JPH0619055A - Silver halide photographic product - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic product showing improve conservation property of a silver halide photographic sensitive material having high picture quality held in a light translucent case and excellent in characteristics for reciprocity law. CONSTITUTION:The silver halide photosensitive material has at least one silver halide emulsion layer on a supporting body. The silver halide emulsion layer contains thiocyanate and a silver halide emulsion which contains silver halide particles containing iridium salt and is sensitized with gold-chalcogens. The photographic product consists of a light-shielding container 22 incorporating the photosensitive material and a light-transmitting sealable container 25, 26 housing the light-shielding container 22. The photosensitive material is assembled in such a manner that a part 24 of the photosensitive material is out of the light-shielding container 22. Moreover, in the silver halide photographic product having such the structure that air can pass through between the inside and the outside of the container 22, a scavenger for gaseous hydrogen cyanate is arranged at either of the positions in the sealable containers 25, 26.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic product containing a silver halide photographic light-sensitive material. In particular, the present invention relates to a photographic product having excellent storage stability of a silver halide photographic light-sensitive material held in a light transmissive case.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic materials are photosensitive. Therefore, it is usually shielded from light and stored before being photographed. However, there are cases where light-shielding is not sufficient for a portion which is not photographed due to a design limitation of a photographic product. For example, in the case of the color negative film of the 135 format, if the case for storing the film cartridge is transparent, the inside cartridge can be easily seen and confirmed, and the transparent case has an advantage that it can be reused as an accessory case.

Recently, however, a surprising phenomenon has been discovered in which the performance of the film varies depending on the brightness of the product that has been stored for a long time on the shelves of the store. Analysis of this phenomenon revealed that light hits the drawer of the film through the paper box that houses the film case, and a certain type of gas is generated, which diffuses to the part that is blocked by the light. It turns out that the performance is changing. Such a phenomenon has never been known in the art. For the purpose of analyzing this gas, the film was forcibly irradiated with intense light and the generated gas was collected, and it was found that hydrogen cyanide gas was contained.

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, JP-A-3-505263 discloses that compounds of palladium, gold and platinum are effective. Here, it is described that fogging due to hydrogen cyanide gas is prevented by including a hydrogen cyanide scavenger at a position where the hydrogen cyanide gas generated from carbon black can be blocked from the photosensitive emulsion.

It is also stated that the position of addition of the scavenger is preferably closer to the carbon black which is the generation source.

However, there is no description suggesting that hydrogen cyanide gas is generated when the light-sensitive material is irradiated with light.

There is no description suggesting that the gas generated from the light-irradiated portion affects the photographic properties of the light-shielded portion.

Further, there is no description that thiocyanate contained in the light-sensitive material causes gas generation.

As disclosed in US Pat. Nos. 2,566,245 and 2,566,263, it is widely known to add a Pd compound to a silver halide photographic light-sensitive material. This is a known technique. In fact, Pd is contained in the emulsion layer or intermediate layer of the silver halide color photographic material.
Is widely practiced, eg 1988
Eastman Kodak Co., Ltd. Rochuster Factory, New York, USA
R-G100 Brownie film (EMUL. No. 2
4 031 13) has a Pd of about 3 × 10 ⁻⁵
This is contained in a black light-shielding paper containing carbon black of about 8% (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, this Pd is effective for fogging which may occur when the same light-sensitive material as this film is commercialized in a film format having a design having a portion to be irradiated with light as in the present invention. Is impossible to predict.

The inventor believes that the following reaction occurs in the light-irradiated portion to generate hydrogen cyanide gas.

AgBr (+ hν; light irradiation) → 2Ag + B
r ₂ (printout) 2AgSCN + Br ₂ → 2AgBr + (SCN) ₂ (SCN) ₂ hydrolysis → HCN From this reaction formula, it can be seen that a scavenger of halogen gas is also effective.

Further, it is expected that the generation of hydrogen cyanide gas will increase when the humidity in the photographic product is high.

On the other hand, the inclusion of an iridium salt in the silver halide grains or on the surface thereof in order to improve the reciprocity law property or the development progress is usually practiced in the photographic industry. However, it has been found that the inclusion of an iridium salt in silver halide grains significantly increases the change in photographic performance due to light irradiation. It is considered that the inclusion of an iridium salt in the silver halide grains increased the generation of halogen gas due to printout and the resistance of the silver halide grains to hydrogen cyanide gas deteriorated. This is a major problem in using silver halide grains containing an iridium salt.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photographic product in which the storability of a silver halide photographic light-sensitive material having a high image quality and excellent reciprocity characteristics, which is retained in a light-transmitting case, is improved. That is.

[0017]

As a result of intensive studies, the object of the present invention could be achieved by the following means.

At least one silver halide emulsion layer containing a gold / chalcogen-sensitized silver halide emulsion containing silver halide grains containing an iridium salt and thiocyanate is provided on a support. 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 being partly located outside the light-shielding container. In a silver halide photographic product having such a structure that a gas can flow between the inside and the outside of the light-shielding container as described above, a hydrogen cyanide gas scavenger is provided at any position in the sealed container. A silver halide photographic product.

The present invention will be described in detail below.

The cyanogen hydrogen gas scavenger in the present invention is a compound which 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 hydrogen cyanide gas.

