US3881933A

US3881933A - Light-sensitive material undergoing little change of latent image formed therein

Info

Publication number: US3881933A
Application number: US397490A
Authority: US
Inventors: Akira Kumai; Keisuke Shiba; Nobuo Yamamoto
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1971-05-18
Filing date: 1973-09-17
Publication date: 1975-05-06
Anticipated expiration: 1992-05-06

Abstract

A gelatino-silver halide photographic emulsion containing 1. AT LEAST ONE OF A MONOMETHINE OR A TRIMETHINE CYANINE DYE HAVING A CATHODE POLAROGRAPHIC HALF WAVE POTENTIAL RANGING FROM -0.9 AND -1.8 VOLT AND AN ANODE POLAROGRAPHIC HALF WAVE POTENTIAL LOWER THAN 1.3 VOLT AND CAPABLE OF FORMING Jaggregate, and 2. AN ORGANIC COMPOUND WHICH CAUSES BRIDGING TO EFFECT A HARDENING ACTION AND, AT THE SAME TIME, REACTS WITH GELATIN RELEASING AN ORGANIC OR AN INORGANIC ACID IS DISCLOSED.

Description

[63] Continuation of Ser. No. 254,720, May 18, 1972.

[30] Foreign Application Priority Data May 18, 1971 Japan 46-33429 [52] [1.8. CI 96/111; 96/27 R; 96/126 [51] Int. Cl. G03c l/30; 0031c 1/14 [58] Field of Search 96/111, 126, 137, 27

[56] References Cited UNITED STATES PATENTS 3,106,468 10/1963 Burness 96/111 3,l28,184 4/1964 Lowe 96/1 I United States Patent 1 1111 3,881,933

Kumai et al. 1 May 6, 1975 LlGHT-SENSlTIVE MATERIAL 3,138,461 6/l944 Ryan 96/111 UNDERGQING LTTLE CHANGE 01: 3,174,861 3/ I965 Himmelmann et al. 96/111 3,305,376 2/[967 Homes et a1. 96/1 11 LATENT IMAGE FORMED THERE 3,542,549 11/1910 Emmi 96/111 [75] Inventors: Akira Kumai; Kelsuke Shiha; Nobuo 3,647,466 3/1972 Bruengger et al. 96/137 Yamamoto a" ofMinami Ashigara, 3,671,260 6/1972 Oftedahi et a1. 96/126 Kanagawa,.lapan 13 Assignee: Fuji Photo Film Co., 1.111.,

Minami Ashigam Karlagawa, Attorney, Agent, or Farm-Rothwell, M1on, Zmn & Japan Macpeak Sughrue [22] Filed: Sept. 17, 1973 [57] ABSTRACT [21] Appl. No.1 397,490

A gelatino-sllver halide photographlc emuls1on con- Related U.S. Appllcatlon Data mining 1. at least one of a monomethine or a trimethine cyanine dye having a cathode polarographic half wave potential ranging from 0.9 and 1.8 volt and an anode polarographic half wave potential lower than 1.3 volt and capable of forming J-aggregate, and

2. an organic compound which causes bridging to effect a hardening action and, at the same time, reacts with gelatin releasing an organic or an inorganic acid is disclosed.

11 Claims, No Drawings BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to a photographic lightsensitive material and, more particularly, it relates to a light-sensitive material comprising at least one lightsensitive layer which comprises a gelatino-silver-halide emulsion sensitized with a sensitizing dye.

2. Description of the Prior Art Gelatino-silver-halide emulsions sensitized with dyes are used for a black and white panchromatic film or a color film, and are particularly important for color films having multi-layer type emulsion layer.

It is well known to one skilled in the art that a certain kind of dyes belonging to the cyanine dyes change the spectral sensitivity of the photographic emulsion when added to a gelatino-silver-halide emulsion. It is also publicly known that this spectral sensitization caused by the addition of a particular dye varies depending upon the type of emulsion used. In addition, it is possible that changes in various conditions in the particular photographic emulsion changes the behavior of the spectrally sensitizing agents.

Silver halide emulsions spectrally sensitized by the addition of dyes are especially of importance in a color film. Because, usually, a color film comprises three different silver halide emulsion layers, each of which records different spectral regions of blue, green and red, respectively, and, after the development, each forms a yellow, a magenta and a cyan dye image, respectively.

However, as has already been reported in Photographic Science and Engineering, Vol. 3, No. 3 page 134 et seq. (I969), it is well known that, when added to an emulsion certain sensitizing dyes have little effect on latent image-regression while others retard regression and even cause image-intensification.

However, especially, color roll films for camera use are often left in a camera for a fairly long period of time after exposure to light before being processed in a prescribed manner.

The best color reproduction can be obtained only when the dye images formed in each of the layers are exactly balanced with each other. Accordingly, it is quite important that the latent images formed in each layer by the exposure to light should not change during the strong period before development, or that at least they should not change in a different way from each other. That is, there is a group of sensitizing dyes which are, as is described above, excellent for the spectral sensitization of the photographic emulsion, but which are not preferred because they increase the change of the latent image with the lapse of time, the image being formed by exposure to light in the photographic emulsion to which the sensitizing dyes are added.

