US3907575A - Spectrally sensitized silver halide photographic emulsion - Google Patents

Abstract

A spectrally sensitized silver halide photographic emulsion having a selectively improved sensitivity at the wave length region ranging from about 580 nm to 640 nm, is provided by incorporating into the emulsion a super sensitizing amount of a combination of at least two carbocyanine dyes as defined hereinafter.

Description

United States Patent [1 1 Shiba et al.

[ Sept. 23, 1975 SPECTRALLY SENSITIZED SILVER HALIDE PHOTOGRAPHIC EMULSION [75] Inventors: Keisuke Shiba; Haruo Takei; Akira Sato; Tadashi lkeda; Atsuo Iwamoto, all of Minami-ashigara,

Japan [73] Assignee: Fuji Photo Film Co., Ltd., Minamiashigara, Japan [22] Filed: Oct. 29, 1973 [21] Appl. No.: 410,572

[30] Foreign Application Priority Data Oct. 27. 1972 Japan 47-107783 [52] US. Cl. 96/124; 96/137 [5 l] Int. Cl.- G03C 1/14 [58] Field of Search 96/124 [56] References Cited UNITED STATES PATENTS 3338.714 8/1967 Ficken ct a]. 96/124 3.432.303 3/1969 Jones et al 96/124 3.679.428 7/1972 Shiba ct al. 96/l24 Primary Examiner-J. Travis Brown Attorney, Agent, or Firm-Stighrue. Rothwell, Mion Zinn and Macpeak [57] ABSTRACT 23 Claims, 20 Drawing Figures US Patent Sept. 23,1975 Sheet 2 of 3 3,907,575

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:5 E0252; 3 2w cg 08 am am av 03 h h :5 E0252; 3 0% 6% 08 8m 6m o? O: E E0252; 5 m Ga Ga own 2% cm; i ll- 5 0% m w 0% 2 6 O E a a: g m 7 n Amm as 15252; O N 0mm 9% gm own own ow? 00% E or- E2523 3 0% 0 08 m 2m 5 c E a: 25 E252; ow O m 9 2% 9% Own ow 2 0: as 15252; O N 0% gm 2% own own ow? p;

US Patent Sept. 23,1975

Sheet 3 0f 3 WAVELENGTH (nm) FIG. 20

SPECTRALLY SENSITIZEI) SILVER HALIDE PHOTOGRAPHIC EMULSION BACKGROUND OF THE INYEN'IION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion which has been very strongly spectrally sensitized over a particular wave length region by the application of a super sensitizing combination. ln greater particularity. the present invention is concerned with a silver halide photographic emulsion which has been spectrally sensitized within the wave length region ranging from 580 mm to 640 mm.

2. Description of the Prior Art An ordinary photosensitive material commonly used in the photographic art has been given an appro riate spectral sensitivitydistribution characteristics over all wave lengths to which the human eye is sensitive. In order to impart much more desirable color reproducibility. a specific spectral sensitivity distribution is required. For this reason. a combination of two or more sensitizing dyes giving rise to super sensitization has been chosen and has been practically employed.

To obtain excellent color reproducibility. it is not desirable for a photographic material to have too much of an extended range of sensitivity. for example. over wave lengths as high as in excess of'660 nm (the wave length at the maximum sensitization). nor to have appreciable sensitivity only in the lower wave length regions. for example. in the region below 58()nm (wave length at the maximum sensitization).

However. great difficulty has been encountered in the art of spectral sensitization. to increase selectivity the sensitivity in the region between 580 nm and 640 mn. so that this has been one of the most important problems to be overcome in this field of technology.

Therefore. a primary object of the present invention is to provide a novel technique for effecting super sensitization by which the sensitivity ofa silver halide photographic emulsion in wave lengths ranging from about 580 nm to 640 nm is increased to a much greater extent.

Another object of the present invention is to provide an improvement in reducing color stains inevitably occurring after development.

Still another object of the present invention is to find a sensitizing dye which doesnotdiffuse into adjacent photosensitive layers so as to sensitize the adjacent layer when one layer of a multi-layered photosensitive material has been spcctrally sensitized selectively so as to attain the objects of the present invention.

SUMMARY OF THE INVENTION The above objects have now been accomplished by incorporating in a silver halide photographic emulsion a combination in a super sensitizing amount of at least one carbocyanine type dye represented by the General l'orn1ula( I] General Formula (I) wherein Z represents a group of atoms necessary for forming a B-naphthoxazole ring or a B-naphthoimidazole ring. the benzene nuclei of which rings may be substituted by a substituent not adversely affecting the sensitivity of the silver halide emulsion. 7. represents a group of atoms necessary for forming a benzothiazole ring. a benzoselenazole ring or a 4.5 dihydronaphtholl.2-l|thiazole ring: A represents a hydrogen atom. an alkyl group (i.e.. an unsubstituted alkyl group e.g.. having up to 4 carbon atoms. preferably up to 3 carbon atoms. or a substituted alkyl group. c.g.. in which the alkyl moiety has up to 4 carbon atoms. preferably up to 3 carbon atoms) or an aryl group. preferably a monoaryl group: R, and R each represents an aliphatic group including a saturated aliphatic group and an unsaturated aliphatic group. for example. an alkyl group and an aralltyl group. which groups may be substituted. with the number of carbon atoms in the alkyl moiety being up to 8. preferably up to 4 with the proviso that at least one of R or R is either a hydroxyalkyl. a carboxyalkyl or a sulfocontaining alkyl group; X represents an acid anion group; and l is l or 2. but when l is l the dye forms an intramolecular salt (betaine-like structure); with at least one of the dyes represented by the General Formula (II) General Formula (II) wherein 7. represents a group of atoms necessary for forming a benzothiazole ring. a B-naphthothiazole ring. a benzoselenazole ring or a 4.5-dihydronaphtho [1.2- d lthiazole ring; Z represents group of atoms necessary for forming a benzoxazole ring or a benzimidazole ring; A: represents a hydrogen atom. an alkyl group (i.e.. an unsubstituted alkyl group e.g.. having up to 4 carbon atoms. preferably by to 3 carbon atoms or a substituted alkyl group. e.g.. in which the alkyl moiety has up to 4 carbon atoms, preferably up to 3 carbon atoms) or an aryl group. preferably a monoaryl group; R and R each represents an aliphatic group including a saturated aliphatic group and an unsaturated aliphatic group. for example. an alkyl group and an aralkyl group. which groups may be substituted. with the number of carbon atoms in the alkyl moiety being up to 8. preferably up to 4 in which at least one of R or R is a hydroxyalkyl. a carboxyalkyl or a sulfo-containing alkyl group: X; represents an acid anion group; In is l or 2. but when m is l. the dye forms an intramolecular salt: or one of the dyes represented by the General Formula (III) General Formula (lIl) wherein Z and 7... each represents a group of atoms necessary for forming a benzothiazole ring. a benzoselenazole ring. a B-naphthothiazole ring or a B-naphthoselenazole ring; A; represents a hydrogen atom. an.