Suitable hydrogen cyanide gas scavengers can be selected from noble metal inorganic or organic compounds. Particularly preferred is palladium (II or IV),
It is a compound of platinum (II or IV). Gold (I or II
The compounds of I) are also preferred. Rhodium (III), Iridium (III or IV) and Osmium (II, II
The compounds of I or IV) are also effective, but in higher amounts are required to have an equivalent effect.

Specific examples of useful inorganic or organic noble metal compounds include, for example, Gmelin Handbook (Gmelin).
Handbook), and commercial products, synthetic products, and in situ synthetic products should be used in such a purity that they do not adversely affect the photographic light-sensitive material.

Typical examples of useful palladium compounds include palladium (II) chloride, palladium (II) bromide, palladium (II) hydroxide, palladium (II) sulfate, palladium (II) thiocyanate, tetrachloropalladium (II). ) Acid salt (sodium salt, potassium salt, ammonium salt), hexachloropalladium (IV) acid salt, tetrabromopalladium (II) acid salt, hexabromopalladium (IV) acid salt, bis (salicylat) palladium (I
I) acid salt, bis (dithiooxalato-S, S ′) palladium (II) acid salt, trans-dichlorobis (thioether) palladium (II), tetraamminepalladium (II) salt, dichlorodiamminepalladium (I).
I), dibromodiammine palladium (II), oxalatodiammine palladium (II), dinitrodiammine palladium (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 (I
I)], di-μ-chloro-bis [chloro (arsine) palladium (II)] and dinitrobis (arsine) palladium (II).

Representative examples of useful platinum compounds are platinum (II) chloride, platinum (IV) chloride, hexafluoroplatinate (IV) acid salt, tetrachloroplatinum (II) acid salt, hexachloroplatinum (IV) acid salt, Trichlorotrifluoroplatinum (IV) acid salt, tetrabromoplatinum (II) acid salt, hexabromoplatinum (IV) acid salt, dibromodichloroplatinum (I
I) acid salt, hexahydroxoplatinum (IV) acid salt, bis (oxalato) platinum (II) acid salt, dichlorobis (oxalato) platinum (VI) acid salt, bis (thiooxalato) platinum (II) acid salt, bis (acetyl) Acetonato) platinum (I
I), bis (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) platinum (II), bis (1,1,1-trifluoro-2,4-pentanedio) Nato) platinum (II), tetrakis (thiocyanato) platinum (II) acid salt, hexakis (thiocyanato) platinum (I
V) acid salt, bis {(Z) -1,2-dicyanoethylene-
1,2-dithiolato} platinum (II) acid salt, dichlorobis (diethylsulfide) platinum (II), tetrachlorobis (diethylsulfide) platinum (IV), bis (glycinato) platinum (II), dichloroglycinatoplatinum (II) )
Acid salt, dichlorobis (triethylphosphine) platinum (I
I), chlorohydridobis (triethylphosphine) platinum (II), tetraammineplatinum (II) salt, tetrachloroplatinum (II) acid salt, dichlorodiammineplatinum (I
I), trichloroammine platinum (II) salt, hexaammine platinum (IV) salt, chloropentaammine platinum (I
V) salt, tetrachlorodiammine platinum (IV), dinitrodiammine platinum (II), dichlorotetrakis (methylamine) platinum (IV) salt, dichloro (ethylenediamine) platinum (II), bis (ethylenediamine) platinum (I)
I) salt, tris (ethylenediamine) platinum (IV) salt,
Dichlorobis (ethylenediamine) platinum (IV) salt, dichlorodihydroxo (ethylenediamine) platinum (I
V), tetrakis (pyridine) platinum (II) salt, dichlorobis (pyridine) platinum (II), bis (2,2′-bipyridine) platinum (II) salt, tetranitroplatinum (II)
Acid salt, chlorotrinitroplatinum (II) acid salt, dichlorodinitroplatinum (II) acid salt, dibromodinitroplatinum (I
I) acid salt, hexanitroplatinate (IV) acid salt, chloropentanitroplatinum (IV) acid salt, dichlorotetranitroplatinum (IV) acid salt, trichlorotrinitroplatinum (IV) acid salt, tetrachlorodinitroplatinum (IV) acid salt Acid salt, dibromodichlorodinitroplatinum (IV) acid salt, trichloro (ethylene) platinum (II) acid salt, di-μ-chloro-bis {chloro (ethylene) platinum (II), trans-dichloro (ethylene) (pyridine) Platinum (II), bis [bis (β-mercaptoethylamine) nickel (II)-
S, S "-] platinum (II) salts, and dichlorodicarbonyl platinum (II).

Gold (I or III), Rhodium (II
I), iridium (III or IV) and osmium (II, III or IV) compounds can be mentioned as well, for example potassium tetrachloroaurate (III), rhodium (III) chloride, potassium hexachloroiridate ( IV), potassium tetrachloroiridate (III) and potassium hexachloroosmate (IV).

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-mentioned specific examples.

In the present invention, the hydrogen cyanide gas scavenger may be present at any position within the sealed container of the 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 cartridge.

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. 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 a suitable concentration, and a water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, such as alcohols, glycols, ketones, esters, amides, etc. Of these, it can be dissolved in a solvent that does not adversely affect the photographic characteristics and added as a solution.

Back layer, emulsion layer, surface protective layer, intermediate layer,
And the antihalation layer is usually a dispersion with a binder, but useful binders include naturally occurring polymeric vehicles such as gelatin and cellulose derivatives and 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 of the binder and the pH according to the kind and amount of the hydrogen cyanide gas scavenger used.