The inventors have now found that this change in the latent image with the lapse of time can be reduced by adding a suitable substance to a photographic emulsion layer together with these sensitizing dyes.

Therefore, a first object of the invention is to obtain a gelatino-silver-halide photographic emulsion layer which is spectrally sensitized by a sensitizing dye having an excellent spectral sensitizing action in a specific wavelength region and, at the same time, undergoes little change of the latent image with the lapse of time, the latent image being formed therein by exposure to light. 5 Another object of the invention is to obtain a color film whose gradation and color reproduction do not change even when left for a fairly long period of time after exposure to light and before development.

Other objects of the invention will become apparent by the following description and the examples.

In the case of the photographic emulsion to be treated by a processing solution, it is especially preferable that the gelatin contained therein should be durable in an aqueous solution thereof. It is especially preferred that this gelatin layer should become durable in the aqueous solution at an elevated temperature as well as at an ordinary temperature since the gelatino-silverhalide photographic emulsion layer can be processed rapidly in a short time by processing it at an elevated temperature. Therefore, many hardeners which are capable of making the gelatin membrane durable in an aqueous solution heated to the higher temperature are known to one skilled in the art and, in fact, they are added to a silver halide photographic emulsion layer. For example, chromium alum, glyoxal, formaldehyde, 2,3-di-bromo-malealdehydric acid, the sodium salt of 2,4-di-chloro-6-hydroxy-S-triazine, etc. are well known.

However, among these hardeners, there are many which are excellent in gelatin membrane-hardening action, but which deteriorate the photographic properties of the emulsion by releasing acid when reacted with gelatin molecules. For example, among the above mentioned hardeners, the sodium salt of 2,4-di-chloro-6hydroxy-S-triazine releases hydrochloric acid, while 2,3-di-bromo-malealdehydic acid releases hydrobromic acid, and other hardeners such as 2-phenoxy-3- chloro-malealdehydic acid releases carbolic acid thus lowering the pH value of the dry emulsion membrane.

The lowering'of the pH in the emulsion layer by the production of acids will cause various changes in the photographic properties and, above all, it is well known to one skilled in the art that it can cause fading of the latent image formed in the emulsion layer with the passage of time (see, for example, Veroeffentlichungen des Wissenschafllichen Zentral Laboratoriums der Photographischen Ableitung Agfa Vol. 3 pages 47-52 (1933) Actually, while 2,4-dichloro-S-triazine derivatives are excellent gelatin hardeners, they have the disadvantage that the latent images formed in a gelatino-silver-halide photographic emulsion layer hardened by the addition thereof will fade with the lapse of time after exposure.

The tendency toward fading of latent image is increased by the use of this type of hardener, which has already been reported, for example, about [bl-type hardeners described below in Photographische Korrespondenz Vol. 105, pages 28-29 (I969) with data.

SUMMARY OF THE INVENTION The inventors have now found that a spectrally sensitized photographic emulsion layer which undergoes extremely little change of the latent image formed therein with the lapse of time can be obtained by adding, among these hardeners, such an organic compound (a gelatin hardener) that produces an organic or an inorganic acid, to the gelatino-silver-halide emulsion layer sensitized in a specific spectral region by the use of spectrally sensitizing dyes which have a latent imageintensifying action as is described herein, whereby the opposing actions of the two toward the change of the latent image with the lapse of time successfully counteract each other.

DETAILED DESCRIPTION OF THE INVENTION As is apparent from the description above, even when such hardeners that have the disadvantage that, while they are excellent in gelatin-hardening action, fading, with the lapse of time, of the latent image formed in the gelatino-silver-halide emulsion layer to which these hardeners are added increases according to a conventional manner" are used, a light-sensitive layer which is excellent in gelatin-hardening action and undergoes little fading of the latent image formed therein can be obtained by the present invention.

The sensitizing dyes employed in the invention give high spectral sensitivity and, at the same time, have an effect of giving strong latensification. The monomethine or trimethine cyanine dyes used for the invention have the characteristics of forming J-aggregate and having a cathode polarographic half wave potential between -O.9 and l.8 volt and an anode polarographic half wave potential lower than 1.3 volt. with respect to the J-aggregate, refer for examaple to C. E. K. Mees The Theory of the Photographic Process Revised; Macmillan, pp. 442 to 444, 450 to 459, 467, 475 or ibid the Third Edition, pp. 214, 240, 245, 254, 268. Furthermore, from the stand point of quantum theory, it is desirable that, in the state wherein the J-aggregate is formed on the surface of silver halide, the minimum vacant electron energy level should be in the vicinity of the conduction band of the silver halide, preferably, a little higher than that, and that the normal electron energy level should be higher than the valence electron band of the silver halide.

