JPH05341449A - Silver halide photographic product - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic product which hardly undergoes a change in the photographic performance during storage and has a wide exposure latitude. CONSTITUTION:This silver halide photographic product consists of a silver halide photosensitive material, a light shielding vessel 22 contg. the photosensitive material and hermetically sealing transparent vessels 25, 26 for housing the light shielding vessel 22. The photosensitive material is obtd. by forming at least one silver halide emulsion layer contg. a thiocyanate and at least two kinds of silver halide emulsions sensitized with gold-chalcogen and different from each other in average particle diameter on a base. The silver halide emulsions are prepd. so that the amt. of a sensitizing dye stuff per unit surface area is increased in the order of decreasing average particle diameter. This photographic product has a gaseous hydrogen cyanide scavenger at a certain position in the hermetically sealing vessels 25, 26.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to silver halide photographic products. More particularly, it relates to photographic products having a wide exposure latitude and having little change in photographic performance during storage.

[0002]

2. Description of the Related Art Generally, the exposure latitude of a silver halide photographic light-sensitive material is widened by mixing silver halide emulsions having different sensitivities or by providing such silver halide emulsions as separate light-sensitive layers. It is known that you can. Japanese Patent Sho 59-45974
JP-A No. 1989-242 discloses a silver halide light-sensitive material containing a mixture of silver halide emulsions having different average grain diameters which have been spectrally sensitized so that the amount of sensitizing dye per unit surface area becomes large. When a silver halide light-sensitive material produced based on this technique was tested, a wide exposure latitude was certainly obtained,
On the other hand, it was found that the fogging and the softening of the fog during storage were remarkable. After analyzing the changes in this photographic performance,
It was found that the gas generated in the silver halide photographic product had an influence. As a result of further detailed investigation of this gas, it was found that this gas was hydrogen cyanide gas, and the photographic performance was changed. Furthermore, it was discovered that, surprisingly, when the light hits the drawer portion of the film through the paper box containing the film case, hydrogen cyanide gas is generated, which greatly deteriorates the photographic performance.

If the silver halide is altered by the influence of hydrogen cyanide gas and the photographic performance is changed, the scavenger of hydrogen cyanide gas should be effective. As a scavenger of hydrogen cyanide gas, Tokuhyo 3-505
No. 263 discloses that compounds of palladium, gold and platinum are effective. Here, it is described that fogging caused by hydrogen cyanide gas generated from carbon black is prevented by including a hydrogen cyanide scavenger at a position where it can be blocked from the photosensitive emulsion. It is also stated that the position of addition of the scavenger is preferably close to the carbon black which is the generation source. However, there is no description suggesting that hydrogen cyanide gas is generated when the photosensitive material is irradiated with light. There is no description suggesting that the gas generated from the light-irradiated portion affects the photographic performance of the light-shielded portion. Further, there is no description that the thiocyanic acid compound contained in the light-sensitive material causes gas generation.

For example, US Pat. No. 2,566,245
No. 2,566,263, it is well known and well known to add a Pd compound to a silver halide photographic light-sensitive material. Actually, Pd is contained in the emulsion layer or the intermediate layer of the silver halide color photographic material.
Is widely practiced, eg 1988
Eastman Kodak Company's Rochuster Factory in New York, USA, valid for December, 2012
R-G100 Brownie film (EMUL.NO.2
4 031 13) has a Pd of about 3 × 10 ^-5.
It is contained in a black light-shielding paper containing about 8% of carbon black (about 0.7 g per one), and this film is hydrogen cyanide gas generated by light irradiation. Is believed to have had no effect.
Further, it is impossible to predict that this Pd is effective against the fog that may occur when the same light-sensitive material is commercialized in a film format having a design having a light-irradiated portion as in the present invention. Is. The present inventor believes that the following reaction occurs in the light-irradiated portion to generate hydrogen cyanide gas.

AgBr (+ hν; light irradiation) → 2Ag + Br ₂ (printout) 2AgSCN + Br ₂ → 2AgBr + (SCN) ₂ (SCN) ₂ hydrolysis → HCN From this reaction formula, it is found that a scavenger of halogen gas is also effective. Will. Further, in the case of a silver halide emulsion having high photosensitivity, it is expected that the bromine gas generated in the printout will increase and the hydrogen cyanide gas will also increase. It is also expected that the generation of hydrogen cyanide gas will increase when the humidity in the photographic product is high.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic product which has little change in photographic performance during storage and which has a wide exposure latitude.

[0007]

As a result of intensive studies, the object of the present invention could be achieved by the following means. That is, (1) at least two silver halide emulsions having different average grain sizes sensitized with gold and chalcogen and at least one silver halide emulsion layer containing thiocyanate are provided on a support. The light-sensitive material comprises a silver halide light-sensitive material, a light-shielding container containing the light-sensitive material, and a light-transmissive sealed container containing the light-shielding container. The light-sensitive material is partially located outside the light-shielding container. And has a structure in which gas can flow between the inside and outside of the light-shielding container, and the silver halide emulsions are prepared so that the amount of sensitizing dye per unit surface area increases in descending order of average grain size. The silver halide photographic product described above, which has a hydrogen cyanide gas scavenger at any position in the sealed container.

(2) The photographic product according to (1), which has a halogen gas scavenger at any position in the sealed container. (3) The photographic product according to (1), wherein hydrogen cyanide gas and a halogen gas scavenger are present in the photographic light-sensitive material. (4) Hydrogen cyanide gas scavenger is Pd, Pt
Alternatively, the photographic product of (1) selected from organic or inorganic compounds of Au. Could be achieved by

The hydrogen cyanide gas scavenger in the present invention is a compound that converts the hydrogen cyanide gas generated when the photosensitive material is irradiated with light into a photographically inactive substance. Therefore, the scavenger should not release any substance that adversely affects the silver halide light-sensitive material as a result of capturing the hydrogen cyanide gas. Suitable hydrogen cyanide gas scavengers can be selected from noble metal inorganic or organic compounds. Particularly preferred are palladium (II or IV) and platinum (II or IV) compounds. Gold (I or III) compounds are also preferred. Rhodium (III), Iridium (III or IV) and Osmium (I
Compounds of I, III or IV) are also effective, but higher amounts are required to have an equivalent effect. Specific examples of useful inorganic or organic noble metal compounds are described in detail, for example, in Gmelin Handbook, and are commercially available products, synthetic products, and ins.
The intu synthetic product should be used in such a purity that it does not adversely affect the photographic light-sensitive material. Representative examples of useful palladium compounds include palladium (II) chloride, palladium (II) bromide, palladium (II) hydroxide, palladium (II) sulfate, palladium (II) thiocyanate, and tetrachloropalladium (II) acid salt. (Sodium salt, potassium salt,
Ammonium salt), hexachloropalladium (IV) acid salt, tetrabromopalladium (II) acid salt, hexabromopalladium (IV) acid salt, bis (salicylato) palladium (II) acid salt, bis (dithiooxalato-S, S ') Palladium (II) acid salt, trans-dichlorobis (thioether) palladium (II), tetraamminepalladium (II) salt, dichlorodiamminepalladium (II), dibromodiamminepalladium (II), oxalatodiamminepalladium (II), dinitrodiamminepalladium (II) (II), bis (ethylenediamine) palladium (II)
Salt, dichloroethylenediaminepalladium (II), bis (2,2'-bipyridine) palladium (II) salt, bis (1,10-phenanthroline) palladium (II) salt,
Tetranitropalladium (II) acid salt, bis (glycinato) palladium (II), tetrakis (thiocyanato) palladium (II) acid salt, dichlorobis (phosphine) palladium (II), di-μ-chloro-bis (chloro (phosphine)) Palladium (II)), di-μ-chloro-bis (chloro (arsine) palladium (II)), dinitrobis (arsine) palladium (II), and the like.