Generally, the noble 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, Vol. 34, 159 (1971) Keiichi Tanaka, The Photographic Society of Japan, Vol. 37, 133 (1974) Keiichi Tanaka, The Photographic Society of Japan, Vol. 39. 73 (1976) Keiichi Tanaka, Journal of Photographic Science 21: 134 (1973) Keiichi Tanaka and Journal of Photographic Science
Science, Vol. 26, p. 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 foreign substance in the form of gelatin in some cases, depending on the conditions. It is preferable to appropriately select and use it.

The addition amount of the hydrogen cyanide gas scavenger in the present invention should be determined within the range where the effect of the present invention remarkably appears, but it is preferably 1/10 per 1 mol of thiocyanate contained in the portion which can be irradiated with light.
It is more than a mole. More preferably 1/2 mole or more and 1 mole per 1 mole of thiocyanate contained in the portion that can be irradiated with light.
It is not more than 00 mol, particularly preferably 1 mol to 10 mol.
It is a mole.

The photographic light-sensitive material of the present invention comprises a support and a silver halide emulsion layer containing a thiocyanate salt and a gold / chalcogen-sensitized silver halide emulsion containing silver halide grains containing an iridium salt. contains. The support is, for example, RD. No. 17643, page 28, RD. N
o. 18716, page 647, right column to page 648, left column, and RD. No. 307105, page 879.

The chalcogen sensitization is performed with at least one of a selenium sensitizer, a sulfur sensitizer and a tellurium sensitizer.

Here, the selenium sensitization is carried out by a conventionally known method. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added at a high temperature,
It is preferably carried out by stirring the emulsion at 40 ° C. or higher for a certain period of time. Selenium sensitization using the unstable selenium sensitizer described in JP-B-44-15748 is preferably used. Specific examples of unstable selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenamides, selenocarboxylic acids and esters, selenophosphate. The kind is mentioned. Particularly preferred unstable selenium compounds are shown below.

I. Colloidal metal selenium II. Organic selenium compound (selenium atom is double-bonded to carbon atom of organic compound by covalent bond) a. Isoselenocyanates Aliphatic isoselenocyanates such as allyl isoselenocyanate b. Selenoureas (including enol type) For example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, dioctyl, tetraoctyl, N- (β-carboxyethyl) -N ′, N′-dimethyl, N ,
Aliphatic selenoureas such as N-dimethyl, diethyl, dimethyl; aromatic selenoureas having one or more aromatic groups such as phenyl and tolyl; heterocycles having heterocyclic groups such as pyridyl and benzothiazolyl Formula selenourea c. Selenoketones, for example, selenoacetone, selenoacetophenone, selenoketones 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-Serenobuchirate III. Other a. Selenides For example, diethyl selenide, diethyl diselenide,
Triphenylphosphine selenide b. Selenophosphates, for example, tri-p-tolylselenophosphate, tri-n-
The preferred type of butylselenophosphate labile selenium compound is described above.
These are not limiting. For the person skilled in the art, speaking of unstable selenium compounds as sensitizers for photographic emulsions,
The structure of the compound is not so important 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 No. 52-34492 can also be used. Examples of the non-unstable selenium compound include selenious acid, potassium selenocyanide, selenazols, and selenazo-
And quaternary ammonium salts of diols, diaryl selenide, diaryl diselenide, 2-thioselenazolidinedione, 2-selenooxozinthione and their derivatives.

The non-labile selenium sensitizer and thioselenazolidinedione compound described in JP-B-52-38408 are also useful.

These selenium sensitizers are added during chemical sensitization by dissolving them in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent, but preferably chemical sensitization. Added before start. 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. In particular, 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 kind and size of silver halide, the temperature and time of ripening, and preferably, 1 x 1 per mol of silver halide
It is 0 ^-8 mol or more, and more preferably 1 × 10 ^-7 mol or more and 1 × 10 ^-4 mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C. or higher,
More preferably, it is 50 ° 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, selenium sensitization is more effective when carried out in the presence of a silver halide solvent.

The silver halide solvent which can be used in the present invention is, for example, US Pat. No. 3,271,
No. 157, No. 3,531,289, No. 3,57.
4,628, JP-A-54-1019 and 54-15.
(A) Organic thioethers described in JP-A-8917, JP-A-53-82408, JP-A-55-77737, and JP-A-5-77437.
(B) thiourea derivative described in JP-A-5-2982, and (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, described in JP-A-53-144319. , (D) imidazoles, (e) sulfites, described in JP-A No. 54-100717.
(F) Thiocyanate.

A particularly preferred solvent is thiocyanate.
And tetramethylthiourea. The amount of the solvent used varies depending on the kind, but in the case of thiocyanate, the preferable amount is 1 per mol of silver halide.
It is not less than × 10 ^-4 mol and not more than 1 × 10 ^-2 mol.

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 period of time.

For the sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate
And cystine, p-toluenethiosulfonate, and rhodanine. In addition, for example, U.S. Pat. Nos. 1,547,944, 2,410,689, 2,278,947, and 2,728,668,
No. 3,501,313, No. 3,656,955, German Patent No. 1,422,868, Japanese Patent Publication No. 5
The sulfur sensitizers described in JP-A-6-24937 and JP-A-55-45016 can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount will vary over a considerable range under various conditions such as pH, temperature, silver halide grain size, but will be 1 × 10 ^-7 mol / silver halide.
It is preferably at least 1 × 10 ⁻⁴ mol.