The general formulae of the sensitizing dyes used in the invention are as follows. General formula (I) wherein Y, and Y each represents an oxygen atom, a sulphur atom, a selenium atom or a CH=CI-l group, Z, and 2: each represents the non-metallic atoms necessary to complete a benzene or naphthalene nucleus, n represents an integer of l or 2, X represents an anionic group usually used for cyanine dyes, P represents an integer of l or 2, and, when p represents 1 an intramolecular salt is formed, R, and R, each represents a lower alkyl group having, preferably, l to about 6 carbon atoms, an allyl group or a substituted alkyl group, and A represents a lower alkyl group having, preferably, 1 to about 3 carbon atoms or a substituted alkyl group. General formula (II) wherein Y;, represents an oxygen atom, a selenium atom, a =NR, group or a group, R and R each represents a methyl group or an ethyl group, R and R each represents a lower alkyl group having, preferably 1 to about 6 carbon atoms, an allyl group or a substituted alkyl group, R, and R, each represents a lower alkyl group having, preferably 1 to about 6 carbons atoms, an allyl group or a substituted alkyl group, 2;, and Z each represents the non-metallic atoms necessary to complete a benzene or a naphthalene nucleus, X{ represents an anionic group usually used for cyanine dyes, q represents an integer of l or 2, and, when q represents 1 an intramolecular salt is formed.

The dyes used for the inventionhave the characteristic of forming J-aggregate.

In the general formula (I), the benzene or naphthalene nucleus completed by Z, or 2 may be substituted with a lower alkyl group having, preferably l to about 6 carbon atoms, a halogen atom, an alkoxycarbonyl group, a phenyl group, an alkoxy group having preferably l to about 4 carbon atoms, a hydroxy group, etc. In the general formula (II), the benzene or naphthalene nucleus completed by Z or Z, may be substituted by a hydrogen atom, a cyano group, an alkoxycarbonyl group, a trifluoromethyl group, an alkylsulfonyl group, an alkylsulfamoyl group, an alkylcarbamoyl group, an acetoxy group, a lower alkyl group having, preferably, 1 to about 4 carbon atoms, an alkoxy group, etc. In the general formula (I) or (II), examples of suitable lower alkyl groups represented by R,, R R R R or R, are methyl, ethyl, propyl, butyl, etc., and examples of the substituted alkyl groups are hydroxyalkyl groups (e.g., a beta-hydroxyethyl group), acetoxyalkyl groups (eg, beta-acetoxyethyl, gamma-acetoxypropyl groups), aralkyl groups (e.g., a benzyl group), substituted alkyl groups having a sulfo or carboxy group (e.g., gammasulfopropyl, delta-sulfobutyl, 2( 3-sulfopropoxy)-ethyl, 2-[2-( 3-sulfopropoxy)ethoxylethyl, beta-carboxyethyl, gamma-carboxypropyl, delta-carboxybutyl groups), etc., and, for example, those described in German Pat. No. 929,080, US. Pat. Nos. 2,537,880 and 2,776,280, British Pat. No. 1,001,480, Japanese patent publication Nos. 4834/60, 14112/65, 23467/65, 2607/67, 15894/70, 27672/70, 27673/ and 32740/70, and the like are used. Examples of the group A in the general formula (I) are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a phenethyl group, a benzyl group, etc. Examples of X, and X{ are a bromide 5 6 ion, an iodide ion, a p-toluenesulfonate ion, a perchlo- Specific examples of the sensitizing dyes used in the rate ion, an ethylsulfate ion, a benzenesulfonate ion, invention are as follows, but the invention is not to be etc. interpreted to be limited only to them.

( Eox(volt) Ered(volt) I l :Z N 1.041 -1.o36 l SQ HN(C H' Eox(vo1t) Ered(volt) 0.535 --l.SOO

so HN 3 cF N (CH2 50 (c21 s0 a Comp n is an example ofa sensitizing dye and 25831/70, 1999/71, and 3699/71, German OLS Nos. in addition a supersensitizing agent which can be used 1,772,956; 1,81 1,542; 1,929,037; 2,01 1,879; together with the sensitizing agent used in the inven- 2,014,896; 2,017,053; 2,030,326; and 2,031,491, etc. tion. The sensitizing dye of the invention may be used can also be applied thereto. either independently or in combination with other dyes 5 Among the cyanine dyes represented by the general or one or more of the above described dyes, as a superformula (I) or (11), especially preferable dyes are those sensitizing agent. represented by one of the following general formula That is, some of the sensitizing dyes of the invention (1]!) to (V1), Genera] formula (11]): are sensitizing dyes and in addition are also supersensitizing agents, for example 10 c ..c =c-c Eox(volt) "I N 0.59s ((312 30; l Eredholt) (CH2 -CH-SO Na 30 In addition to the foregoing, supersensitizing agent wherein Y,, Z, and Z, are the same as defined in the the sensitizing art described in the Japanese patent general formula (1), and R and R each represents a publication Nos. 4932/68, 4933/68, 4936/68, sulfoalkyl group, which may be the same or different. 22884168, 2530/69, 32753/69, 264'70/70, 27671/70, Additional specific examples thereof are as follows.