alkyl group (i.e.. an unsubstituted alkyl group e.g.. having up to 4 carbon atoms. preferably up to 3 carbon atoms or a substituted alkyl group. e.g.. in which the alkyl moiety has up to 4 carbon atoms. preferably up to 3 carbon atoms) or an aryl group; R and R each represents an aliphatic group including a saturated ali phatie group and an unsaturated aliphatic group. for example. an alkyl group and an aralkyl group. which groups may be substituted. with the number of carbon atoms in the alkyl moiety being up to 8. preferably up to 4. with at least one of R or R being either a hydroxyalkyl. a carboxyalkyl or a sulfo-containingalkyl group; X;, represents an acidanion group; n is l or 2. but when n is l. the dye forms an intramolecular salt,

BRIEF DESCRIPTION OF THE ACCOMPANYIN DRAWINGS I FIGS. 1-19 are spectrograms of the color super sensitizing dye combinations of this invention and of other dyes for comparison of samples as produced in the Example hereinafter.

FIG. 20 is a graphical presentation of the transmission characteristics of Spl. Sc-SO and Sc-56 filters.

DETAILED DESCRIPTION OF THE INVENTION Typical examples of the heterocyclic rings represented by Z of the sensitizing of the General Formula (I) include. for example. both those rings which are unsubstituted and which are substituted with substituents such as halogen atoms. alkyl groups. acyl groups. aryl groups. cyano groups. hydroxy groups. alcoholate groups. amino groups. etc.. such as benzothiazole. 5- chlorobenzothiazolc. S-bromobenzothiazole. 5- fluorobenzothiazole. 5-methylbenzothiazole. 5- methoxybenzothiazole. 5-methylcarbonylbenzothiazole. 5-earboxybenzothiazole. S-methoxycarlmnylbenzothiazole. 5-phenylbenzothiazole. 5- cyanobenzothiazole. 5-trifluoromethylbenzothiazole. 5-hydroxybenzothiazole. 5-aminobenzothiazole. 5.6- dichlorobenzothiazole; 5-methyl-6- methoxybenzothiazole. 5.6-dimethylbenzothiazole. 5.6-dimethoxybenzothiazole. 5.6-diethoxybenzothiazole. benzoselenazole. 5-chlorobenzoselenazole. 5-bromobenzoselenazole. 5-methylbenzoselenazole. 5-methoxybenzoselenazole. 4.5-dihydronaphtho[ l .2- dl-thiazole. 6-cyano-4.5-dihydronaphtho[ 1.2- zllthiazole. 6-ethyl-4.5-dihydronaphtho[ l.2-d]thia2ole. 8-chloro-4.5-dihydronaphtho-[ 1.2-z1]thiazole and like rings. The carbon chain length range of the alkyl moicty for the substituent groups on the above heterocyclic groups can be. c.g.. up to 4. preferably up to 2.

Examples of heterocyclic rings formed by Z of the General Formula (II). which may also be substituted with the same substituents as are described for the heterocyclic rings for Z include rings such as. for example. benzothiazole. 5-ehlorobenxothiazole. 5- bromobenzothiazole. 5-methylbenzothiazole. 5- methoxybenzothiazole. 5.6-dimethylbenzothiazole. 5.o-dimethoxybenzothiazole. 5-ethoxybenzothiazole. 5-methyl-6-methoxybcnzothiazole. 5-methyl-6- ethoxybenzothiazolc. 5-ethoxy-6-methylbenzothiazole. 5-hydroxy-omethylbenxothiazole. 5- phenylbenzothiazole. 5-hydroxybenzothiazole. 5- cyanobenzothiazole. 4.5-dihydronaphtho-[ 1.2- dlthiazole. 6-ethyl-4.5-dihydronaphtho[ l.2-/]thiazole.

S chloro-rl.5-tlihydronaphthol l .l-rlhhiazolc. benzose lenazole. 5 -chloi obenzoselenazole. 5- methylbenzoselcnazole. 5-mcthoxybenzoselenazole. 5.(w-diinethylbenzoselenazole. 5.6- dimethoxybenzosclenazolc. 5-phenylbenzoselenazole. fi-naphthobenzothiazole. etc.

Example ofheterocyclic rings formed by 7. of the General Formula (II). which may be substituted also with substituents such as those described withregard to 2:. include rings such as for example. benzoxazole. 5- methylbenzoxazole. 5-methoxybenzoxazole. 5.6-dimethylbenzoxazole. 5.(i-dimethoxybenzoxazole. 5- phenylbenzoxazole. benzimidazole. 5- chlorobenzimidazole. 5.(v-diehlorobenzimidazole. S-trifluoromethylbenzimidalole. etc. V

Examples of heterocyclic rings formed by Z.-, and 2,. ofthe General Formula (III which may be also substituted respectively with substituents such as those described with regard to Z include. for example. rings such as bengothiazole. 5-ehlorobenzothiazole. 5- bromobenzothiazole. S-methylbenzothiazole. 5- methoxybenzothiazole. 5-acetylbenzothiazole. 5-

methoxycarbonylbenzothiazole. S-ethoxycarbonylbenzothiazole. ,5-phenylbenzothiazole. 5- cyano benzothiazole. 5 hydroxybenzothiazole. benzoselenazole. 5-chlorobe'nzoselenazole. 5-

. methylbenzoselenaiole. ,5-me,thoxybenzoselenazole.

5-phenylbenzoselenazole. B-naphthothiazole. B-naphthoselenazole. etc.

A A and A in the General Formulae (I). (II) and (III). respectively. each represent.for example. a hydrogen atom. a methyl group. an ethyl group. a propyl group. a phenyl group. a phenethyl group. etc.