Representative examples of useful platinum compounds are platinum (II) chloride, platinum (IV) chloride, and hexafluoroplatinum (IV).
Acid salt, tetrachloroplatinate (II) acid salt, hexachloroplatinum (IV) acid salt, trichlorotrifluoroplatinum (IV) acid salt,
Tetrabromoplatinate (II), Hexabromoplatinum (IV)
Acid salt, dibromodichloroplatinum (II) acid salt, hexahydroxoplatinum (IV) acid salt, bis (oxalato) platinum (II) acid salt, dichlorobis (oxalato) platinum (IV) acid salt, bis (thiooxalato) platinum (II) ) Acid salt, bis (acetylacetonato) platinum (II), bis (1,1,1,5,5,5)
-Hexafluoro-2,4-pentanedionato) platinum (II), bis (1,1,1-trifluoro-2,4-pentanedionato) platinum (II), tetrakis (thiocyanato) platinum (II) acid Salt, hexakis (thiocyanato) platinum (IV) salt, bis {(Z) -1,2-dicyanoethylene-1,2-dithiolato} platinum (II) salt, dichlorobis (diethylsulfide) platinum (II), tetra Chlorobis (diethyl sulfide) platinum (IV), bis (glycinato) platinum (II), dichloroglycinatoplatinum (II) acid salt,
Dichlorobis (triethylphosphine) platinum (II), chlorohydridobis (triethylphosphine) platinum (I
I), tetraammine platinum (II) salt, tetrachloroplatinum (II) salt, dichlorodiammine platinum (II), trichloroammine platinum (II) salt, hexaammine platinum (IV)
Salt, chloropentaammineplatinum (IV) salt, tetrachlorodiammineplatinum (IV), dinitrodiammineplatinum (I
I), dichlorotetrakis (methylamine) platinum (IV)
Salt, dichloro (ethylenediamine) platinum (II), bis (ethylenediamine) platinum (II) salt, tris (ethylenediamine) platinum (IV) salt, dichlorobis (ethylenediamine) platinum (IV) salt, dichlorodihydroxo (ethylenediamine) platinum (IV) ), Tetrakis (pyridine) platinum (II) salt, dichlorobis (pyridine) platinum (II), bis (2,2′-bipyridine) platinum (II) salt, tetranitroplatinate (II) salt, chlorotrinitroplatinum (II) ) Acid salt, dichlorodinitroplatinum (II) acid salt, dibromodinitroplatinum (II) acid salt, hexanitroplatinum (IV) acid salt, chloropentanitroplatinum (IV) acid salt, dichlorotetranitroplatinum (IV) acid salt, Trichlorotrinitroplatinate (IV), tetrachlorodinitroplatinate (IV), dibromodichlorodinitroplatinate (IV), trichloro Ethylene) platinum (II) salt, di -μ- chlorobis {chloro (ethylene)} platinum (II), trans- dichloro (ethylene)
(Pyridine) platinum (II), bis (bis (β-mercaptoethylamine) nickel (II) -S, S ″)-platinum (I
I) salts, dichlorodicarbonyl platinum (II) and the like.

Gold (I or III), Rhodium (III), Iridium (III or IV) and Osmium (II, III or IV)
Examples of the compound of ) And the like. As long as the effects of the present invention can be obtained, the inorganic or organic compound of the noble metal is not limited to the above specific examples. In the present invention, the hydrogen cyanide gas scavenger may be located at any position within the sealed container of the silver halide photographic product. It may be formed by coating or kneading on the inner surface of the sealed container, or may be formed by coating or kneading on the parts forming the light-shielding container. Particularly preferably, the hydrogen cyanide gas scavenger is present in the photographic light-sensitive material. The photographic light-sensitive material usually comprises a support, a back layer, an emulsion layer, a surface protective layer, an intermediate layer and an antihalation layer, and the hydrogen cyanide gas scavenger of the present invention is directly added to these layers for coating. It is applied alone with a suitable solvent or binder. As a method for adding the hydrogen cyanide gas scavenger, a method usually used when adding an additive to a photographic light-sensitive material can be applied. For example, a water-soluble compound is prepared as an aqueous solution having an appropriate concentration, and a water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, such as alcohols, glycols, ketones, esters and amides. Of these, it can be dissolved in a solvent that does not adversely affect the photographic characteristics and added as a solution.

The backing layer, emulsion layer, surface protective layer, interlayer and antihalation layer are usually binder dispersions, but useful binders include naturally occurring polymeric vehicles such as gelatin and cellulose derivatives and Included are synthetic vehicles such as polyvinyl alcohol and its derivatives, acrylate and methacrylate polymers, butadiene-styrene polymers and similar materials. When the hydrogen cyanide gas scavenger is directly added to these layers, it is necessary to carefully select the conditions such as the concentration and pH of the binder according to the type and amount of the hydrogen cyanide gas scavenger used. Generally, the precious metal compound and gelatin interact with each other, and the viscosity of the system may remarkably increase depending on the conditions. For example, regarding the interaction between palladium (II) ion and gelatin, the Journal of the Photographic Society of Japan, 34, 159 (197).
1) Keiichi Tanaka, Journal of the Photographic Society of Japan, Vol. 37, page 133 (1974) Keiichi Tanaka, Journal of the Photographic Society of Japan, Volume 39, page 73 (1976) Keiichi Tanaka, Journal of Photographic Science, Volume 21, page 134 (197)
3) Keiichi Tanaka and Journal of Photographic Science Vol. 26, page 222 (1978) Keiichi Tanaka. Since the palladium (II) ion has a strong bond with the amide bond and the amino acid residue of gelatin, it may form a lumpy foreign substance of gelatin under certain conditions. It is preferable to select and use. The addition amount of the hydrogen cyanide gas scavenger in the present invention should be determined within a range in which the effect of the present invention remarkably appears, but is preferably 1/10 mol or more per 1 mol of thiocyanate contained in the portion which can be irradiated with light. is there.
It is more preferably ½ mol or more and 100 mol or less, and particularly preferably 1 mol to 10 mol, per 1 mol of thiocyanate contained in the portion that can be irradiated with light.