(CH2)5SO3 c H o I 2 5 o l C-CH=C-CH c I m \N c H s a 5 General formula (IV):

Ta s (2 5 W W N\ 2 C CH-CH=CH-K w N W wherein R and R each represents a sulfoaikyl group, a trifluoromethyl group, and alkoxycarbonyl group or which may be the same or diflerent, W W W, and an alkylsulfonyl group. W each represents a chlorine atom, a bromine atom, For example, the following compound is illustrative.

. l (cn hso (CH MSO Na General formula (V):

wherein R,, R X, and p are the same as defined in the general formula (I).

Specific examples thereof are as follows.

wherein Z,, 2,, R,, R X and p are the same as defined in the general formula (I).

Specific examples thereof are as follows.

-CH :Ic I I l 62,15 0 x The aforesaid cathode polarographic half wave potential Ered can be strictly measured by volt-ammetry.

This is, it is measured in an acetonitrile solution (1X10- mol-4X10 mol) at 25C with the use of a dropping mercury electrode using saturated calomel electrode as a reference electrode, and using tetra-npropylammonium perchlorate as a supporting electrolyte. The anode polarographic half wave potential Eox can be measured in the same manner as in the Ered value with the use of a rotating platinum electrode using sodium perchlorate as a supporting electrolyte. A more detailed procedure is described in the German O.L.S. No. 2,010,762.

The sensitizing dyes employed in the invention are used, preferably, in an amount of from l l0 to 1X10 mol per 1 mol of silver halide. The amount of the dye can be varied depending on the property of the emulsion and the dye employed. The sensitizing dyes are added in any conventional manner, for example, by dissolving them in water, methanol. ethanol, pyridine, methyl cellosolve, acetone, etc. Other procedures described in Japanese Patent Application No. 8231/70, Japanese patent publication No. 23389/69, 27555/69, and 22948/69, U.S. Pat. No. 3,485,634; 3,342,605; and 2,912,343, German O.L.S. No. 1,947,935, etc. may be used.

The gelatin hardeners used according to the invention are those which react with gelatin and cause bridging to effect a hardening action and, at the same time, produce an organic or an inorganic acid as a byproduct. Examples of those which release hydrohalic acids are 2,3-dihalogenomalealdehydic acids (U.S. Pat.

No. 2,080,019), 2,4-dich1oro-S-triazines (U.S. Pat. No. 3,325,287), chloropyrimidine derivatives (British Pat. No. 1,193,290), polymers having a chlorotriazine ring as a side chain (U.S. Pat. No. 3,362,827, German O.L.S. No. 1,921,363), dichlorophosphoamide derivatives (British Pat. No. 974,723, and 1,004,658, U.S. Pat. No 3,125,449), halomethyl derivatives (British Pat. No. 990,275), and phosphonitrilechloride derivatives (US, Pat. No. 3,186,848). Examples of those which release phenol derivatives are 2-phenoxy-3- halogeno-malealdehydic acid derivatives (British Pat. No. 1,192,775, U.S. Pat. No. 3,579,374), etc. Especially preferred hardeners are organic compounds which release hydrochloric acid, hydrobromic acid, carbolic acid, or carbolic acid derivatives. in practice, these gelatin hardeners are dissolved in a solvent which is miscible with water and does not affect the photographic emulsion, such as water, methanol, dimethylformamide, etc. and added at an any stage before coating them onto the emulsion. Suitable hardening effects can be brought about by adding them in an amount of, preferably, from 1 to 100 g, and in an optimum range, from 5 to 60 g, per 1 kg based on the dry weight of the gelatin contained in a coating composition which contains gelatin.

Specific examples of the above described hardeners are as follows.

N A 02 N 50 cm (HUGO j/ CS2 CH1: N

(f) Copolymer of 80 mol of the compound represented by the following formula; C} M cm cl and 20 mol of acrylic acid.

- g: P c1 OH H 0 C-CO-NH-CHZ-CHZ-NH-CO-CHZBI BrH Cl-C-CHO HOOC- -O-C-COOH C1-C-CHO The gelatino-silver-halide photographic emulsions used according to the invention are high speed emulsions, especially, a silver brom oiodide emulsion. However, the present invention is applicable to other silver halide emulsions such as silver chlorobromide, pure silver bromide, etc. A high speed silver bromoiodide emulsion usually contains less than mol percent of silver iodide, and is usually chemically sensitized with a sulfur sensitizing agent and/or a gold sensitizing agent to such an extent that optimum sensitivity is obtained, and is further spectrally sensitized with the aforesaid spectrally sensitizing agents. As sulfur sensitizing agents, sodium thiosulfate, triethylthiourea, allylisothiourea and, as gold sensitizers, HAuChAH O, AuSCN, etc. may be used in a conventionally known manner. In addition, various palladium compounds such as palladium chloride can also be used in combination.