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. Typical examples are chloroauric acid salt, potassium chloroorate, oric trichloride, and potassium oleate.
Rick thiocyanate, potassium iodo-rate, tetracyano-oric acid, ammonium orothiocyanate, and pyridyl trichlorogold.

The amount of the gold sensitizer added 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, gold / sulfur sensitization
Selenium sensitization, gold / tellurium sensitization, gold / sulfur / selenium sensitization,
It can be selected 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,
For example, ammonium salts, potassium salts and sodium salts are preferably used.

The thiocyanate may be used alone for gold / chalcogen sensitization, or may be mixed with a gold sensitizer for use. 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 in the desalting step. US Pat. No. 3,320,06 for the use of thiocyanate in grain formation.
9 and 4,434,226.

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 for exchanging a halogen gas generated when a light-sensitive material is irradiated with light, with 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.

It is generally known that gelatin acts as a halogen gas scavenger, and that its 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, preferred compounds as the halogen gas scavenger in the present invention are, for example, sulfide compounds, nitrites, semicarbazides, sulfites, hydroquinones, ethylenediamine, acetone cesicacarbazone and p-hydroxyphenylglycine.

As a particularly preferred compound, a compound represented by the following general formula (H) can be mentioned.

[0058]

[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 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, 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 A group, an arylsulfonamido group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylacyloxy group and an arylacyloxy group are preferable.

These groups may be further substituted with the same substituents as those mentioned above.

Specific examples of the compound represented by the above general formula (H) are shown below.

[0062]

[Chemical 2]

[0063]

[Chemical 3]

[0064]

[Chemical 4]

[0065]

[Chemical 5]

[0066]

[Chemical 6] The addition position of the hydroquinone which is a halogen gas scavenger may be any of a protective layer, an intermediate layer, a non-photosensitive layer such as a back layer provided on the side opposite to the emulsion surface of the film, or a silver halide emulsion layer. . More preferably, it is added to a layer farther from the support on the emulsion layer side of the support.

The amount of halogen gas scavenger added is 0.05 to 1 g / m ² , more preferably 0.1 to 1 g / m ² .
It is 0.5 g / m ² .

The silver halide photographic product of the present invention contains a silver halide photosensitive material in a light-shielding container housed in a light-transmitting hermetically sealed container, and a part of the photosensitive material is exposed in the hermetically sealed container. The remaining part is placed in the light-shielding container. The light shielding container has a structure in which gas can flow inside and outside.

The light-shielding container of the present invention includes a cassette for a sheet film, but is typically a patrone for a roll film. Patrones for roll film,
It has a spool shaft around which the silver halide light-sensitive material is wound in a roll shape, and a film outlet for loading and unloading the light-sensitive material,
Patrol for storing the spool rotatably around the axis
It has a main body. In order to shield light, the spool has a flange so that it can be removed from the gap between the cap and the spool shaft provided on the side edge of the body of the patrone, which is typically cylindrical. The external light that is about to enter the container is blocked. Further, it is preferable that 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 used in Japanese Utility Model No. 61-34.
No. 526.

The photographic product of the type of the present invention corresponds to, for example, the currently mainstream 135-format roll film, and one embodiment thereof is shown in FIG. In FIG. 1, the silver halide photographic light-sensitive material is housed in a metal cartridge 22 as a light-shielding container with a plastic spool 21 as a mandrel, and is partially (24) pulled out from a film drawing-out portion 23 via a light-shielding ribbon. There is. A film of several cm is usually pulled out for the convenience of film loading, and this portion 24 corresponds to a position where light can be irradiated.
Alternatively, air flows between the inside and the outside through the gap of the cartridge 22. The above-mentioned photographic products are usually stored in an outer box made of paper and are on the market, but if they are stored for a long period of time under external light, the photographic performance is deteriorated by the light passing through the outer box.

The cartridge containing the silver halide photographic light-sensitive material is sealed by a cartridge case 25 and a cartridge cap 26 as a hermetic container. The sealed container is designed to block harmful gases to the photosensitive material and suppress the permeation of excess water vapor, but the permeability of gas and water vapor is greatly affected by the structure and material of the cartridge case 25 and cartridge cap 26. It

The humidity in the sealed container is preferably kept constant, and in the present invention, the relative humidity is 55% at 25 ° C.
Above, more preferably 55% to 70%, particularly preferably 55% to 65%, the effect of the invention is remarkable.

It is meant that the humidity in the sealed container is kept constant.
12 at 25 ° C when the humidity difference between the outside air and the case is 20%
It means that the humidity inside the case changes less than 10% after a lapse of months.

It is preferable for the present invention to keep the inside of the sealed container 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 is
For example, it can be measured by a capacitance type humidity measuring device such as a Humicap humidity sensor manufactured by VAISALA.

In the present invention, the sealed container is light transmissive. Light-transmissive means that the portion pulled out from the film pull-out portion can be substantially exposed to external light,
The average transmittance thereof is preferably 1% or more, more preferably 10% or more.

In the present invention, the plastic material which can be used for the sealed container 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 are 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.