The photographic light-sensitive material of the present invention contains a silver halide emulsion which is sensitized with gold and chalcogen and contains thiocyanate on a support. The support is, for example, RD. N
o. 17643, page 28, RD. No. 18716
Page 647 right column to page 648 left column, and R
D. No. 307105, page 879. The silver halide emulsion in the present invention is sensitized with gold / chalcogen. Chalcogen sensitization is a selenium sensitizer,
It is applied by at least one of a sulfur sensitizer and a tellurium sensitizer. Here, the selenium sensitization is performed by a conventionally known method. That is, it is usually carried out by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Selenium sensitization using the unstable selenium sensitizer described in JP-B-44-15748 is preferably used. Specific unstable selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenamides,
Examples include selenocarboxylic acids and esters, and selenophosphates. Particularly preferred unstable selenium compounds are shown below. I. Colloidal metal selenium II. Organic selenium compound (selenium atom double-bonded to carbon atom of organic compound by covalent bond) a. Isoselenocyanates Aliphatic isoselenocyanates such as allyl isoselenocyanates b. Selenoureas (including enol type) For example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, dioctyl, tetraoctyl, N- (β-carboxyethyl) -N ′, N′-dimethyl, N, N -Aliphatic selenoureas such as dimethyl, diethyl, dimethyl; aromatic selenoureas having one or more aromatic groups such as phenyl, tolyl;
Heterocyclic groups such as pyridyl and benzothiazolyl
Heterocyclic selenoureas having c. Selenoketones, for example, selenoacetone, selenoacetophenone, selenoketone having an alkyl group bonded to> C = Se, selenobenzophenone d. Selenoamides For example, selenoacetamide e. Selenocarboxylic acids and esters For example, 2-selenopropionic acid, 3-selenobutyric acid, methyl
3-Selenobutyrate III. Other a. For example, diethyl selenide, diethyl diselenide, triphenylphosphine selenide b. For example, tri-p-tolyl selenophosphate, tri-
-n-Butylselenophosphate Unstable selenium compounds have been described above in terms of preferred types.
These are not limiting. Speaking of those skilled in the art as unstable selenium compounds as sensitizers for photographic emulsions,
The structure of the compound is not critical as long as selenium is unstable and the organic part of the selenium sensitizer molecule carries selenium and has no role except to make it unstable in the emulsion. Is generally understood. In the present invention, the unstable selenium compound having such a broad concept is advantageously used.

Japanese Patent Publication No. 46-4553, Japanese Patent Publication No. 52-3
Selenium sensitization using the non-labile selenium sensitizers described in JP-B No. 4491 and JP-B-52-34492 can also be used. Examples of the non-labile selenium compound include selenious acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles, diaryl selenides, diaryl diselenides, 2-thioselenazolidinediones, and 2-selenooxo. Included are ginthion and their derivatives. The non-labile selenium sensitizer and thioselenazolidinedione compound described in JP-B-52-38408 are also useful. These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent and added at the time of chemical sensitization, but preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one kind, and two or more kinds of the above selenium sensitizers can be used in combination. Particularly, the combined use of an unstable selenium compound and a non-unstable selenium compound is preferable. The addition amount of the selenium sensitizer used in the present invention varies depending on, for example, the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and preferably silver halide. The amount is 1 × 10 ⁻⁸ mol or more, and more preferably 1 × 10 ⁻⁷ mol or more and 1 × 10 ⁻⁴ mol or less, per mol. When the selenium sensitizer is used, the temperature of chemical ripening is preferably 45 ° C. or higher, more preferably 5
It is 0 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary. For example, the effect of the present invention can be obtained in a wide range of pH from 4 to 9. In the present invention, it is more effective to carry out the selenium sensitization in the presence of a silver halide solvent. Examples of the silver halide solvent that can be used in the present invention include, for example, US Pat.
No. 1,157, No. 3,531,289, No. 3,5
74,628, JP-A-54-1019, 54-1.
(A) organic thioethers described in 58917,
(B) thiourea derivatives described in JP-A Nos. 53-82408, 55-77737 and 55-2982,
(C) Silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A No. 53-144319, JP-B No. 54-100717.
(D) imidazoles, (e) sulfite,
(F) Thiocyanate. Particularly preferred solvents include thiocyanate and tetramethylthiourea. The amount of the solvent used varies depending on the kind, but in the case of thiocyanate, for example, the preferable amount is from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol per mol of silver halide. Sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time. The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Known sulfur sensitizers can be used for the above-mentioned sulfur sensitization. Examples thereof include thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine.
Others, for example, U.S. Pat. Nos. 1,547,944, 2,410,689, 2,278,947,
No. 2,728,668, No. 3,501,313
No. 3,656,955, German Patent No. 1,422,868, Japanese Patent Publication No. 56-24937, and Japanese Patent Application Laid-Open No. 55-45016. You can also The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount, pH, temperature, varies over a range corresponding under various conditions such as the size of the silver halide grains, the silver halide per mol 1 × 10 ^-7 mol, 1 × 10 ^{- It} is preferably ⁴ mol or less. As the gold sensitizer for gold sensitization in the present invention, the oxidation number of gold may be +1 or +3, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, and pyridyl trichlorogold. The addition amount of the gold sensitizer varies depending on various conditions, but as a guide, it is 1 × 10 1 per mol of silver halide.
^It is preferably ^-7 mol or more and 1 x 10 ^-4 mol or less.

Gold / chalcogen sensitization is gold / sulfur sensitization and gold / sulfur sensitization.
Selenium sensitization, gold / tellurium sensitization, gold / sulfur / selenium sensitization,
It can be used by selecting from gold / sulfur / tellurium sensitization, gold / selenium / tellurium sensitization and gold / sulfur / selenium / tellurium sensitization. A thiocyanate is used together with these gold / chalcogen sensitizations. As thiocyanate,
Ammonium salt, potassium salt, sodium salt and the like are preferably used. The thiocyanate may be used alone during gold / chalcogen sensitization, or may be used in combination with a gold sensitizer. The thiocyanate may be added dividedly or continuously. In the present invention, thiocyanate is more preferably used not only during gold / chalcogen sensitization but also during grain formation or during the desalting step. US Pat. Nos. 3,320,069 and 4,4 describe the use of thiocyanates in grain formation.
34,226.

