group.

c14 )3 Sc? 7. The silver halide photographic emulsion of Llilllll 1, wherein A is a hydrogen atom a methyl group, or an ethyl group, R and R each is a methyl group. an ethyl group, a propyl group, an ally] group. a carhoxynlkyl group or a sulfoalkyl group.

8. The silver halide photographic emulsion of claim 1, wherein said emulsion additionally contains phenol or naphol series cyan coupler,

9. A silver halide photographic material comprising a support having thereon the silver halide emulsion ol claim I.

Claims

1. A SILVER HALIDE PHOTOGRAPHIC EMULSION WHICH IS SPECTRALLY SENSITIZED SO THAT IT HAS A MAXIMUM SENSITIVITY WAVE LENGTH WITHIN THE REGION OF 580 NM - 64O NM, CHARACTERIZED BY CONTAINING IN A SUSPERSENSITIZING AMOUNT THE COMBINATION OF: AT LEAST ONECARBOCYANINE DYE REPRESENTED BY GENERAL FORMULA (I) AND AT LEAST ONE DYE REPRESENT BY GENERAL FORMULA (III):

2. The silver halide photographic emulsion of claim 1, wherein the hetero ring formed by Z2, Z5 and Z6 is substituted with at least one substituent, said substituent being selected from the group consisting of an alkyl group, a halogen atom, a monoaryl group, an alkoxy group, a hydroxy group, an alkoxy carbonyl group, a cyano group, an amino group, an aminocarbonyl group, a monoaryloxy group and an acyl group.

3. The silver halide photographic emulsion of claim 1, wherein Z2 is a benzoxazole, 5-methyl benzoxazole, 5,6-dimethyl benzoxazole, 5-chlorobenzoxazole, 5-chloro-6-methyl benzoxazole, 5-bromobenzoxazole, 5-phenyl benzoxazole, 5-tolyl benzoxazole, 5-methoxy benzoxazole, 5-hydroxy benzoxazole, 5-methoxycarbonyl benzoxazole, 5-ethoxycarbonyl benzoxazole, 5-trifluoromethyl benzoxazole, 5-cyanobenzoxazole, 5-aminobenzoxazole, 5-phenoxybenzoxazole, or 5-acetyl benzoxazole ring; wherein A1, and A3 each is a hydrogen atom, a methyl, ethyl, propyl, phenethyl or phenyl radical; wherein R1, R2, R5 and R6 each is a methyl, ethyl, propyl, allyl, 2-carboxyethyl, 4-carboxybutyl, 3-carboxypropyl, 2-methoxyethyl, 3-sulfopropyl, 3-sulfobutyl,2-(3-sulfopropoxy)ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, 2-bromoethyl, or p-sulfophenethyl; Z5 is a ring as described for Z2, or 5-chlorobenzimidazole, 5,6-dichlorobenzimidazole, 5-trifluoromethylbenzimidazole, 5-methoxycarbonyl benzimidazole or 5-cyano-6-chlorobenzimidazole ring; and X1, and X3 each represents an iodine, bromine, chlorine, p-toluene sulfonic acid, benzene sulfonic acid, ethyl sulfate, perchlorate, or rhodan ions.

4. The silver halide photographic emulsion of claim 1, wherein said dye of the general formula (I) is

5. The silver halide photographic emulsion of claim 1, wherein said dyes of the general formula (I), and (III) are present at a level of from about 5 X 10 3 to 1 X 10 6 mol of dye per mol of silver and wherein the molar ratio of the amount of dye of the general formula (II) and (III) to the amount of dye of the general formula (I) is about 1:100 to 1:1.

6. The silver halide photographic emulsion of claim 1, wherein Z1 is a Beta -naphthothiazole ring, Z2 is a benzoxazole ring which is suBstituted at the 5-position with a chlorine atom, a trifluoromethyl group, a methyl group or a phenyl group and A1 is an ethyl group.

7. The silver halide photographic emulsion of claim 1, wherein A3 is a hydrogen atom, a methyl group, or an ethyl group, R5 and R6 each is a methyl group, an ethyl group, a propyl group, an allyl group, a carboxyalkyl group, or a sulfoalkyl group.

8. The silver halide photographic emulsion of claim 1, wherein said emulsion additionally contains phenol or naphol series cyan coupler.

9. A silver halide photographic material comprising a support having thereon the silver halide emulsion of claim 1.