R R R R R and R, each represents. for example. a methyl group. and ethyl group. a propyl group. an allyl group. a hydroxyalkyl group (c.g.. a 2- hydroxyethyl group. a 3-hydroxyethyl group. etc.). a carboxyalkyl group (e.g.. a l-earboxyethyl groupfa 3-earboxypropyl group. a 4-earboxybutyl group. etc.). an alkoxyalkyl group (c.g.. a Z-methoxyethyl group etc). a sulfo-containing alkyl group (c.g.. a 3- sultopropyl group. a 3-sulfobutyl group. a 2 -[3-sulfopropoxy ]ethyl group. a 2-hydroxy-3 sulfopropyl group. a 3-sulfopropoxyethoxyethylgroup. etc-.. a haloalkyl group (e.g.. a 2-bromoethyl group etc. an aminoalkyl group (e.g.. a morpholinoalkyl group. etc.). a cyan'oalkyl group. a sulfoaralkylgroup (e.g.. a p-sulfophenethyl group etc.).

X T. Xfand Xfeach represents. for example. an iodide ion. a bromide ion. a chloride ion. a p-toluenesulfonie acid ion. a benzene sulfonic acid ion. an ethyl sulfuric acid ion. a perchlorate ion and arhodanate ion and like acid anions which are usually contained in cyanine type dye salts.

The chemical structure of the sensitizing dye represented by the General Formula (I) can be characterized as being a'nonsymmetrical carbocyanine dye hav' ing at the nitrogen atom of the nitrogen-containing heterocyclic ring atleast one substituted alkyl group selected from the group consisting of hydroxyalkyl. earboxyalkyl and sulfo-containing alkyl groups. and also having its maximum sensitivity wave length preferably at the region between 580 nm and 625 nm. The sensitizing dye is also characterised by the tendency to form J-aggregates.

Moreover. the dye of the General Formula (I) is characterized as having the capability of enhancing the spectral sensitivity hen used in combination with a dye of the General Formula (ll) or of the (ieneral l-ormula (lll). without its maximum sensitivity being shifted towards the range of wave lengths longer than The chemical structures of sensitizing dyes each represented by the General Formulae (ll) and (III) are characterized as having substituent group or groups selected from the group consisting of hydroxyalkyl. carboxyalkyl and sulfo-containing alkyl groups which may be bonded to either one or preferably both nitrogen atoms of the nitrogen-containing heterocyelie nucleus.

By using these particular dyes. it now has become possible to impart high red sensitivity with minimum amount of addition while not shifting the maximum sensitivity towards the too long wave length region. and also to reduce color stains which form after development even when a fairly large amount of the dye is used.

The super sensitizing activity exerted by the combination of the particular dyes according to the present invention is highly resistant against any inhibiting activity to spectral sensitization due to the presence of color couplers.

For instance. the combination of color sensitizing dyes of the present invention does not increase fogging tendencies. nor is accompanied by diffusion of the dye into adjacent emulsion layer so as to eventually sensitize the layertsilver halide) when it is applied to the one of the multi-layered photosensitive emulsion layers.

The super sensitizing technique according to the present invention is useful for the production of orthopan type photosensitive emulsions. coupler-inemulsion type color photosensitive emulsions of a multi-layered structure as disclosed. e.g.. in US Pat. No. 3.480.434 and British Pat. No. l.252.()66. especially for the production of emulsions to be used as reversal or negative color photosensitive materials.

-Preferredexamples of the sensitizing dyes used in the present invention are illustrated by the examples given as follows. but it should be noted that the sensitizing dyes of this invention are not limited to these specific examples only.

Examples of dyes represented by the General Formula (l):

0 fz 5 s C-CH=C-CH=C 11 \N CH 3 c H (CH2)5SO3 2 5 C-CH=C-CH=C t CH 3 i (CH2)5SO5H (cti so C-CH=C-CH=C \N% \N OCH E) l I 4 3 i t c H (CH2)5SO5 2 5 (cit sog ill-t The silver halide photographic emulsion used in this invention can be prepared using conventional techniques. and contains therein fine particles of silver chloride. silver bromide. silver iodide and mixtures thereof which have been produced by precipitation in accordance \vith.c.g.. the single jet process. the double jet process or a combination of these processes. followed by ripening.

These emulsion preparations are described in. for example. Trivelli Smith The Photographic Journal. Vol.

79. pp. 330-338. C.E.K. Mees. The Theory ofP/zolographic Process. MacMillan and Grafkides Photographic- C'hemI's-Iry. Vol. 1 pp. 327336. Fauntain Press. It is preferred that the silver halide contains at least 90 1110171 silver bromide and less than 7 mol'/( silver iodide. A preferred halogen composition in mob/r of iodide is no more than mol /r. for example from 2 mol /1 to 7 mob/r.

The use of silver iodobromide or silver iodochloride is especially preferred.

The average particle diameter (e.g.. as measured by the projected area method in numeral mean) desirably is within the range of from 0.04 ,u. to 2 u.

The silver halide photographic emulsion used in this invention can be sensitized according to conventional sensitizing methods including. for example, using gold sensitization (as disclosed in U.S. Pat. Nos. 2.540.085; 2.597.856; 2.597.915; 2.399.083. ctc.). sensitization using Group VIII metal ions of the periodic table. sulfur sensitization (as disclosed in U.S. Pat. Nos. 1.574.944; 2.278.947; 2.440.206; 2.410.689; 3.189.458; 3.415.649. etc). reduction sensitization (as disclosed in U.S. Pat. Nos. 2.518.698; 2.419.974; 2.983.610. etc.). and using various combinations of two or more of the above described sensitizing methods.

Typical examples of chemical sensitizers include thiourea. sodium thiosulfate. cystine and the like sulfur-containing sensitizers; potassium cbloroaurate. aurous thiosulfate. potassium chloropalladate. and the like noble metal sensitizers: tin chloride. phenyl hydrazine. rcductone and the like reducing sensitizers. etc.

Other sensitizers such as polyoxyethylene compounds (as disclosed in U.S. Pat. No. 2.716.062). polyoxypropylene compounds having an oxonium or ammonium group (as disclosed in U.S. Pat. Nos. 2.271.623: 2.288.226; and 2.334.864) can also be included.