The silver halide light-sensitive material of the present invention comprises
The ISO sensitivity is preferably 100 to 3200,
It is more preferably 400 to 3200. The halogen gas scavenger in the present invention is a compound that converts a halogen gas generated when a photosensitive material is irradiated with light into a photographically inactive substance. Therefore, the scavenger should not release a substance that adversely affects the silver halide light-sensitive material as a result of capturing the halogen gas. Generally, it is known that gelatin acts as a halogen gas scavenger, and that the action is a function of pH and pAg of the system. However, in the present invention, the following compounds are preferably present as halogen gas scavengers at any position in the sealed container of the photographic product. That is, the compound preferable as the halogen gas scavenger in the present invention is, for example, a sulfide compound, a nitrite, a cesicarbazide, a sulfite, a hydroquinone, ethylenediamine, acetone semicarbazone, p-
Hydroxyphenylglycine. Particularly preferred compounds include compounds represented by the following general formula (H).

[0017]

[Chemical 1] In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a group capable of substituting for a benzene nucleus. Examples of the substituent in the general formula (H) include a halogen atom (eg, fluorine, chlorine, bromine atom), an alkyl group (eg,
Methyl, ethyl, n-propyl, t-butyl, n-amyl, i-amyl, n-octyl, n-dodecyl, n-octadecyl group and the like, particularly preferably having 1 to 32 carbon atoms),
Alkenyl group, aryl group, acyl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group,
Arylthio group, alkylacylamino group, arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfa group A moyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylacyloxy group, an arylacyloxy group and the like are preferable. These groups may be further substituted with the same substituents as those mentioned above. Specific examples of the compound represented by the general formula (H) are shown below.

[0018]

[Chemical 2]

[0019]

[Chemical 3]

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6] The position of addition of the hydroquinone, which is a halogen gas scavenger, may be either a protective layer, an intermediate layer, a non-photosensitive layer such as a back layer provided on the opposite side of the emulsion surface of the film, or a silver halide emulsion layer. . More preferably, it is added to a layer more distant from the support on the emulsion layer side of the support. Addition amount of halogen gas scavenger is 0.0
5 to 1 g / m ² , more preferably 0.1 to 0.5 g / m
^{Is 2} .

In the silver halide photographic product of the present invention, the photographic light-sensitive material is stored in a sealed container. Further, a part of the light-sensitive material may be arranged in a position where light can be irradiated after sealing, the rest is arranged in a position where light is shielded, and a structure in which air flows between the irradiated part and the light-shielded part. . As a silver halide photographic product of this type, for example, the currently mainstream 13
5 format roll film is equivalent. FIG. 1 shows a photographic product of this type in the open state. That is, the silver halide photographic light-sensitive material is housed in a metal cartridge 22 with a plastic spool 21 as a mandrel and partially pulled out from a film pull-out portion 23 via a light-shielding ribbon. For the convenience of film loading, a film of several cm is usually pulled out, and this portion 24 corresponds to a position where light can be irradiated. Through the gap between the film pulling portion 23 or the cartridge 22, the light shielded portion and the air Circulate. The cartridge 22 containing the silver halide photographic light-sensitive material is sealed by a hermetic container including a cartridge case 25 and a cartridge cap 26. The hermetically sealed container is designed to block gases harmful to the photosensitive material and suppress excessive permeation of water vapor, but the permeability of gas and water vapor is greatly affected by the structure and material of the hermetically sealed container. It is preferable that the humidity in the sealed container is kept constant. In the present invention, when the relative humidity at 25 ° C. is 55% or more, more preferably 55% to 70%, and particularly preferably 55% to 65%. The effect of is remarkable.

To keep the humidity in the sealed container constant means that
12 at 25 ° C when the humidity difference between the outside air and the inside of the case is 20%
It means a state where the humidity change inside the case is 10% or less after a lapse of months. It is preferable for the present invention that the inside of the sealed container is near normal humidity. Specifically, at 25 ° C., the relative humidity in the sealed container is preferably 50% or more and 70% or less, more preferably 55% or more and 68% or less. The equilibrium humidity referred to in the present invention is a value measured at 25 ° C., and can be measured by a conventional method (equilibrium humidity can be measured, for example, by VAISALA Co., Ltd.).
It can be measured by a capacitance-type humidity measuring instrument such as a Humicap humidity sensor manufactured by Hamamatsu. In the present invention, the sealed container is light transmissive (transparent or translucent). The light-transmitting property means that the portion drawn out from the film drawing-out portion can be substantially exposed to external light, and the average transmittance thereof is preferably 1% or more, more preferably 10% or more.

The plastic material which can be used for the hermetically sealed container in the present invention includes addition polymerization of an olefin having a carbon-carbon double bond, ring-opening polymerization of a small ring compound, and polycondensation of two or more polyfunctional compounds. (Condensation polymerization), polyaddition, and addition condensation of a phenol derivative, a urea derivative, a melamine derivative and a compound having an aldehyde can be used for the production.

The raw material of the plastics material is an olefin having a carbon-carbon double bond, for example, styrene,
Typical examples include α-methylstyrene, butadiene, methyl methacrylate, butyl acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine, N-vinylcarbazole, N-vinylpyrrolidone, vinylidene cyanide, ethylene and propylene. Can be mentioned. Examples of small ring compounds include ethylene oxide, propylene oxide, glycidol, 3,3
-Bischloromethyloxetane, 1,4-dioxane,
Typical examples include tetrahydrofuran, trioxane, ε-caprolactam, β-propiolactone, ethyleneimine, and tetramethylsiloxane.

As the polyfunctional compound, for example, carboxylic acids such as terephthalic acid, adipic acid and glutaric acid, isocyanates such as toluene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate, alcohols such as ethylene glycol, propylene glycol and glycerin. Typical examples include amines such as hexamethylenediamine, tetramethylenediamine, and paraphenylenediamine, epoxies, and the like. Also, phenol derivatives, urea derivatives,
Typical examples of the melamine derivative include phenol, cresol, methoxyphenol, chlorophenol, urea and melamine. Further, as a compound having an aldehyde, formaldehyde, acetaldehyde, octanal, dodecanal, benzaldehyde, etc. are representative. These raw materials may be used alone or in combination of two or more, depending on the target performance.

When a plastic material is produced using these raw materials, a catalyst or a solvent may be used.
As the catalyst, (1-phenylethyl) azodiphenylmethane, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis (2-methylpropane), benzoyl peroxide, cyclohexanone peroxide, potassium persulfate Radical polymerization catalyst such as, sulfuric acid, toluenesulfonic acid, trifluorosulfuric acid, perchloric acid, trifluoroboron, cationic polymerization catalyst such as tin tetrachloride, n
-Butyllithium, sodium / naphthalene, 9-fluorenyllithium, anionic polymerization catalysts such as phenylmagnesium bromide, triethylaluminum / tetrachlorotitanium-based Ziegler-Natta (Ziegle
r-Natta) type catalyst, sodium hydroxide, potassium hydroxide, potassium metal, etc. are used.