As anti-fogging agents, benzotriazole, nitrobenzimidazole, S-nitroindazole, l-phenyl-S- merc aptotetrazole, 4-hydroxy-6-methyl-l ,3 ,3a,7 tetrazaindene, etc. are used.

As coating agents, anionic and non-ionic agents such as saponin, sodium dodecylbenzenesulfonate, sucrose monolaurate, polyethyleneglycol nonylphenylether, etc. can be added in a suitable amount.

The invention is applicable for usual black and white films or multi-layer color sensitive materials containing no color coupler and, in addition, it is also applicable to a superposed color sensitive material wherein an emulsion spectrally red-sensitized with spectrally sensitizing agents and containing a cyan coupler, an emulsion spectrally green-sensitized with spectrally sensitizing agents and containing a magenta coupler, a yellow filter layer which can be bleached, and a blue sensitive emulsion containing a yellow coupler, are coated on a support in turn. Each layer is often coated in the order described above. However, this order can be altered depending upon the purpose of use. Furthermore, auxiliary layers such as a filter layer, a intermediate layer, an anti-halation layer, a protective layer, etc. may be additionally provided. The emulsions are coated, for example, on paper, polymer laminated paper, glass, cellulose triacetate, or films of synthetic filmforming resin such as polyesters, polyamides, polystyrenes, etc. Of the above supports, cellulose triacetate and polyesters are prefered. A suitable coating amount of the emulsion is prefered to be within a range of from about to about 200 mg of silver per 100cm or a thickness of from about 5 to ,u of emulsion after drying.

The invention will now be explained in greater detail by reference to the following examples which are for the purposes of illustration.

EXAMPLE I 500 g portions of a high speed gelatino-silverbromoiodide negative emulsion (5.5 mol percent in silver iodide content) containing 0.32 mol of silver halide per 1 kg were weighted out, and heated to C to dissolve, the emulsion being previously chemically sensitized with sodium thiosulfate and chloroauric acid in a conventional way to such an extent that suitable sensitivity can be obtained. The spectrally sensitizing dyes given in the table 1 were added to the emulsions with stirring and, after stirring for an additional 15 minutes, were allowed to stand. To these were added 20 cc portions of a 1 percent aqueous solution of 4-hydroxy-6- methyl-l,3,3a,7-tetrazaindene, then, the hardeners described in Table l were added thereto and, in addition, 5 cc portions of a 4 percent saponin aqueous solution were added. Thereafter, the emulsions were coated on a cellulose triacetate film base previously undercoated, then dried.

On the other hand, in the measurement of the melting point of the emulsion membrane, the melting point was determined by raising the temperature of water wherein each sample having been coated three days before was dipped, until the emulsion membrane melted or peeled from the film base. The temperature at which these phenomena occurred was regarded as the melting point.

Then, four strips were cut from each of the emulsioncoated samples for testing, and two of them l) and (2) were exposed to a tungsten light source (2854K) through a blue filter (a BPN filter made by the Fuji Photo Film Co., Ltd.) and a yellow filter (an SC- filter made by the Fuji Photo Film Co., Ltd.), respectively, and both through a neutral wedge. After leaving for 5 days at 50C under a 70 percent relative humidity, these were developed for 4 minutes at 20C with the use of a developer having the following composition.

Immediately before this development, the other two strips (3) and (4) which had been stored in a room at a temperature of 20C for these 4 days were exposed in the same manner as described above, and developed at the same time as l) and (2), and additionally, fixed, washed, dried to obtain negative images. The H and D curves were drawn in a conventional manner using an optical densitometer, and the sensitivity at the point of an optical density of +0.2 in fogging was calculated. The sensitivity is given in the table as the ratio of the sensitivity of l or (2) to that of (3) or (4). These values can be regarded as a measure of the rate of change of the latent image" in the case in which the samples were left for 4 days at 50C under a percent relative humidity. This storage condition is known to correspond to the case of being left for about 3 months in a usual room condition.

Composition of the Developer:

Metol 0.3 g Potassium Pyrosulfile 1.4 g Anhydrous Sodium Sulfite 38 g Hydroquinone 6 g Sodium carbonate monohydrate 22.5 g Citric Acid 0.7 g Water to make up 1000 cc Table 1 Contmued Test sensitizing Dye Hardener Changing Ratio MP.

of Latent Image of No. (56) (50C, 65% Sample RH, for 4 days) 69 (1X10-") 136 112 32 70 150 132 32 7| 40 b 15 136 132 72 40 b 30 120 120 73 40 b 45 H2 112 100 74 U (5 l0") 10 100 100 32 75 20 110 110 31 76 40 100 100 32 77 U [(SXHJ") l0 152 160 32 M (DUO-3) 2U 78 U (5)60) 10 h 30 126 130 100 M (lXl0"") 20 79 P (1x10) 20 132 132 31 80 40 142 160 32 81 P (l (l0) 20 160 160 31 L 6X10) 10 82 P (1Xl0'-") 20 l 5 130 130 72 L (5Xl()) 10 83 N (lxlu- 20 150 150 32 84 40 145 145 32 85 j 60 86 86 86 20 j 60 110 No.6, 7, 8,14,15, 20, 21, 26, 31, 32, 36, 40, 41, 44, 30 45, 46, 50, 51, 54, 55, 59, 60, 64, 67, 68, 71, 72, 73, 78, 82, 86 and 87 are combinations of the invention. The other test Nos. are given for comparison.