The emulsion ofthe invention can further contain antifoggants such as nitrohenzazoles. e.g.. nitrobenzimidazole as disclosed in British Pat. No. 403.789. platinate salts. e.g.. ammonium chloroplatinate. as disclosed in US. Pat. Nos. 2.566.263: and 2.566.245. etc.. stabilizers such as 4hydroxy-6-methyl-l.3.3a.7- tetrazaindenc. thiazolium salts as disclosed in US. Pat Nos. 2.131.038 and 2.694.716. azaindenes. e.g.. 4- hydrosy-6-methyl-l.3.311.7-tetrazaindcne as disclosed in L'.S. Pat. Nos. 2.886.437 and 2.444.605. urazoles as disclosed in U.S. Pat. No. 3.287.135. sulfocatechols as disclosed in Pat. No. 3.236.652. oximes. mercaptotetrazoles as disclosed in Pat. .\'os. 2.403.927. 3.266.897. and 3.397.987. nitrons. polyvalent metal salts as disclosed in l'.S. Pat. No. 2.839.405. thiuronium salts as disclosed in 11.8. Pat. 3.220.839. salts of metals such as palladium. platinum and gold as disclosed in L'.S. Pat. Nos. 2.566.263 and 2.597.915. organic and inorganic hardeners such as formaldehyde. chromium alum. l-hydrosy-3.5 dichlorotriazine st diuni salt. glyoxal. dichloroacrolein. etc.. coating aids such as saponin. alkylaryl sulfonates such as sodium alkyl benzene sulfonates as disclosed in U.S. Pat. No. 2.600.831 and amphoteric compounds as disclosed in U.S. Pat. No. 3.133.816. etc.

The silver halide emulsion used in the present invention can be super sensitized by the combination with other sensitizing dyes and heterocyclic compounds under such condition that the wave length ofthe maximum sensitization is within the range of from approximately 580 nm to 640 nm.

For instance. it is possible to effect super sensitization by the use of dyestuffs such as those selected from the imidazolocarbocyanine dyes. imidazolooxacarbocyanine dyes. imidazolo-indocarbocyanine dyes. 2.2'-quinocyanine dyes. pseudocyanine dyes. simple merocyanine dyes. dimethine merocyanine dyes. styryl dyes (including styryl bases) etc.; and compounds such as imidazole (including imidazolinium) compounds. pyrazolone compounds. naphthothiazole compounds. benzothiazole compounds. triazole compounds. tetrazole compounds. etc.. as disclosed in C.E.K. Mees The Theory oft/1e Photographic Process. MacMillan and Frances M. Hamer The (yanine Dyes And Related (ompoioids. lnterscience Publishers. For example. these dyes include polymethine dyes having sulfoor carboxy-substituted alkyl group(s) as the N-substituent of the basic heterocyclic nucleus.

The use of the above described dyes and compounds also improves the inhibition of fogging and improves storability.

The silver halide emulsion used in this invention can contain color couplers such as are disclosed in U.S. Pat. Nos. 3.476.563; 3.516.831; 3.515.557; and 3.582.322 and dispersing agents therefor whenever it is used as a color photosensitive material. Of the various color couplcrs. a cyan type coupler is especially preferred. Of these couplers especially favorable are a phenolic type coupler disclosed in U.S. Pat. No. 2.698.794; and a naphthol type coupler.

The silver halide photographic emulsion used in this invention can contain as a protective colloid gelatin or acylated gelatin such as phthalated gelatin. malonated gelatin. succinated gelatin; cellulose compounds such as hydroxycthyl cellulose and carboxymethyl cellulose. dextrin and the like soluble starches; hydrophilic polymers such as polyvinyl alcohol. polyvinyl pyrrolidone. polyacrylamide and polystyrene sulfonic acid.

Other additives such as plasticizers as dimension stabilizers. latex polymers and matting agents can be added as well.

The finished emulsion can be applied onto a suitable support such as a baryta paper. a resin coated paper. a synthetic paper. a triacetate film. a polyethylene terc phthalate film. a glass plate and other plastic bases.

The sensitizing dyes used in the present invenrion is added as a solution in a water-miscible solvent such as methanol. ethanol. methyl cellusohc. pyridine etc.

Each sensitizing dye of the general formula (1). (11) and (111) is used in a conventional super color sensitizing amount. that is. 5 X 10 mol to 1 X 10 mol of each respective dye per mole of silver.

The molar ratio of the dye of the General Formula (11) or (111) used to the dye of the General Formula (1) can broadly be that amount sufficient to supersensitize but. is preferably from :1 to 1:5.

It is particularly desirable that the molar ratio of the dye of the (jeneral Formula (I) be higher than that of the dye of the General Formula (lll 'l'he dyes used in the present invention can be used as well in the spectral sensitization according to the s method described in German Patent Offenlegungsschrift No. 2.104.283 and US. Pat. No. 3.649.286.

The present invention now will be explained in greater detail by reference to the following examples tometer equipped with a light source of a color temperature of 5400K through various filters attaehedirespeetively thereto. including ablue filter (Sp-l). a yellow filter (Se-50). and a red filter (Sc-56) manufactured by the Fuji Photo Film Co.. Ltd.

Meanwhile. another ex posure was effected .in order to obtain a spectrogram using a diffraction grating spectrograph having a tungsten light source of a color temperature of 2(166K.

The thus exposed samples were developed using a dewhich should in no way be construed as limiting the It) scope of the present invention. Unless otherwise indivelopcr liquid (D 1 having the following composicated, all parts and percents are by weight. tion. at 20C for 2 minutes, then stopped. fixed and rinsed with water to give strips with a given black -andwhite image. Composition of the Developer Liquid 7 15 (D 9): EXAMPLE I Silver halide grains were precipitated in accordance watt-r 500 cc t Metol I 2 with the double et process. physically ripened using Anhwmus swiumsumw 970g conventional methods. and desalted followed by ehcmllydroquinone s ical ripening to Provide a silver iodobromide emulsion fi Mmwhrdrlds oassi L e 5 with an iodide content of 7 mol /z. The average diamew l make 1 lim ter of the silver halide grains contained in the resulting emulsion was 0.42 micron. The emulsion contained 0.52 mol silver halide per kilogram thereof. One kilo- 7Q gram of the emulsion was weighed and put in a pot. and then the pot was immersed in a thermostatic bath kept Densitometry testing was carried on these strips using at 50C to effect dissolution. On the-other hand. methaan S-type densitometer manufactured bythe Fuji Photo nol solutions containing the sensitizing dyes ofthe pres- Film Col. Ltd.. so as to obtain a blue filter sensitivity ent invention and solutions containing other comparim (S,,). a yellow filter sensitivity (S,-) a d d g i ivi son sensitizing dyes were respectively prepared and (S,,) and fog. respectively. added in a given amount to the emulsion and mixed The standard of optical density at which the sensitivunder stirring at 40C. The resulting emulsion was furity was determined was (fog l 0 .20). ther combined with 10 cc ofa 0.1% by weight aqueous The results obtained are "shown in Table l as relative solution of4-hydroxy-6-methyl-l.3.3a-7-tetrazaindene. values. Experiments Nos. ll. 13 and l5"'wer e carried 10 cc of a 171 by weight aqueous solution of l-hydroxyout for the purposes of comparison; 3.5-dichlorotriazine sodium salt and 10 cc of a l% by The spectral transmittance curves of the Sp-l filter. weight aqueous solution of sodium dodecylbenzene sulfilter Sc-50 filter and 50-56 filter are shown in FIGQZO. fonate under stirring. The spectrograms thus obtained are shown in FIGS.