The solvent is not particularly limited as long as it does not inhibit the polymerization, but examples thereof include hexane, decalin, benzene, toluene, cyclohexane, chloroform, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran and the like. In molding the plastics of the present invention, a plasticizer is mixed with the plastics as necessary. As the plasticizer, for example, trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sebacate, methyl amyl ketone, nitrobenzene, γ-valerocratone, di-n-octyl succinate, bromonaphthalene, butyl palmitate, etc. are typical. It is a thing.

Specific examples of the plastics material used in the present invention are listed below, but the invention is not limited thereto.

P-1 Polystyrene P-2 Polyethylene P-3 Polypropylene P-4 Polymonochlorotrifluoroethylene P-5 Vinylidene chloride resin P-6 Vinyl chloride resin P-7 Vinyl chloride-vinyl acetate copolymer resin P-8 Acrylonitrile -Butadiene-styrene copolymer resin P-9 methyl methacrylic resin P-10 vinyl formal resin P-11 vinyl butyral resin P-12 polyethylene phthalate P-13 teflon P-14 nylon P-15 phenol resin P-16 melamine resin Particularly preferred plastic materials for the invention are polystyrene, polyethylene, polypropylene and the like. The light-shielding container of the present invention includes a cassette for sheet film, but is typically a cartridge for roll film.
A cartridge for a roll film has a spool shaft around which a silver halide photosensitive material is wound, a film outlet for taking the photosensitive material in and out, and a cartridge main body for accommodating the spool rotatably around an axis. In order to shield light, the spool has a flange, and the spool is attempted to enter the container through the gap between the spool shaft and the cap provided on the side edge of the typically cylindrical body of the cartridge body. Block the outside light. Further, preferably, a light shielding member is provided at the film outlet so that the film can be pulled out and rewound smoothly. This light shielding member is described in Japanese Utility Model Publication No. 61-34526. In the present invention, spectral sensitization is performed with a sensitizing dye before mixing silver halide emulsions having different average grain sizes. A sensitizing dye is added to at least two silver halide emulsions having different average grain sizes so that the amount of dye per unit surface area increases in order of increasing average grain size, preferably 10% or more. The grain size distribution of the silver halide emulsion to be mixed may be a polydisperse emulsion, but is preferably monodisperse (95% of silver halide grains have a grain size within ± 40% of the average grain size). . A method for producing a monodisperse emulsion is described in, for example, JP-B-48-36890 and JP-A-5-58.
4-48520, JP-A-54-65521, US Pat. No. 2,592,250, JP-A-54-158220.
And JP-A-63-151618. The method for measuring the average grain size of silver halide grains is described in detail, for example, in "The Theory of Photographic Process" (P.100 by James). The emulsion grain surface area can be calculated from the grain shape and grain distribution. When it has a remarkably irregular particle shape, it can be measured by utilizing the adsorption of a dye.

The addition of the dye in the present invention may be carried out at any position during the formation of silver halide grains, after the grain formation, at the time of washing with water, before chemical sensitization and after chemical sensitization. When the dye is added, for example, it is preferable to vigorously mix the emulsion so that it is adsorbed on the surface of the silver halide emulsion grains as uniformly as possible. The temperature, pH and pAg of the emulsion upon addition can be determined by the characteristics of the emulsion and the characteristics of the dye. Further, it is desirable to set a time until the adsorption equilibrium of the dye is reached after the addition of the dye and before the mixing of the emulsion. As the spectral sensitizing dye used in the present invention, a methine dye is usually used, and a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, and a hemioxonol dye. Is included. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, pyrroline, oxazoline, thiazoline, pyrrole, oxazole, thiazole, selenazole, imidazole, tetrazole, pyridine, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and an aromatic hydrocarbon ring is fused to these nuclei The nucleus, that is, indolenine, benzindolenine, indole, benzoxadol, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole, quinoline and the like can be applied. These nuclei may be substituted on carbon atoms. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, pyrazolin-5-one, thiohydantoin, 2-
Thiooxazolidine-2,4-dione, thiazoline-
A 5- to 6-membered heterocyclic nucleus such as 2,4-dione, rhodanine and thiobarbituric acid can be applied. Among the above dyes, the sensitizing dye particularly useful in the present invention is a cyanine dye.

For example, German Patent No. 929,080,
US Pat. Nos. 2,493,748 and 2,503,7
No. 76, No. 2,519,001, No. 2,912,
No. 329, No. 3,656,956, No. 3,67
No. 2,897, No. 3,694,217, No. 4,0
25,349, 4,046,572, and 2,
No. 688,545, No. 2,977,229, No. 3,397,060, No. 3,552,052, No. 3,527,641, No. 3,617,293,
No. 3,628,964, No. 3,666,480
No. 3, ibid. 3,672,898, ibid. 3,679,42
No. 8, No. 3,703,377, No. 3,814,6
09, 3,837,862 and 4,026.
344, British Patent Nos. 1,242,588, and 1,
No. 344, 281, No. 1,507, 803, Japanese Examined Patent Publication No. 44-14030, No. 52-24844, No. 43-
No. 4936, No. 53-12375, JP-A No. 52-11.
No. 0618, No. 52-109925, No. 50-808.
The sensitizing dyes described in No. 27 can be used.

To incorporate the sensitizing dyes used in the silver halide photographic products of the present invention in silver halide, they may be dispersed directly in the emulsion, or they may be dispersed in water, methanol, ethanol, It may be added to the emulsion by dissolving it in a solvent such as acetone, methyl cellosolve or fluoroalcohol alone or in a mixed solvent. When it is added to the silver halide emulsion, it may be added during the process of forming the silver halide grains, or may be added afterwards to the silver halide grains produced in advance. When added in the process of forming silver halide grains, the process in which silver and halogen react,
It can be added just before the physical ripening process or the chemical ripening (post ripening) process, during the chemical ripening process, or immediately after the chemical ripening process.

Further, these are dissolved alone or in a solvent which is substantially immiscible with water such as phenoxyethanol, and then dispersed directly in water or a hydrophilic colloid or using a surfactant, and this dispersion is dispersed in an emulsion. May be added to.

The addition amount of the sensitizing dye used in the silver halide photographic product of the present invention varies remarkably depending on the kind of silver halide emulsion, but usually 4 × 10 ^-6 mol to 8 × 10 ^-3 mol per mol of silver halide. It is a mole.

The light-sensitive material used in the silver halide photographic product of the present invention has at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. The number of layers and the layer order of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited as long as they are provided. As a typical example, a silver halide photographic light-sensitive material having at least one color-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layer is generally used. Are sequentially arranged from the support side in the order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, for example, JP-A-61-437 is used.
No. 48, No. 59-113438, No. 59-11344.
No. 0, No. 61-20037 and No. 61-20038 may contain a coupler and a DIR compound, and may contain a color mixing inhibitor as is commonly used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
For example, JP-A-57-112751, JP-A-62-200.
No. 350, No. 62-206541, No. 62-2065
As described in No. 43, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
For example, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL) / high sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL) order or BH / BL / GL / GH / R
H / RL order or BH / BL / GH / GL / RL /
It can be installed in the order of RH.

Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in Japanese Patent Publication No. 6, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is disposed and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion layer from the side distant from the support in the same color-sensitive layer. / High-speed emulsion layer / low-speed emulsion layer may be arranged in this order.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve the color reproducibility, US Pat.
No. 63-89850, and BL, G described in the specification.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides. About 2 mol% is particularly preferred.
To silver iodobromide or silver iodochlorobromide containing up to about 10 mol% silver iodide.

The silver halide grains in a photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having regular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 micron or less or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid.
716 (November 1979), page 648, ibid. Thirty
7105 (Nov. 1989), pages 863-865, and "Graph Kite's Physics and Chemistry", published by Paul Montel, P. Glafkides, Chemieet.
Phisique Photographie, P
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff).
in, Photographic Emulsion
Chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
otographic Emulsion, Focal
It can be prepared using the method described in Press, 1964).

US Pat. Nos. 3,574,628, 3,655,394 and British Patent 1,413,7.
The monodisperse emulsion described in No. 48 is also preferable.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which grains are formed, or a type having a latent image in both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and No. 18716. No. 307105, the relevant parts are summarized in the table below.

The light-sensitive materials used in the silver halide photographic products of the present invention include at least two types of photosensitive silver halide emulsions having at least one of the following characteristics: grain size, grain size distribution, halogen composition, grain shape, and sensitivity. The above emulsion,
It can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer.
The fogged silver halide emulsion inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but is 0.01 to 0.75 as an average grain size.
μm, particularly 0.05 to 0.6 μm is preferable. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or number of silver halide grains are ± 40 of the average grain size). %) Is preferable.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide grain which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. ..

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average value of circle equivalent diameters of projected areas) of 0.01 to 0.5 μm, more preferably 0.02 to 2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. However, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance before adding this to the coating liquid. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 648 page right column 866 page 2. Sensitivity enhancer page 648 page right column 3. Spectral sensitizer, page 23-24 page 648 right column-866 ~ 868 Supersensitizer 649 page right column 4. Whitening agent page 24 647 page right column 868 page 5. Antifoggant, pages 24-25 25 page 649 right column 868-870 page stabilizer 6. Light absorber , Pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column UV absorber 7. stain inhibitor page 25, right column 650 page, left column to page 872, right column 8. dye image stabilizer page 25, page 650 Left column page 872 9. Hardener page 26 651 page left column 874 to 875 10. Binder page 26 651 page left column 873 to 874 page 11. Plasticizers and lubricants page 27 650 page right column 876 page 12. Coating Auxiliary agent, page 26-27, page 650, right column, page 875-876, surfactant 13.Static page 27, page 650, right column, page 876-877, anti-blocking agent, matting agent, page 878-879. Prevent deterioration In order to stop the reaction, it is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503.

The light-sensitive materials used in the silver halide photographic products of the present invention include, for example, US Pat. It is preferable to include the mercapto compound described in No.

The light-sensitive material used in the silver halide photographic product of the present invention contains a fog agent, a development accelerator and a halogenation agent described in JP-A-1-106052, irrespective of the amount of developed silver produced by the development processing. It is preferred to include compounds that release silver solvents or their precursors.

Dyes or EP317,308A, US Pat. Fourth, 42
It is preferred to incorporate the dyes described in JP-A No. 0,555 and JP-A-1-259358.

Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 17643, VII-CG, and the same No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in EP 249,473A are preferred.

As the magenta coupler which can be used in combination with the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,619 is preferred.
No. 4,351,897, European Patent No. 73,63.
6, U.S. Pat. Nos. 3,061,432, and 3,72.
No. 5,067, Research Disclosure No. Two
4220 (June 1984), JP-A-60-33552.
No., Research Disclosure No. 24230
(June 1984), JP-A-60-43659 and JP-A-60-43659.
No. 1-72238, No. 60-35730, No. 55-1
No. 18034, No. 60-185951, U.S. Patent Nos. 4,500,630, 4,540,654, 4,556,630, and International Publication WO88 / 0479.
Those described in No. 5 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
52,212, 4,146,396, and 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
No. 4,775,616, No. 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212 and 4,296,4
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Furthermore, JP-A-64-553 and 64-55
No. 4, No. 64-555, and No. 64-556, pyrazoloazole couplers, and U.S. Pat. No. 4,818,
The imidazole couplers described in No. 672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A.
No. etc.

As couplers in which the color forming dye has an appropriate diffusibility, US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No.
17643, Item VII-G, ibid. VII of 307105-
Section G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-
39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are RD1 described above.
7643, section VII-F and ibid. 307105, VII-
Patents described in paragraph F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

RD. No. The bleaching accelerator releasing couplers described in 11149, 24241, JP-A-61-201247 and the like are effective in shortening the processing time having a bleaching ability, and particularly, the tabular silver halide grains described above. The effect is great when it is added to the photosensitive material using. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-1576.
Nos. 38 and 59-170840 are preferable. Also, JP-A-60-107029 and JP-A-60-25
2340, JP-A-1-44940, and 1-4568.
Compounds which release a fogging agent, a development accelerator and a silver halide solvent by an oxidation-reduction reaction with an oxidized product of a developing agent described in No. 7 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A , A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Examples thereof include releasing couplers.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate,
Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-di-ethylpropyl) phthalate), phosphoric acid Or phosphonic acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2) -Ethylhexylphenylphosphonate), benzoic acid esters (eg 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg N, N-). Ethyl dodecanamide, N, N-
Diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg bis (2-ethylhexyl) sebacate, Dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-butoxy-5-ter).
t-octylaniline) and hydrocarbons (eg paraffin, dodecylbenzene, diisopropylnaphthalene). The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably, an organic solvent having a temperature of 50 ° C. or more and about 160 ° C. or less can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps of the latex dispersion method, effects and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

In the light-sensitive material used in the silver halide photographic product of the present invention, phenethyl alcohol and JP-A-63 are used.
No. 257747, No. 62-272248, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethyl described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as phenol, 2-phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

The present invention is preferably applied to various color photographing materials. Typical examples are a color negative film for general use and a slide color reversal film.

Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid. 18
716, right column, page 647 to left column, page 648, and ibid.
307105, page 879.

The film swelling speed T _1/2 of the light-sensitive material used in the silver halide photographic product of the present invention is preferably 30 seconds or less, more preferably 20 seconds or less. The film swelling speed T _1/2 is
It can be measured according to a method known in the art. For example, A. Green
Photographic Sun Ens and Engineering (Photogr. Sci. Eng.)
It can be measured by using a swellometer (swelling meter) of the type described in Vol. 19, No. 2, pp. 124-129, T
_1/2 is defined as the time required to reach 1/2 of the saturated film thickness, with 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material used in the silver halide photographic product of the present invention is provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. It is preferable. In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber,
An antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surface slipping agent and the like are preferably contained. The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material used in the silver halide photographic product of the present invention is described in RD. No. 17643
28-29, ibid. 18716, page 651, left column to right column, and the same No. Development processing can be performed by a usual method described on pages 880 to 881 of 307105.