EXAMPLE 2 To 1,000 parts of a coarse grained high speed silver bromoiodide photographic emulsion containing 16 g of gelatin and 6.0 g of silver bromoiodide per 100 g of the emulsion (silver iodide content being 6.0 mol percent based on the total silver halide) were added the spectrally sensitizing dyes given in Table 2, 20 parts of a 1 percent aqueous solution of 4-hydroxy-6-methyll,3,3a,7-tetrazaindene as an an anti-fogging agent parts of a 5 percent alkaline solution of the cyan color coupler (T) of the following formula, hardeners given in Table 2, and, as a coating agent, 40 parts of a l percent aqueous solution of sodium dodecylbenzenesulfonate, in order, at 40C with sufficient stirring, then coated on a cellulose triacetate film base previously undercoated in a conventional manner, and dried (3.3 microns in dry film thickness).

SO Na l S0 Na 18 37 midity. The other control film strip was stored in a refrigerator at 20C during this period, then, exposed in the same manner as described above and immediately developed according to the processing as follows together with the foregoing strips.

1. Color Development (at 20C, for 8 minutes) 6. Washing (at 20C, for 5 minutes) 7. Second Fixing (at 20C, for 5 minutes) Conducted in the same manner as the first fixing. 8. Washing (for 20 minutes) All of the resulting cyan dye images formed on the strips were subjected to sensitometry through a red filter using an optical densitometer. The sensitivity was measured at a fogging point of +0.2, and the relative sensitivity of the sensitivity of the strip incubated after exposure to that of the control strip was regarded as the index of the change of the latent image with the lapse of time after exposure.

The melting points of the emulsion membranes were optimum sensitivity can be obtained, then, coated on a cellulose triacetate film base having been previously undercoated in a conventional way, dried (3.5 microns in dry film thickness).

measured in the same manner as described in Example 5 Two film strips were cut from each of the resulting 1. seven emulsion-coated samples, and each of the two Table 2 Test Spectrally Hardener Changing Ratio M.P.

Sensitizing of Latent Image of No. Dye with the Lapse Sample of Time (36) [mol concc g/Kg (2)}(4) (yellow (C) centralion gelafilter] tin 88 92 BI 89 b I5 88 42 90 b 30 7O 66 9! P(lXl) 40 140 32 92 [L (l l0) 20 156 32 M 20 93 P(lXl0) 40 b l l2(] 40 94 P ixiu 40 b 30 108 68 95 BJIHXIO) 20 b l26 43 96 ELHXIO) 20 b H2 70 in Table 2, No. 93, 94, 95, and 96 are the combinafilm strips was exposed to a 5400K light through a neutions ofthe invention. The other test Nos. are given for 30 tral grey wedge for 1/100 C then k p in a mom comparison. at 50C under a 70 percent relative humidity for 1 week. The other control film strip was stored in a re- EXAMPLE 3 frigerator at 20C during this period, then, exposed in 8 g of a magenta color coupler l-(2,4',6'- the same way as described above, and immediately detrichlorophenyl)-3-3"-(2"',4"'-di-tertiary-arnylveloped together with the aforesaid strips at 20C for phenoxyacetamide)benzamide -5-pyrazolone was 12 minut s sing the following developer. weighed out, and dissolved in a mixture of 25 cc of ethyl acetate and 4 cc of di-ri-butyl phthalate at the reflux temperature of ethyl acetate. The resultlng mixture 2 AmineddiethYlaminowluene Hydrochloride 2 i g was poured into a mixture of 65cc of a 10 percent gela- 4O Anhydrous Sodium Suifiie 2 g tin aqueous solution and a 5 percent aqueous solution Anhylmus 5"" Carbon 20 3 a Potassium Bromlde 2 g of sodium triisopropylnaphthalenesulfonate at 50 C in Benzy] Alcohd 2 8 about l minute with sufficient stirring, then passed gl/ater I th f H t0 [flake "P d through a colloid mill 5 times. Thereafter, the mill was a of e O owmg processmg was rinsed with 25 cc of water, and the resulting dispersion 45 Rinsing l5 sec. was solidified on a cooling plate cooled to 5C, cut into wgfig' F'xmg g strips, air-dried at 78C under a percent relative hu- Bleaching for 2 minutes using a solution containing 50 g of red prussiate and midity. The total dry dispersion weighed 18.5 g and, 2080f Potassium bromide Per 1 L when this was re-dispersed in gelatin, the grain dlame- Rinsing 15 sec, ter of the dispersed grains was larger than 0.5 micron 50 a? i l"- and no crystal separation was observed. 32