The resulting finished emulsion was then applied 40 l to 19. onto a cellulose triacetate base film in a dried thickness lt wil be understood from the values in Table l and of 5 microns and dried to obtain samples of the photothe corresponding spectograms thereof that the combisensitive material. nations of particular super sensitizing dyes in accor- Each film sample was cut into strips. One of the strip dance with the present invention exhibits remarkably pieces was wedge-exposed by irradiating with a sensi- 'atlvantageous effects; i

Table l Value too low .to bemeasured Type and Type and l'ype and S Y SR SB Quantity of Quantity of Quantity (Rela- (Rela- (Rela- Fog- Spectro- No Dyes l'setl [)tes l'sed of Dyes L'sed live) live) live) ging gram X 10 "mol X l0 mol 10 "'mol Value Value Value 2 its ,0: [00 0.07 4 205 I40 100 0.07 s s :10 14X 100 0.|0 Fig. l l

till-B) l I 40 41 100 0.08 Fig.5 It 2 (it 0.08 till-B) 4 100 100 100 0.08 Fig. l 3 (l'.-\) s i I :34 205 xx 0.09

s 4 250 238V 74 0.10 Fig. I 3 2 til-(i 4 175 I25 96 0.00

s zixr-is 92 0.00 Fig. 2 4' 3 tll( s :Is 100 77 0.07 i

s s 218 74 0.10 Fig. 2 5 3 (Ill-Al 2 7 s0 240 0.06 l

i 4 its 124 so 0.00 ,Fig. 3 6 tl-Al s 2 :34

Table lCont1nued Value too low to be measured Type and Type and Type and S Y SR SB Quantity 01' Quantity of Quantity (Rela' (RelalRela- Fog- Spectro- No Dyes Used Dyes Used 01' Dyes Used live) live) live) ging gram X lt)""n1ol X 10 ""mol I()""ml Value Value Value 4 258 'Zl'l 8H (1.08 Fig. 3 7 4 (ll-A) 4 160 11x 92 0.06

- x 1x6 140 x4 0.07 Fi 4 x (ILA) 4 1111-13) 1 215 165 92 007 (FM 4 4 1 250 205 xx 007 Fi 4 9 5 (LC) 2 150 130 100 0.07 Fi 6 13 4 230 190 96 0.09 x 234 190 92 0.10 Fi 5 10 (LC) x 1111-151 1 x 224 xx 0.0x Fi 5 12 x 4 25x 2 15 xx 00x 6 11C) 2 (ll-A) x 220 165 007 Fi 6 14 7 2 114 77 96 0.06 Fi 7 15 4 175 140 xx 0.06 x 212 1x5 x0 0.07 (LC) 8 (Ill-C) 2 2x11 260 xx 0.0x Fi 7 16 x x 257 230 53 0.0x x (0F) 2 xx 77 71 0.06 Fi x 17 x 155 125 70 0.07 (III-D) 2 x0 74 104 0.07 4 96 114 0.07 Fi x 1x (ll-F) 2 (1111)) 4 1x0 174 100 0.07 Fig. 9 19 (LC) x (ll-F) 2 (111-1)) 4 267 225 xx 0.10 Fi 9 20 9 (1-F) 2 110 96 94 0.07 Fi 1021 4 110 x4 0.07 x 135 124 75 0.09 (11 1)) 4 x6 100 0.07 x 1x6 124 97 0.0x Fi 10 22 (l-F) 2 ("D1 x 1x6 142 x5 0.0x Fi 10 23 x x 175 142 75 0.09 10 (111 1 1 x2 x4 7x 0.09 Fi 11 24 4 146 71 0.09 111-1)) x (iii-F1 1 232 192 xx 0.0x (l-F) x 111 1)) x (Ill-F) 1 250 204 65 0.11 Fig. 1125 11 (l-F) 4 (Ill-F) 1 216 1x0 611 0.0x Fi 1226 4 4 216 192 63 0.0x 1D) 1 51 49 100 0.0x Fig. 12 x 4 x0 x6 90 0.0x (l-F) 4 (1)) 1 174 7x 0.011 Fi 12 7 4 4 170 155 67 0.011 12 (FF) 2 (ll-A) x 210 150 x5 0.0x Fi 13 29 4 x 205 150 7x 0.0x 13 (l-F) x (llLB) 1 150 142 71 0.07

x 4 154 150 611 0.11 Fi 14 30 (C) 1 5x 45 71 0.0x (C) 4 15x 110 65 0.10 Fig. 14 31 (l-F) x (C) 1 150 120 6x 0.10

x 4 150 126 6x 0.10 Fi 14 32 14 (l-G) 2 135 12x 100 0.0x 4 200 15 2 100 0.0x x 224 175 100 0.10 Fi 15 33 (ill-G) 1 40 3x 97 0.07 Fi 15 34 4 63 6x xx 0.10 (l-G) x (Ill-G) 1 216 1x5 93 0.0x Fi 15 35 15 (M11 x (Ill-F) 1 26x 210 94 0.011 Fi 1636 (l-(i) x (D) 1 224 1x6 97 0.09 Fi 16 37 16 (LG) x (ND) 11 (Ill-F) 1 277 210 75 0.09 Fig. 17 3x 17 (ll-B) 2 1 10 100 0.07 4 200 142 9x 0.0x x 202 142 91 0.10 Fi 1x 39 (LG) 2 (ll-B) x 243 175 91 0.13 Fi 1x 40 1x (II-K) 2 9x x5 x4 0.07 4 125 100 70 0.07 (ll-K) x x2 70 50 0.07 Fi 19 41 4 (111-111 2 145 130 74 0.0x (LG) 4 4 2 200 x4 0.10 Fi 1942 The combination of the sensitizing dyes having super materials such as cathode ray tube (CRT). holography sensitizing activity in accordance with the present inand facsimie Systems etc. vention is utilized favorably for the spectral sensitization of a silver halide photographic emulsions to be When used in a color photosensitive material. it is used in a red sensitive layer of a color photosensitive preferable to provide a magenta or a red external filter upon or adjacent to the red-sensitive silver halide emulsion layer obtained according to this invention, so as to give such an effect that the green sensitivity of the photosensitive material is substantially reduced with respect to its red sensitivity. In order to form such a filter layer. various dyestuffs described in a number of patent specifications can be employed, e.g.. thus such as described in Japanese patent publication Nos.

l8459/l966, 3504/1968, 13168/1968, 22069/1964: Japanese patent application Nos. 98474/1971, 42668/1971, and 42667/1971; US. Pat. Nos. 3,440,051; 3,468,883; 3.294.539; 3,379,533; 3,352,680; 3.379.533; 3,389,994; 3,384,487; 3,423,207; 3,493,375; 3,486,897; 3,48l,927; 3,497,502; 3.573.289; 3,560,2l4; 3,6l5,432; and

3,282,699; British Pat. No. 506,385.