The color developing solution used in the development processing of the light-sensitive material used in the silver halide photographic product of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3 -Methyl-4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and sulfates thereof, Hydrochloride or p-toluene sulfonate may be mentioned. Among these, especially 3-methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds may be used in combination depending on the purpose.

The color developing solution contains, for example, a pH buffer such as an alkali metal carbonate, borate or phosphate, chloride salt, bromide salt, iodide salt, benzimidazole,
It is common to include development inhibitors or antifoggants such as benzothiazoles or mercapto compounds. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

When the reversal process is carried out, the black and white development is usually carried out before the color development. This black-and-white developer contains a known black-and-white developing agent, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. The classes can be used alone or in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally 3 liters or less per 1 square meter of the light-sensitive material. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = (contact area between treatment liquid and air (cm ² )) ÷ (volume of treatment liquid (cm ³ )) The above aperture ratio is preferably 0.1 or less, more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. To reduce the aperture ratio, not only the steps of color development and black and white development, but also the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The time of color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature and high pH and using a high concentration of color developing agent. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. A typical bleaching agent is an iron (III) complex salt,
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid or complex salts of citric acid, tartaric acid, malic acid, etc. Can be used. Of these, aminopolycarboxylic acid iron (II) complexes including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts.
I) Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: for example US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95631, No. 53-.
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-28426, Research Disclosure No. 17129 (July 1978), a compound having a mercapto group or a disulfide group; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-208.
32, No. 53-32735, U.S. Pat. No. 3,70.
Thiourea derivatives described in 6,561; West German Patent No. 1,
127,715, iodide salts described in JP-A-58-16235; West German Patents 966,410 and 2,74.
No. 8,430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Other JP-A Nos. 49-40943, 49-59644, 53-94927, 54-35727. , 55-
26506 and 58-163940;
Bromide ions can be used. Among them, a compound having a mercapto group or a disulfide group is preferable because of its large accelerating effect, and in particular, US Pat. No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-9563.
The compounds described in No. 0 are preferable. Furthermore, US Pat.
The compounds described in No. 552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, specifically, acetic acid,
Propionic acid and hydroxyacetic acid are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Is most commonly used, with ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for adjusting the pH, preferably imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methyl. It is preferable to add 0.1 to 10 mol / liter of an imidazole such as imidazole.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to increase the effect, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect or eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material used in the present invention is generally subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as coupler), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and various other types. It can be set in a wide range depending on the conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is
f the Society of Motion P
image and Television Eng
iners 64, P. 248-253 (195
It can be obtained by the method described in the May 5 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate and the suspended matter produced adheres to the photosensitive material. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, calcium ion described in JP-A-62-288838,
The method of reducing the magnesium ion can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, Hygiene Engineering Society, “Microbial Sterilization, Sterilization, and Antifungal Technology” (1982) Industrial Technology Association, Japan Society for Antibacterial and Antifungal, “Encyclopedia of Antibacterial and Antifungal Agents” (1986)
It is also possible to use the bactericide described in.

The pH of the washing water in the processing of the light-sensitive material used in the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but are generally in the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. To be selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543
All known methods described in Nos. 58-14834 and 60-220345 can be used.

In addition, there is a case where further stabilization treatment is carried out after the water washing treatment, and as an example thereof, a stabilizer containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in US Pat. No. 3,342,597,
No. 3,342,599, Research Disclosure No. 14,850 and the same No. Schiff base type compounds described in JP-A Nos. 15,159,159, aldol compounds described in JP-A No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. be able to.

The silver halide color light-sensitive material used in the present invention is, if necessary, for the purpose of promoting color development.
Various 1-phenyl-3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

[0108]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 (Preparation of Emulsion I) An emulsion having an average aspect ratio of 6.0, an equivalent spherical diameter of 0.65 μm and a coefficient of variation of 25% was prepared with reference to JP-A-3-172836 (Emulsion B of Example 1). This emulsion optimally sensitized with gold and sulfur is designated as emulsion I-1. Then, a sensitizing dye (ExS-7) of 7.7 × 10 ⁻⁴ mol / mol Ag was added at 60 ° C. with good stirring, and 2
Adsorbed for 0 minutes. This is designated as emulsion I-2. Emulsion I-
In Example 2, the sensitizing dye is ExS-4 / ExS-5 / ExS.
Emulsion I-3 was prepared by replacing the mixed dye of -6 = 1 / 6.5 / 2.5.

(Preparation of Emulsion II) JP-A-1-46741
With reference to (Emulsion G of Example 1), an emulsion having an average aspect ratio of 3.5, an equivalent spherical diameter of 0.4 μm and a variation coefficient of 30% was prepared. This emulsion optimally sensitized with gold and sulfur is designated as emulsion II-1. Then 8.5 × 10 ⁻⁴ mol / mol Ag
The sensitizing dye (ExS-7) was added at 60 ° C. with good stirring and adsorbed for 20 minutes. This is designated as Emulsion II-2.

(Preparation of Emulsion III) JP-A-54-4852
1, referring to JP-A-54-49938, a side length of 0.5 μ
An octahedral emulsion having m and a coefficient of variation of 15% was prepared. This emulsion optimally sensitized with gold and sulfur is designated as emulsion III-1. Next, 3.8 × 10 ⁻⁴ mol / mol Ag sensitizing dye (E
xS-7) was added at 60 ° C. with good stirring and allowed to adsorb for 20 minutes. This is designated as Emulsion III-2.

(Preparation of Emulsion IV) An octahedral emulsion having an edge length of 0.75 μm and a coefficient of variation of 12% was prepared in the same manner as Emulsion III. This emulsion is optimally sensitized with gold and sulfur and is emulsion IV.
-1. Next, a sensitizing dye (ExS-7) of 2.9 × 10 ⁻⁴ mol / mol Ag was added at 60 ° C. with good stirring, and adsorption was carried out for 20 minutes. This is designated as Emulsion IV-2.

(Preparation of Emulsion V) The pAg of Emulsion III was adjusted to prepare a cubic emulsion having a side length of 0.4 μm and a coefficient of variation of 10%. This emulsion which was optimally sensitized with gold and sulfur was designated as emulsion V-1. Then 3.8 × 10 ^-4 mol / mol Ag
Sensitizing dye (ExS-4 / ExS-5 / ExS-6 = 1
/6.5/2.5) was added at 60 ° C. with good stirring, and adsorption was carried out for 20 minutes. The characteristics of the obtained emulsion are shown in Table 1 below together with the sensitizing dye used.