Methanol solutions of the sensitizing dyes given in Table 3, 5 parts of a 1 percent aqueous solution of 4- hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a fogging All of the resulting magenta dye images formed on agent, 5 parts of the above described magenta color the strips were subjected to sensitometry through a coupler dispersion, an aqueous solution of the harden green filter using an optical densitometer. The sensitivers given in Table 3, and 3 parts of l percent aqueous ity is given as a relative sensitivity of the sample incusolution of sodium dodecylbenzenesulfonate as a coatbated at 50C under a 70 percent relative humidity to ing agent were added in order with sufficient stirring that of the control sample. per lOO parts of the high speed gelatino-silver-halide The melting points of the samples were measured in negative emulsion which contained 60 g of gelatin and 60 g of silver bromoiodide (5 mol percent in silver iodide content) per 1 kg and was chemically sensitized in a conventionally known manner to such an extent that water in a conventional way as is employed by one skilled in the art of photographic industry after a 1 week period between the coating and drying of the samples.

a Table 3 Test Spectrally Hardener Changing Ratio M.P.

sensitizing Dye of Latent Image of No. l with the Lapse Sample of Time (mol cong/Kg (2)/(4) (yellow ("C) centration) cc gelafilter] 97 C (1)00) 40 I72 35 98 b 20 80 62 99 e l() 85 l I00 C (1x10 40 b H0 6| lOl C (U00 40 e l0 I06 l00 102 D (IMO- 40 I42 F (5Xl0) 20 mil D 0x10") b 20 I00 60 As is obvious from the results contained in Tables 1 to 3, in the combination of the sensitizing dye and the hardener in the invention, the changing rate of the latent image with the lapse of time is extremely near the ideal of [00 percent or no change. Therefore the object of the invention has effectively completed.

One the other hand, in the samples prepared for comparison, it can be seen that the changing rate deviates relatively greatly from the idea] 100 percent.

While the invention has been described in detail and in terms of various embodiments there of, it will be apparent to one skilled in the art that various changes and Y Ila Y r x f 1 l C=CH(-C CH-)C I x z n l 1i R R General formula (I) wherein Y, and Y, each represents an oxygen atom, a sulphur atom, a selenium atom, or a CH#IH group, Z. and 2, each represents the non-metallic atoms necessary to complete a benzene or a naphthalene nucleus, n represents an integer of l or 2, X, represents an anionic group, p represents an integer of l or 2, and, when p is I, an intramolecular salt is formed, R, and R each represents a lower alkyl group, an allyl group or a substituted alkyl group, and A represents a hydrogen atom, a lower alkyl group or a substituted alkyl group; or the following general formula (II) z 3 4 I /C CHCH-CHC\ J I,

l I General formula (II) 3 4 wherein Y, represents an oxygen atom, a sulphur atom, a selenium atom, a =NR,, group of a group, R, and R each represents a methyl group or an ethyl group, R and R each represents a lower alkyl group, an allyl group or a substituted alkyl group, R and R, each represents a lower alkyl group, an allyl group or a substitued alkyl group, 2;, and Z, each represents the non-metallic atoms necessary to complete a benzene or a naphthalene nucleus, X, represents an anionic group, q represents an integer of l or 2, and,

when q is 1 an intramolecular salt is formed,

wherein said substituted alkyl group for R R, R,, R R, or R, is a hydroxyalkyl group, an acetoxyalkyl group, an aralkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxy substituted by a lower alkyl group having from 1 to about 6 carbon atoms, a halogen atom, an alkoxycarbonyl group, a phenyl group, or an alkoxy group having from 1 to about 4 carbon atoms, wherein said benzene or naphthalene nucleus completed by Z, or Z, is substituted by a hydrogen atom, a cyano group, an alkoxycarbonyl group, a trifluoromethyl group, an alkylsulfonyl group, an alkylsulfamoyl group, an alkylcarbamoyl group, an acetoxy group, a lower alkyl group, or an alkoxy group, and wherein X, and X, each are a bromide ion, an iodide ion, a p-toluene sulfonate ion, a perchlorate ion, an ethyl sulfate ion or a benzene sulfonate ion.

6. The gelatino-silver halide photographic emulsion fading preventing method of claim 4 wherein said dye of the general formula (i) or (ii) has the general formula (iii) General formula (III) group, and wherein said substituted alkyl group for group; the general formula (IV) f s N 1 N CH I 2 C: -ClI=CH -C General formula (IV) w w A is an aralkyl group.