The use of a material which selectively absorbs wave lengths in the region shorter than 570 nm is especially desirable.

Moreover, such processes as those described in German Pat. Offenlegungsschrift No. 2.008.882; US. Pat. Nos. 3,425,834 and 3,282,699; Belgian Pat. Nos. 682,413; 685,292; 703,939 and 627,308: Japanese patent publication Nos. 21766/1965; 13498/1968; 15896/1970; 10254/1968, etc., can be employed. These materials can be used for inhibiting irradiation and to prevent halation as well they are incorporated in a halation preventing layer.

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. In a silver halide photographic emulsion spectrallysensitized to have its maximum sensitivity in a wave length region of at least from 580 nm to 640 nm, the improvement which comprises said silver halide photographic emulsion containing a super sensitizing amount of a combination of at least one earbocyanine dye represented by the General Formula (I):

wherein Z represents a group of atoms necessary for forming B-naphthoxazole ring or fi-naphthoimidazole ring; Z represents a group of atoms necessary for forming benzothiazole ring or a benzoselenazole ring; A represents a hydrogen atom, an alkyl group or an aryl group; R and R each represents an aliphatic group with the proviso that at least one of R or R is a hydroxyalkyl group, a carboxyalkyl group or an alkyl group having a sulfo group; X represents an acid anion and l is l or 2. with the proviso that when l is l the dye forms an intramolecular salt; with at least one dye of the General Formula (ll) benzimidazole ring; A represents a hydrogen atom, an,

alkyl group or an aryl group; R and R each represents an aliphatic group with the proviso that at least one of R or R is a hydroxyalkyl group, a carboxyalkyl group or an alkyl group having a sult'ogroup: X is an acid anion: m is l or 2. but with the proviso that when m is l, the dye forms an intramolecular salt; or of the General Formula (Ill) wherein Z and Z each represents a group of atoms necessary for forming a benzothiazole ring. benzoselenazole ring, B-naphthothiazole ring or B-naphthoselenazole ring; A;, represents a hydrogen atom. an alkyl group, or an aryl group; R and R each represents an aliphatic group with the proviso that at least one of R or R, is a hydroxyalkyl group. a carboalkoxy group or an alkyl group having a sulfo group; X; represents an acid anion group, n is l or 2, but with the proviso that when n is l the dye forms an intramolecular salt.

2. The silver halide photographic emulsion of claim 1, in which said heterocyclic ring formed by Z is a ,B-naphthoxazole ring, the heterocyclic ring formed by Z is a benzothiazole ring or a benzoselenazole ring in which the 5-position is either unsubstituted or substituted with a chlorine atom, a trifluoromethyl group. an alkoxycarbonyl group, a methyl group, a methoxy group or a phenyl group; and A is an ethyl group.

3. The silver halide emulsion of claim 1, in which said heterocyclic ring formed by Z is a ,B-naphthoimidazole ring; said heterocyclic ring formed by Z is a benzothiazole ring or a benzoselenazole ring in which the 5- position is either unsubstituted or substituted with a chlorine atom, a trifluoromethyl group, an alkoxycarbonyl group, a methyl group, a methoxy group or a phenyl group; and A is a hydrogen atom.

4. The silver halide photographic emulsion of claim I, in which A is a hydrogen atom or an ethyl group; and R and R are each a methyl group, an ethyl group, a propyl group, an allyl group, a carboxyalkyl group or a sulfoalkyl group.

5. The silver halide photographic emulsion of claim 1, in which A;, is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a phenyl group; and R and R are each a methyl group, an ethyl group, a propyl group, an allyl group, a carboxyalkyl group or a sulfoalkyl group.

6. A color photosensitive material containing in combination a sensitizing amount of at least one carbocyanine dye represented by the General Formula (I) of claim 1 and at least one dye selected from the group consisting of a dye represented by the General Formula (ll) of claim 1 and a dye represented by the General Formula (Ill) of claim 1.

7. The silver halide photographic emulsion of claim 1, wherein A A and A each represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group; and R R R3, R R and R each represents, an alkyl group, an allyl group, a hydroxyalkyl group, a carboxyalkyl group, an alkoxyalkyl group, a sulfo-containing alkyl group, a haloalkyl group, an aminoalkyl group, a

cyanoalkyl group, or a sulfoaralkyl group.

8. The silver halide photographic emulsion of claim 7, wherein A A and A each represents a hydrogen a phenyl group, or a phenethyl group; and R,, R R R R and R, each represents. an alkyl group. an allyl group, a hydroxyalkyl group. a carboxyalkyl group. an alkoxyalkyl group. a sulfo-containing alkyl group. a haloalkyl group, an aminoalkyl group. a cyanoalkyl group, or a sulfoaralkyl group.

9. The silver halide photographic emulsion of claim 1, wherein said rings for Z; are substituted rings. said substituents being halogen atoms. alkyl groups, trifluoromethyl groups. alkoxy groups. alkylcarbonyl groups. carboxy groups, alkoxycarbonyl groups. acyl groups. aryl groups. cyano groups, hydroxy groups. alcoholate groups, or amino groups.

10. The silver halide photographic emulsion of claim 1, wherein the ring formed by Z is benzothiazole, 5 chlorobenzothiazole. S-bromobenzothiazole. 5- fluorobenzothiazole, S-methylbenzothiazole. 5- methoxybenzothiazole, S-methylcarbonylbenzothiazole. S-carboxybenzothiazole, S-methoxycarbonylbenzothiazole, 5phenylbenzothiazole. cyanobenzothiazole. 5-trifluoromethylbenzothiazole. S-hydroxybenzothiazole, S-aminobenzothiazole. 5.6- dichlorobenzothiazole, 5-methyl-6- methoxybenzothiazole. 5.6-dimethylbenzothiazole, 5.6-dimethoxybenzothiazole, 5.6-diethoxybenzothiazole, benzoselenazole, 5-chlorobenzoselenazole, S-bromobenzoselenazole. 5-methylbenzoselenazole, or 5-methoxybenzoselenazole.