[0113]

[Table 1] Example 2 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a film 101 which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount converted to silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Film 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ⁻³ HBS-1 0.20 Second Layer (Intermediate Layer) Emulsion G Silver 0.065 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1. 04 Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ⁻⁵ ExS-2 1.8 × 10 ⁻⁵ ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-10 .10 Gelatin 0.87.

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ⁻⁴ ExS-2 1.6 × 10 ⁻⁵ ExS-3 5.1 × 10 ⁻⁴ ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS- 1 0.10 Gelatin 0.75 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.0 × 10 ⁻⁴ ExS-3 3. 4 × 10 ⁻⁴ ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1. 20 6th layer (intermediate layer) Cpd-1 0.10 HBS- 0.50 gelatin 1.10.

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 Eighth layer (medium sensitivity green sensitive emulsion layer) ) Emulsion D Silver 0.80 ExS- ⁴ 3.2x10 ^-5 ExS-5 2.2x10 ^-4 ExS-6 8.4x10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY −1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ⁻³ Gelatin 0.90 9th layer (high-sensitivity green-sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1x10 ^-5 ExS-6 3.2x10 ^-4 ExC-1 0.010 ExM-10 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 gelatin 1.44.

10th layer (yellow filter layer) Yellow colloidal silver 0.030 Cpd-1 0.16 HBS-1 0.60 gelatin 0.60 11th layer (low-sensitivity blue-sensitive emulsion layer) Emulsion I-2 silver 0.20 Emulsion II-2 Silver 0.20 ExY-1 0.020 ExY-2 0.27 ExY-3 0.50 ExY-4 0.020 ExC-7 7.0 × 10 ^-3 HBS-1 0. 28 Gelatin 1.10 12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86 13th layer (1st protective layer) UV-4 0.11 UV-5 0.17 HBS-1 5.0x10 ^-2 gelatin 1.00.

Fourteenth layer (second protective layer) Emulsion G Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ⁻² B-2 (diameter 1.7 μm) 0 .10 B-3 0.10 S-1 0.20 Gelatin 1.20 Further, in each layer, storability, processability, pressure resistance, anti-mold, and
W-1 to improve antibacterial properties, antistatic properties and coating properties
To W-3, B-4 to B-6, F-1 to F-
17 and iron salt, lead salt, gold salt, platinum salt, iridium salt,
Contains rhodium salt. Emulsions A to G are shown in Table 2 below. The compounds used are shown in Chemical formulas 7 to 21 below.

[0119]

[Table 2] In Table 2, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. Specifically, each emulsion was sensitized with gold and chalcogen under the conditions shown in Table 3 below. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0120]

[Table 3]

[0121]

[Chemical 7]

[0122]

[Chemical 8]

[0123]

[Chemical 9]

[0124]

[Chemical 10]

[0125]

[Chemical 11]

[0126]

[Chemical formula 12]

[0127]

[Chemical 13]

[0128]

[Chemical 14]

[0129]

[Chemical 15]

[0130]

[Chemical 16]

[0131]

[Chemical 17]

[0132]

[Chemical 18]

[0133]

[Chemical 19]

[0134]

[Chemical 20]

[0135]

[Chemical 21] Films 101 to 112 as shown in Table 4 below were produced.

[0136]

[Table 4] The above films 101-112 are in 135 format 2
Four shots were processed into a patrone form, the humidity was adjusted to 25 ° C and 65%, and the patrone was stored in a transparent patrone and a completely shaded patrone in a dark place. The ratio of the area of the light-shielded part that is stored in the cartridge and the area of the film extraction part is 1:
It is 0.05. After irradiating 10,000 lux for 24 hours with respect to these, it was stored under the condition of 60 ° C. and 60% for 3 days, and the film in the part stored in the cartridge was cut out and passed through a continuous wedge at a color temperature of 4800 ° K to pass 1 /. 1
It was exposed for 00 seconds.

After exposing the color photographic light-sensitive material as described above, it was processed by the method described below. (Processing method) Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 3 minutes 00 seconds 38 ° C Water washing 30 seconds 24 ° C Settling 3 minutes 00 seconds 38 ° C Water washing (1) 30 seconds 24 ° C Water washing (2) 30 seconds 24 ℃ Stability 30 seconds 38 ℃ Dry 4 minutes 20 seconds 55 ℃.

Next, the composition of the processing liquid will be described. (Color developer) (Unit g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 water was added to 1.0 liter pH 10.05 (bleaching solution) ( Unit g) Ethylenediaminetetraacetic acid ferric ammonium trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 3-Mercapto-1,2,4-triazole 0.08 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia Water (27%) 6.5 ml Water was added to 1.0 liter pH 6.0 (fixing Liquid) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / l) 290.0 ml Water added 1.0 liter pH 6.7 (Stable solution) (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1 , 4-Bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5 As a result, by using the emulsion of the present invention as a mixture, high sensitivity was obtained. It was found that rich gradation was obtained and gradation change during storage was small. Example 3 Cpd-3 was added to the film 103 of Example 2 in the eleventh and twelfth layers at 0.2 g / m ² and 0.02 g / m, respectively.
^{The following} table 5 shows the results of the same experiment as in Example 2 except that the film 201 with ² added was prepared.

[0139]

[Table 5] From the above, it can be seen that the hydroquinone derivative known as a halogen gas scavenger further contributes to the reduction of fog. Example 4 Films 301 to 304 were prepared by changing the emulsion of the seventh layer of the films 101 and 103 of Example 2 as shown in Table 6 below, and the same experiment as in Example 2 was conducted. The results are shown in Table 6 at the same time. The same effect was obtained in the green-sensitive layer.

[0140]

[Table 6]

[Brief description of drawings]

FIG. 1 is a diagram showing an open state of an example of a silver halide photographic product of the present invention.

[Explanation of Codes] 21 ... Spool, 22 ... Patrone, 23 ... Film drawing section, 24 ... Exposure section 25 ... Patrone case, 26 ... Patrone cap.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location G03C 1/07 1/09 1/16 1/18 1/34

Claims (2)

[Claims] 1. A support comprising at least two silver halide emulsions having different average grain sizes sensitized with gold and chalcogen and at least one silver halide emulsion layer containing thiocyanate. The light-sensitive material comprises a silver halide light-sensitive material, a light-shielding container containing the light-sensitive material, and a light-transmissive sealed container containing the light-shielding container, and the light-sensitive material is partially located outside the light-shielding container. And has a structure in which gas can flow between the inside and the outside of the light-shielding container, and the silver halide emulsion is prepared so that the amount of sensitizing dye per unit surface area increases in descending order of average grain size. A silver halide photographic product, characterized in that it has a hydrogen cyanide gas scavenger at any position in the sealed container. 2. The photographic product according to claim 1, which has a halogen gas scavenger at any position in the sealed container.