Examples of polyfunctional compounds include 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, paraphenylenediamine, and epoxies. Examples of the phenol derivative, urea derivative and melamine derivative include phenol, cresol,
Representative examples include methoxyphenol, chlorophenol, urea, melamine and the like. Further, as the compound having an aldehyde, formaldehyde, acetaldehyde, octanal, dodecanal, benzaldehyde and the like are representatively mentioned. 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, Radical polymerization catalysts such as potassium persulfate, sulfuric acid, toluenesulfonic acid, trifluorosulfuric acid, perchloric acid, trifluoroboron, cationic polymerization catalysts such as tin tetrachloride, n-butyllithium, sodium / naphthalene, 9-fluorenyllithium Anionic polymerization catalysts such as phenylmagnesium bromide, triethylaluminum / tetrachlorotitanium-based Ziegler-Natta catalysts, sodium hydroxide, potassium hydroxide, potassium metal and the like 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.

When molding plastics as the hermetically sealed container of the present invention, a plasticizer is mixed with the plastics if 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 for the hermetically sealed container in the present invention are shown 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.

In the present invention, the silver halide grains of at least one silver halide emulsion layer on the support contain an iridium salt.

A silver halide emulsion is usually prepared by a grain formation step (addition of silver ions and halogen ions and physical ripening),
It consists of a desalting process and a chemical sensitization process. The time of addition of the iridium salt can be selected from among grain formation, desalting step and chemical sensitization.

That is, in the process of forming silver halide emulsion grains, the addition of a silver salt solution or the physical ripening may be carried out,
It may be done before the start of chemical sensitization or just before the end.

The amount of the iridium salt used in the present invention cannot be uniquely determined depending on the addition method and the type of silver halide, but it is 10 ^-9 to 1 per mol of silver halide.
It is 0 ^-3 mol, preferably 10 ^-8 to 10 ^-4 mol.

Examples of the iridium salt that can be used in the present invention include hexachloroiridium (III)
Acid salt, hexachloroiridium (IV) acid salt, hexabromoiridium (III) acid salt, hexabromoiridium (IV) acid salt, hexaiodoiridium (III) acid salt, hexaiodoiridium (IV) acid salt, pentachlorocarbonyl Iridium (III) acid salt, pentachlorotetracarbonyliridium (III) acid salt, pentachloronitrosyliridium (IV) acid salt, tris (oxalato) iridium (III) acid salt, hexakis (thiocyanato) iridium (III) acid salt, Hexakis (thiourea) iridium (III) acid salt, dichlorotetranitroiridium (III) acid salt, and hexacyanoiridium (III) acid salt are mentioned.

The water-soluble iridium salt is an aqueous solution having a suitable concentration, and the water-insoluble or poorly soluble iridium salt is a suitable organic solvent miscible with water, such as alcohols,
Of glycols, ketones, esters, amides, etc., dissolved in a solvent that does not adversely affect photographic characteristics,
It can be added as a solution.

The silver halide grains contained in the photographic emulsion of the present invention are silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide,
The halogen composition may be either silver chloride or silver iodochloride. Preferred is silver bromide, silver iodobromide, silver chlorobromide or silver iodochlorobromide.

The silver halide grains of the present invention may have at least two layered structures having substantially different silver halides or have a uniform composition in the silver halide grains.

In an emulsion having a layered structure having different halogen compositions, a high silver iodide layer is formed in the core portion and an outermost layer (shell portion) is formed.
It may be an emulsion containing a low silver iodide layer, or a silver iodobromide or silver chloroiodobromide emulsion containing a low silver iodide layer in the core part and a high silver iodide layer in the outermost layer. Further, even an emulsion containing a high silver chloride layer and a low silver chloride layer in the core part is a silver chloroiodobromide or silver chlorobromide emulsion containing a low silver chloride layer in the core part and a high silver chloride layer in the outermost layer. Good.
Furthermore, the layered structure may consist of three or more layers.

The silver halide emulsion is usually chemically sensitized. For chemical sensitization, for example, H. H. Frieser, Di Grundragel
Dell Photography Shen Plotse Mitt Gilberhalogeniden (Die Grundlagen)
der Photographischen Proz
ess mit Silberhalogenise
n) (Academia Michel Ferragus Gezel Shackt 1
968) The method described on pages 675 to 734 can be used.

That is, a compound containing sulfur capable of reacting with active gelatin or silver (eg, thiosulfates, thioureas,
Sulfur sensitization method using mercapto compounds, rhodanins); Reduction sensitization method using reducing substances (eg, primary tin salt, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); noble metal compounds (eg, , Gold complex salts, Pt, Ir, Rd, etc.
A noble metal sensitizing method using a group metal complex salt), a selenium sensitizing method using a selenium compound (selenoureas, selenoketones, selenides, selenophosphates, etc.) can be used alone or in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds);
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiazoazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; carboxyl groups and sulfone groups Heterocyclic mercapto compounds having water-soluble groups such as: thioketo compounds such as oxazoline thione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and many others known as antifoggants or stabilizers can be added.

The timing of addition of these antifoggants or stabilizers is usually carried out after chemical sensitization, but more preferably during the chemical ripening or before the start of the chemical ripening. That is, in the process of forming silver halide emulsion grains, during the addition of the silver salt solution, after the addition until the start of chemical ripening, during the chemical ripening (during the chemical ripening time, preferably within 50% from the start, More preferably within 20% of the time).

The amount of the above compound added cannot be uniquely determined by the method of addition and the amount of silver halide.
Preferably 10 ^-7 to 10 mol per mol of silver halide
^{It is -2} mol, more preferably 10 ^-5 to 10 ^-2 mol.