11. The silver halide photographic emulsion of claim 1 wherein said rings for Z Z Z and Z are substituted rings, said substituents being halogen atoms, alkyl groups. trifluoromethly groups, alkoxy groups. alkylcarbonyl groups. carboxy groups, alkoxycarbonyl groups. acyl groups, aryl groups. cyano groups. bydroxy groups. or amino groups.

12. The silver halide photographic emulsion of claim 1, wherein the ring formed by 2;; is benzothiazole. 5- chlorobenzothiazole. 5-bromobenzothiazole. 5- methylbenzothiazole, S-methoxybenzothiazole,

5 ,6-dimethylbenzothiazole, 5 ,o-dimethoxybenzothiazole, S-ethoxybenzothiazole. 5-methyl-6- methoxybenzothiazole, 5-methyl-6- ethoxybenzothiazole, 5-ethoxy-6-methylbenzothiazole, 5-hydroxy--methylbenzothiazole, 5- phenylbenzothiazole, 5-hydroxybenzothiazole, 5- cyanobenzothiazole. benzoselenazole. 5- chlorobenzoselenazole, 5-methylbenzoselenazole, 5- methoxybenzoselenazole, 5.6- dimethylbenzoselenazole. 5.6- dimethoxybenzoselenazole, 5-phenylbenzoselenazole, or Bnaphthobenzothiazole. the ring formed by Z is benzoxazole, S-methylbenzoxazole, 5- methoxybenzoxazole. 5,6-dimethylbenzoxazole, 5.6-dimethoxybenzoxazole, S-phenylbenzoxazole. benzimidazole. S-chlorobenzimidazole. 5,6- dichlorobenzimidazole, or 5-trifluoromethylbenzimidazole, and the ring formed by 2,, and 2,; each is benzothiazole. 5-chlorobenzothiazole. 5- bromobenzothiazole. S-methylbenzothiazole. 5- methoxybenzothiazole, 5-acetylbenzothiazole, 5-

methoxycarbonylbenzothiazole, S-ethoxycarbonylbenzothiazole. S-phenylbenzothiazolel 5 cyanobenzothiazole. S-hydroxybenzothiazole, benzoselenazole, 5-chlorobenzoselenazole, 5- methylbenzoselenazole, 5-meth0xybenzoselenazole, 5-phenylbenzoselenazole. B-naphthothiazole.- or B-naphthoselenazole.

13. The silver halide photographic emulsion of claim 1, wherein the silver halide of said emulsion is silver chloride. silver bromide. silver iodide or mixtures thereof.

14. The silver halide photographic emulsion ofclaim 13. wherein said silver halide contains at least 90 moW: silver bromide and less than 7 moW: silver iodidev 15. The silver halide photographic emulsion of claim 14, wherein the average particle diameter of the particles of said silver halide ranges from 0.04 p. to 2 ;.l..

16. The silver halide photographic emulsion olclaim 1, wherein each ol said sensitizing dyes is present in said emulsion at a level of 5 X 10" mol to l X 10" mole per mol of silver.

17. The silver halide photographic emulsion of claim 1, wherein the molar ratio of said dyes of the General Formula (II) or (ll l) to said dye of the General Formula -Continucd COOCH wherein said sensitizing dye of the General Formula (II) is (II-A)

Claims (23)

1. IN A SILVER HALIDE PHOTOGRAPHIC EMULSION SPECTRALLY SENITIZED TO HAVE ITS MAXIMUM SENSITIVITY IN A WAVE LENGTH REGION OF AT LEAST FROM 580 NM TO 640 NM, THE IMPROVEMENT WHICH COMPRISES SAID SILVER HALIDE PHOTOGRAPHIC EMULSION CONTAINING A SUPER SENSITIZING AMOUNT OF A COMBINATION OF AT LEAST ONE CARBOCYANINE DYE REPRESENTED BY THE GENERAL FORMULA (I):

2. The silver halide photographic emulsion of claim 1, in which said heterocyclic ring formed by Z1 is a Beta -naphthoxazole ring, the heterocyclic ring formed by Z2 is a benzothiazole ring or a benzoselenazole ring in which the 5-position is either unsubstituted or substituted with a chlorine atom, a trifluoromethyl group, an alkoxycarbonyl group, a methyl group, a methoxy group or a phenyl group; and A1 is an ethyl group.

3. The silver halide emulsion of claim 1, in which said heterocyclic ring formed by Z1 is a Beta -naphthoimidazole ring; said heterocyclic ring formed by Z2 is a benzothiazole ring or a benzoselenazole ring in which the 5-position is either unsubstituted or substituted with a chlorine atom, a trifluoromethyl group, an alkoxycarbonyl group, a methyl group, a methoxy group or a phenyl group; and A1 is a hydrogen atom.

4. The silver halide photographic emulsion of claim 1, in which A2 is a hydrogen atom or an ethyl group; and R3 and R4 are each a methyl group, an ethyl group, a propyl group, an allyl group, a carboxyalkyl group or a sulfoalkyl group.

5. The silver halide photographic emulsion of claim 1, in which A3 is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a phenyl group; and R5 and R6 are each a methyl group, an ethyl group, a propyl group, an allyl group, a carboxyalkyl group or a sulfoalkyl group.

6. A color photosensitive material containing in combination a sensitizing amount of at least one carbocyanine dye represented by the General Formula (I) of claim 1 and at least one dye selected from the group consisting of a dye represented by the General Formula (II) of claim 1 and a dye represented by the General Formula (III) of claim 1.

7. The silver halide photographic emulsion of claim 1, wherein A1, A2, and A3, each represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group; and R1, R2, R3, R4, R5 and R6 each represents, an alkyl group, an allyl group, a hydroxyalkyl group, a carboxyalkyl group, an alkoxyalkyl group, a sulfo-containing alkyl group, a haloalkyl group, an aminoalkyl group, a cyanoalkyl group, or a sulfoaralkyl group.

8. The silver halide photographic emulsion of claim 7, wherein A1, A2 and A3 each represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a phenyl group, or a phenethyl group; and R1, R2, R3, R4, R5 and R6 each represents, an alkyl group, an allyl group, a hydroxyalkyl group, a carboxyalkyl group, an alkoxyalkyl group, a sulfo-containing alkyl group, a haloalkyl group, an aminoalkyl group, a cyanoalkyl group, or a sulfoaralkyl group.