4. The gelatino-silver halide photographic emulsion fading preventing method of claim 3, wherein said organic compound is selected from the group consisting of 2,3-dihalogenomalealdehydic acids, 2,4-dichloro-S- triazines, chloropyrimidines, chlorotriazine ring side wherein R and R each represents a sulfoalkyl group and wherein W, W,, W, & W, each represents a chlorine atom, a bromine atom, a trifluoromethyl group, an alkoxy carbonyl group or an alkylsulfonyl group; the general formula (V) wherein R,, R,, X, and p are as defined in claim 2, or

chain containing polymers, dichlorophosphoamides, the general formula (VI) /Y1|/"\ '1 l ca= o f eneral formula (VI) halomethyls, phosphonitrile chlorides and 2-phenoxywherein Z,, 2,, R,, R,, X, and p are as defined in claim 3-halogeno-malealdehydic acids.

5. The gelatino-silver halide photographic emulsion fading preventing method of claim 4, wherein said benzene or naphthylene nucleus completed by Z, or Z, is

7. The gelatino-silver halide photographic emulsion fading preventing method of claim 4, wherein the cyanine dye is selected from the group consisting of 3,881,933 37 38 8. The gelatino-silver halide photographic emulsion and fading preventing method of claim 3 wherein the organic compound is selected from the group consisting 5 Cl-C-COOH Q n u Cl--C-CHO Cl-G-CHO Cl 9. The gelatino-silver halide photographic emulsion fading preventing method of claim 4, wherein said cyanine dyes are present at a level ranging from lXl0- to lX10-- mol per mole of silver halide, and wherein said organic compound is present at a level ranging from about I to about I00 g per Kg of gelatin in said emulsion on a dry basis.

10. The gelatino-silver halide photographic emulsion fading preventing method of claim 4, where said silver halide is silver chlorobromide, silver bromide or silver bromoiodide.

11. The gelatino-silver halide photographic emulsion fading preventing method of claim 10, wherein said silver halide is silver bromoiodide.

l 1. i I! t

Claims

1. A METHOD FOR PREVENTING FADING OF A LATENT IMAGE IN AN EXPOSED GELATINO-SILVER HALIDE PHOTOGRAPHIC EMULSION WHICH COMPRISES ADDING TO SAID PHOTOGRAPHIC EMULSION (1) AT LEAST ONE OF A MONOMETHINE OR A TRIMETHINE CYANINE DYE HAVING A CATHODE POLAROGRAPHIC OR A TRIMMETHINE CYANINE DYE HAVING A AND-1.8 VOLT AND AN ANODE POLARGRAPHIC HALF WAVE POTENTIAL LOWER THAN 1.3 VOLT AND CAPABLE OF FORMING J-AGGREGATE, AND (2) AN ORGANIC COMPOUND WHICH CAUSES BRIDGING TO EFFECT A HARDENING ACTION BY REACTION WITH GELATIN AND, AT THE SAME TIME, REACTS WITH GELATIN RELEASING AN ORGANIC OR AN INORGANIC ACID.

2. The gelatino-silver halide photographic emulsion fading preventing method of claim 1 wherein the fading preventing components consist essentially of components (1) and (2).

3. The gelatino-silver halide photographic emulsion fading preventing method of claim 1 wherein the cyanine dye is represented by the following general formula (I):

4. The gelatino-silver halide photographic emulsion fading preventing method of claim 3, wherein said organic compound is selected from the group consisting of 2,3-dihalogenomalealdehydic acids, 2,4-dichloro-S-triazines, chloropyrimidines, chlorotriazine ring side chain containing polymers, dichlorophosphoamides, halomethylS, phosphonitrile chlorides and 2-phenoxy-3-halogeno-malealdehydic acids.

5. The gelatino-silver halide photographic emulsion fading preventing method of claim 4, wherein said benzene or naphthylene nucleus completed by Z1 or Z2 is substituted by a lower alkyl group having from 1 to about 6 carbon atoms, a halogen atom, an alkoxycarbonyl group, a phenyl group, or an alkoxy group having from 1 to about 4 carbon atoms, wherein said benzene or naphthalene nucleus completed by Z3 or Z4 is substituted by a hydrogen atom, a cyano group, an alkoxycarbonyl group, a trifluoromethyl group, an alkylsulfonyl group, an alkylsulfamoyl group, an alkylcarbamoyl group, an acetoxy group, a lower alkyl group, or an alkoxy group, and wherein X1 and X2 each are a bromide ion, an iodide ion, a p-toluene sulfonate ion, a perchlorate ion, an ethyl sulfate ion or a benzene sulfonate ion.

6. The gelatino-silver halide photographic emulsion fading preventing method of claim 4 wherein said dye of the general formula (i) or (ii) has the general formula (iii)

7. The gelatino-silver halide photographic emulsion fading preventing method of claim 4, wherein the cyanine dye is selected from the group consisting of

8. The gelatino-silver halide photographic emulsion fading preventing method of claim 3 wherein the organic compound is selected from the group consisting of

9. The gelatino-silver halide photographic emulsion fading preventing method of claim 4, wherein said cyanine dyes are present at a level ranging from 1 X 10116 6 to 1 X 10116 3 mol per mole of silver halide, and wherein said organic compound is present at a level ranging from about 1 to about 100 g per Kg of gelatin in said emulsion on a dry basis.