In the present invention, it is advantageous to use gelatin as a preservative (binding or protective colloid) for the photographic emulsion, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives. Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
Various synthetic hydrophilic polymer substances such as a single or copolymer such as polyvinyl imidazole and polyvinyl pyrazole can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Pho
t. Japan. No. The enzyme-treated gelatin as described in pages 16 and 30 (1966) may be used, or a hydrolyzate or an enzymatic hydrolyzate of gelatin may be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds are added to gelatin. What is obtained by reaction is used.

Specific examples of the dispersion medium used in the present invention include Research Disclosure (RESEARCH).
DISCROSURE) Volume 176, No. 17643
(December 1978), Section IX.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc .; nucleus in which alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine A nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus 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, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-
A 5-6 membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

A typical example thereof is US Pat. No. 2,688,54.
No. 5, No. 2,977,229, No. 3,397,060
No. 3,522,052, No. 3,527,641
Issue 3, Issue 3,617,293, Issue 3,628,924
Issue 3, Issue 3,666,480, Issue 3,672,898
Issue No. 3,679,428 Issue 3,703,377
Issue No. 3,769,301 Issue No. 3,814,609
No. 3,837,862, 4,026,707
No., British Patent Nos. 1,344,281 and 1,507,
No. 803, Japanese Patent Publication No. 43-4936, No. 53-12, 3
No. 75, JP-A Nos. 52-110,618 and 52-10.
No. 9,925.

In addition to the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

The dye may be added to the emulsion at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,628,9.
No. 69 and No. 4,225,666, it is also possible to add spectral sensitization at the same time as chemical sensitization as described in JP-A-58-113,928. It can be carried out prior to chemical sensitization as described, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add these said compounds separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It is also possible to add it after the feeling, and it is possible to add it after the sensation.
It may be at any time during the formation of the silver halide grains, including the method taught in 3,756.

The addition amount is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 1 × 10 ⁻² mol, but about 5 × when the silver halide grain size is 0.2 to 1.2 μm.
10 ^{-5 to} 6 × 10 ^-3 mol is more effective.

Although the above-mentioned various additives are used in the light-sensitive material of the present technology, various additives other than the above can be used according to the purpose.

More specifically, these additives are described in Research Disclosure Item 17643 (1978).
December) and Item 18716 (197)
(September and November), and the relevant parts are summarized in the table below.

Additive type RD17643 RD18716 1 Chemical sensitizer page 23 648 page right column 2 Sensitivity enhancer same as above 3 Spectral sensitizer, page 23 to page 648 page right column to supersensitizer page 649 page right column 4 Brightener page 24 5 Antifoggant page 24 to 25 page 649 Right column and stabilizer 6 Light absorber, Filter page 25 to 26 page 649 Right column to Dye UV absorber 650 page left column 7 Stain inhibitor page 25 right Column 650 Page left-right column 8 Dye image stabilizer Page 25 9 Hardener 26 page 651 Page left column 10 Binder page 26 Same as above 11 Plasticizer, lubricant 27 page 650 Page right column 12 Coating aid, surface active agent Pages 26 to 27 Id. 13 Antistatic Agents, page 27 Id. Various color couplers can be used in the photographic material of the present invention. Specific examples thereof include Research Disclosure (RD) No. 17643, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
No. 4,326,024, No. 4,401,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,02.
Nos. 0 and 1,476,760 are preferable.

As the magenta coupler, 5-pyrazolone type compounds and pyrazoloazole type compounds are preferable, for example, US Pat. Nos. 4,310,619 and 4,351,89.
7, EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630.
Nos. 4,540,654 are particularly preferred.

Examples of cyan couplers include phenol-type and naphthol-type couplers. For example, US Pat. Nos. 4,052,212, 4,146,396, 4,228,233 and 4,296. No. 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. 4,334,011, 4,327,173, West German Patent Publication No. 3,329,729, European Patent 121,
365A, U.S. Pat. Nos. 3,446,622 and 4,
333, 999, 4,451, 559, 4,4
27,767 and EP 161,626A are preferred.

Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No. 17643, Section VII-G, U.S. Pat. No. 4,1.
63,670, JP-B-57-39413, US Pat. Nos. 4,004,929 and 4,138,258, and British Patent 1,146,368 are preferable.

Examples of couplers in which the color forming dye has an appropriate diffusibility include, for example, US Pat. No. 4,366,237, British Patent 2,125,570, and European Patent 96,57.
Those described in No. 0 and West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, 4,367,282, and British Patent No. 2,102,173.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler which releases the development inhibitor is the above-mentioned R
D17643, Patents described in VII to F, JP-A-57-151944, JP-A-57-154234, and JP-A-57-154234.
Those described in 0-184248 and U.S. Pat. No. 4,248,962 are preferable.

Examples of the coupler capable of releasing a nucleating agent or a development accelerator imagewise during development include those disclosed in British Patent No. 2,
097,140, 2,131,188, JP-A-5
Those described in 9-157638 and 59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include, for example, US Pat. No. 4,13.
Competitive couplers described in US Pat. No. 4,427, US Pat.
283,472, 4,338,393, 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60
185950, 62-24252 and other DIR redox compounds or DIR coupler releasing couplers,
The couplers described in European Patent No. 173,302A, which release dyes that recover color upon release, RD. No. 11449 and 24241, bleach-accelerating release couplers described in JP-A-61-201247 and the like, and ligand releasing couplers described in US Pat. No. 4,553,477 and the like.

The coupler used in the present invention can be introduced into the photographic 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.

Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (eg, 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-diethylpropyl) phthalate), phosphoric acid or Esters of phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate) Over DOO, di-2-ethylhexyl phenyl phosphonate), benzoic acid esters (e.g., 2
-Ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g., N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (For example, isostearyl alcohol, 2,4-di-t
ert-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-tert-octylaniline), hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
An organic solvent having a temperature of about 160 ° C. or lower 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 and effects of the latex dispersion method 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.

The present invention can be applied to various color light-sensitive materials. Typical examples include a color negative film for general use and a color reversal film for slides.

When the present invention is applied to a color photographic material, it can be applied to a photographic material in which various photographic materials and layer structures are combined with special color materials.

A representative example thereof will be illustrated. Japanese Patent Publication 47-49
031, Japanese Patent Publication No. 49-3843, Japanese Patent Publication No. 50-21
248, JP-A-59-58147, JP-A-59-6.
0437, JP-A-60-227256, JP-A-61
-4043, JP-A-61-43743, JP-A-61
A combination of the coupling speed and diffusibility of a color coupler and the layer constitution such as No. 42657. JP-B-49-15495, U.S. Pat. No. 3,843,469
No. 2, the same color-sensitive layer is divided into two or more layers,
JP-B-53-37017, JP-B-53-37018
JP-A-51-49027, JP-A-52-1430
16, JP-A-63-97424, JP-A-53-97.
831, JP-A-62-200350, JP-A-59-
No. 177551, the arrangement of high-sensitivity layers and low-sensitivity layers, the arrangement of layers having different color sensitivities, and the like can be mentioned.

Suitable supports that can be used in the present invention are, for example, those described in RD. No. 17643, page 28, ibid.
18716, page 647, right column to page 648, left column.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pp. 28-29, and ibid. Development can be carried out by a usual method described in the left column to the right column of 651 of 18716.

Preferred embodiments of the present invention are listed below. (1) The photographic product according to claim 1 or (1) above, which contains a halogen gas scavenger at any position in the sealed container of the photographic product. (2) The photographic product according to (1) or (1) above, wherein a hydrogen cyanide gas or a halogen gas scavenger is present in the photographic light-sensitive material. (3) The photographic product according to claim 1, wherein the scan cyanogen gas is a Pd organic or inorganic compound. (4) The photographic product according to claim 1, wherein the relative humidity in the sealed container is 55% or more at 25 ° C. (5) The above (2), wherein the photographic light-sensitive material is a color photographic material.
(4) Photo product as described. (6) The hydrogen cyanide gas scavenger in the photographic product is 1/10 mol or more per 1 mol of thiocyanate contained in the part which can be irradiated with light, or the above (2).
~ (5) Photo product described. (7) The hydrogen cyanide gas scavenger in the photographic product is 1/2 mol or more per 1 mol of thiocyanate contained in the portion which can be irradiated with light, or the above (2) to
(5) The photographed product shown.

Examples will be shown below, but the present invention is not limited to these.

[0134]

【Example】

(Example 1) Onto an undercoated cellulose triacetate film support, each layer having the composition shown below was coated in multiple layers to prepare Sample 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 in terms of 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.

(Sample 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 2 , 5-di-t-pentadecylhydroquinone 0.18 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-1 0.10 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- 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 ( Middle layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10 7th layer (low-sensitivity green 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 8th layer (medium-sensitivity green-sensitive emulsion layer) emulsion D silver 0.80 ExS-4 3.2 × 10 ^{- 5 ExS-5 2.2 × 10 -4} ExS-6 8.4 × 10 -4 ExM-2 0.13 xM-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 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 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 Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60 11th layer (low sensitivity blue emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY -4 0.020 HBS-1 0.28 Gelatin 1.10 12th layer (medium speed blue emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS- 1 0.050 Gelatin 0.78 13th layer (High sensitivity blue feeling Agent 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 14th layer (first protective layer) Emulsion G silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00 Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter about 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter about 1.7 μm) 0.10 B -3 0.10 S-1 0.20 Gelatin 1.20 Furthermore, storability, processability, pressure resistance, antifungal,
To improve antibacterial property, antistatic property and coating property, W-
1 to W-3, B-4 to B-6, F-1 to F
-17, iron salt, and lead salt are contained.

[0136]

[Table 1] In Table 1, emulsions were prepared as described below.

[0137]

[Chemical 7]

[0138]

[Chemical 8]

[0139]

[Chemical 9]

[0140]

[Chemical 10]

[0141]

[Chemical 11]

[0142]

[Chemical 12]

[0143]

[Chemical 13]

[0144]

[Chemical 14]

[0145]

[Chemical 15]

[0146]

[Chemical 16]

[0147]

[Chemical 17]

[0148]

[Chemical 18]

[0149]

[Chemical 19]

[0150]

[Chemical 20]

[0151]

[Chemical 21] (Production Method of Emulsion A) 1000 ml of an aqueous solution containing 6 g of gelatin having an average molecular weight of 10,000 and 4.5 g of KBr was stirred at 30 ° C. and stirred with an aqueous AgNO ₃ (7.3 g) solution and KBr (5.3 g).
g) The aqueous solution was added with a double jet. Gelatin was added to bring the temperature to 60 ° C. After adjusting the electric potential to 0 mV with respect to the saturated calomel electrode, AgNO ₃ (141.1 g)
The aqueous solution and the KBr aqueous solution were added with a double jet while accelerating the flow rate. At this time, the saturated calomel electrode is -2
The silver potential was kept at 0 mV. Aqueous silver nitrate solution (AgNO
₃ 4.2 g) and a KI aqueous solution (4.1 g) were added over 5 minutes, the silver potential was set to −50 mV, and the silver nitrate aqueous solution (AgNO ₃ 60 g) and the KBr aqueous solution were accelerated with a double jet for 10 minutes. Added over. At this time, the silver potential was maintained at -50 mV with respect to the saturated calomel electrode. After desalting, gelatin was added and a sensitizing dye was added, followed by optimal gold, sulfur and selenium sensitization.