9. The silver halide photographic emulsion of claim 1, wherein said rings for Z2 are substituted rings, said substituents being halogen atoms, alkyl groups, trifluoromethyl groups, alkoxy groups, alkylcarbonyl groups, carboxy groups, alkoxycarbonyl groups, acyl groups, aryl groups, cyano groups, hydroxy groups, alcoholate groups, or amino groups.

10. The silver halide photographic emulsion of claim 1, wherein the ring formed by Z2 is benzothiazole, 5-chlorobenzothiazole, 5-bromobenzothiazole, 5-fluorobenzothiazole, 5-methylbenzothiazole, 5-methoxybenzothiazole, 5-methylcarbonylbenzothiazole, 5-carboxybenzothiazole, 5-methoxycarbonylbenzothiazole, 5-phenylbenzothiazole, 5-cyanobenzothiazole, 5-trifluoromethylbenzothiazole, 5-hydroxybenzothiazole, 5-aminobenzothiazole, 5,6-dichlorobenzothiazole, 5-methyl-6-methoxybenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-diethoxybenzothiazole, benzoselenazole, 5-chlorobenzoselenazole, 5-bromobenzoselenazole, 5-methylbenzoselenazole, or 5-methoxybenzoselenazole.

11. The silver halide photographic emulsion of claim 1 wherein said rings for Z3, Z4, Z5 and Z6 are substituted rings, said substituents being halogen atoms, alkyl groups, trifluoromethly groups, alkoxy groups, alkylcarbonyl groups, carboxy groups, alkoxycarbonyl groups, acyl groups, aryl groups, cyano groups, hydroxy groups, or amino groups.

12. The silver halide photographic emulsion of claim 1, wherein the ring formed by Z3 is benzothiazole, 5-chlorobenzothiazole, 5-bromobenzothiazole, 5-methylbenzothiazole, 5-methoxybenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5-ethoxybenzothiazole, 5-methyl-6-methoxybenzothiazole, 5-methyl-6-ethoxybenzothiazole, 5-ethoxy-6-methylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, 5-phenylbenzothiazole, 5-hydroxybenzothiazole, 5-cyanobenzothiazole, benzoselenazole, 5-chlorobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5,6-dimethylbenzoselenazole, 5,6-dimethoxybenzoselenazole, 5-phenylbenzoselenazole, or Beta -naphthobenzothiazole, the ring formed by Z4 is benzoxazole, 5-methylbenzoxazole, 5-methoxybenzoxazole, 5,6-dimethylbenzoxazole, 5,6-dimethoxybenzoxazole, 5-phenylbenzoxazole, benzimidazole, 5-chlorobenzimidazole, 5,6-dichlorobenzimidazole, or 5-trifluoromethylbenzimidazole, and the ring formed by Z5 and Z6 each is benzothiazole, 5-chlorobenzothiazole, 5-bromobenzothiazole, 5-methylbenzothiazole, 5-methoxybenzothiazole, 5-acetylbenzothiazole, 5-methoxycarbonylbenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenylbenzothiazole, 5-cyanobenzothiazole, 5-hydroxybenzothiazole, benzoselenazole, 5-chlorobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5-phenylbenzoselenazoLe, Beta -naphthothiazole, or Beta -naphthoselenazole.

13. The silver halide photographic emulsion of claim 1, wherein the silver halide of said emulsion is silver chloride, silver bromide, silver iodide or mixtures thereof.

14. The silver halide photographic emulsion of claim 13, wherein said silver halide contains at least 90 mol% silver bromide and less than 7 mol% silver iodide.

15. The silver halide photographic emulsion of claim 14, wherein the average particle diameter of the particles of said silver halide ranges from 0.04 Mu to 2 Mu .

16. The silver halide photographic emulsion of claim 1, wherein each of said sensitizing dyes is present in said emulsion at a level of 5 X 10 3 mol to 1 X 10 6 mole per mol of silver.

17. The silver halide photographic emulsion of claim 1, wherein the molar ratio of said dyes of the General Formula (II) or (III) to said dye of the General Formula (I) ranges from 100:1 to 1:5.

18. The silver halide photographic emulsion of claim 1, wherein said sensitizing dye of the General Formula (I) is

19. A light-sensitive silver halide photographic element comprising a support and having thereon the silver halide photographic emulsion of claim 1.

20. The photographic element of claim 19, wherein A1, A2, and A3, each represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group; and R1, R2, R3, R4, R5 and R6 each represents, an alkyl group, an allyl group, a hydroxyalkyl group, a carboxyalkyl group, an alkoxyalkyl group, a sulfo-containing alkyl group, a haloalkyl group, ann aminoalkyl group, a cyanoalkyl group, or a sulfoaralkyl group.

21. The photographic element of claim 20, wherein A1, A2 and A3 each represents a hydrogen atom, a methyl group, an ethyl group, an ethyl group, a propyl group, a phenyl group, or a phenethyl group; and R1, R2, R3, R4, R5 and R6 each represents, an alkyl group, an allyl group, a hydroxyalkyl group, a carboxyalkyl group, an alkoxyalkyl group, a sulfo-containing alkyl group, a haloalkyl group, an aminoalkyl group, a cyanoalkyl group, or a sulfoaralkyl group.

22. The photographic element of claim 19, wherein said rings for Z2 are substituted rings, said substituents being halogen atoms, alkyl groups, trifluoromethyl groups, alkoxy groups, alkylcarbonyl groups, carboxy groups, alkoxycarbonyl groups, acyl groups, aryl groups, cyano groups, hydroxy groups, alcoholate groups, or amino groups.

23. The photographic element of claim 19, wherein the ring formed by Z2 is benzothiazole, 5-chlorobenzothiazole, 5-bromobenzothiazole, 5-fluorobenzothiazole, 5-methylbenzothiazole, 5-methoxybenzothiazole, 5-methylcarbonylbenzothiazole, 5-carboxybenzothiazole, 5-methoxycarbonylbenzothiazole, 5-phenylbenzothiazole, 5-cyanobenzothiazole, 5-trifluoromethylbenzothiazole, 5-hydroxybenzothiazole, 5-aminobenzothiazole, 5,6-dichlorobenzothiazole, 5-methyl-6-methoxybenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-diethoxybenzothiazole, benzoselenazole, 5-chlorobenzoselenazole, 5-bromobenzoselenazole, 5-methylbenzoselenazole, or 5-methoxybenzoselenazole.

Images