(Production Method of Emulsion B) 1000 ml of an aqueous solution containing 6 g of gelatin having an average molecular weight of 20,000 and 4.5 g of KBr.
Was stirred at 40 ° C. and AgNO ₃ (7.3 g) aqueous solution and KB were added.
An aqueous solution of r (5.3 g) was added with a double jet. Gelatin was added to bring the temperature to 65 ° C. After adjusting the potential to 0 mV with respect to the saturated calomel electrode, AgNO ₃ (14
1.1 g) aqueous solution and KBr (containing 3.0 mol% of KI)
The aqueous solution was added with a double jet while accelerating the flow rate.
At this time, the silver potential was maintained at -20 mV with respect to the saturated calomel electrode. Silver nitrate aqueous solution (AgNO ₃ 4.2g) and KI
After adding an aqueous solution (4.1 g) over 1 minute, the silver potential was set to −50 mV, and an aqueous silver nitrate solution (AgNO ₃ 60) was added.
g) and KBr aqueous solution were added with a double jet over 10 minutes while accelerating the flow rate. At this time, the silver potential was maintained at -50 mV with respect to the saturated calomel electrode. After desalting,
After adding gelatin and a sensitizing dye, optimum gold, sulfur and selenium sensitization was performed.

(Production Method of Emulsion C) 1000 ml of an aqueous solution containing 6 g of gelatin having an average molecular weight of 20,000 and 4.5 g of KBr.
Was stirred at 40 ° C. and AgNO ₃ (7.3 g) aqueous solution and KB were added.
An aqueous solution of r (5.3 g) was added with a double jet. Gelatin was added to bring the temperature to 65 ° C. After adjusting the potential to 0 mV with respect to the saturated calomel electrode, AgNO ₃ (14
5.3 g) aqueous solution and KBr aqueous solution were added by double jet while accelerating the flow rate. At this time, the silver potential was maintained at -20 mV with respect to the saturated calomel electrode. Silver potential -80m
V and KI aqueous solution (4.1 g) was added over 10 minutes, and then silver nitrate aqueous solution (AgNO ₃ 60 g) and KBr were added.
The aqueous solution was added with a double jet over 18 minutes while accelerating the flow rate. At this time, for the saturated calomel electrode −
The silver potential was kept at 80 mV. After desalting, gelatin was added and a sensitizing dye was added, followed by optimal gold, sulfur and selenium sensitization.

(Production Method of Emulsion D) 1000 ml of an aqueous solution containing 7 g of gelatin having an average molecular weight of 20,000 and 4.5 g of KBr.
Was stirred at 50 ° C. and AgNO ₃ (7.3 g) aqueous solution and KB were added.
An aqueous solution of r (5.3 g) was added with a double jet. Gelatin was added to bring the temperature to 70 ° C. After adjusting the electric potential to 10 mV with respect to the saturated calomel electrode, AgNO ₃ (1
An aqueous solution (45.3 g) and a KBr (containing 8.2 mol% KI) aqueous solution were added by a double jet while accelerating the flow rate. At this time, the silver potential was maintained at -30 mV with respect to the saturated calomel electrode. After adding the silver nitrate aqueous solution (AgNO ₃ 8.7 g) and the KI aqueous solution (7.1 g) over 5 minutes,
The silver potential was set to +20 mV and the silver nitrate aqueous solution (AgNO ₃ 5
1.3 g) and an aqueous KBr solution were added with a double jet over 50 minutes while accelerating the flow rate. At this time, the silver potential was maintained at +20 mV with respect to the saturated calomel electrode. After desalting, gelatin was added and a sensitizing dye was added, followed by optimal gold, sulfur and selenium sensitization.

(Production Method of Emulsion E) 1000 ml of an aqueous solution containing 8 g of gelatin having an average molecular weight of 20,000 and 4.5 g of KBr.
Was stirred at 60 ° C. and AgNO ₃ (7.3 g) aqueous solution and KB were added.
An aqueous solution of r (5.3 g) was added with a double jet. Gelatin was added to bring the temperature to 75 ° C. After adjusting the electric potential to 20 mV with respect to the saturated calomel electrode, AgNO ₃ (1
A 45.3 g) aqueous solution and a KBr (containing 7.0 mol% KI) aqueous solution were added with a double jet while accelerating the flow rate. At this time, the silver potential was maintained at -20 mV with respect to the saturated calomel electrode. A silver nitrate aqueous solution (AgNO ₃ 9.0 g) and a KI aqueous solution (8.8 g) were added over 20 minutes, and then the silver potential was set to −30 mV, and the silver nitrate aqueous solution (AgNO 3
₃ 51 g) and was a KBr aqueous solution were added over 50 minutes by the double jet while the flow rates were accelerated. At this time, the silver potential was maintained at -30 mV with respect to the saturated calomel electrode. After desalting, gelatin was added and a sensitizing dye was added, followed by optimal gold, sulfur and selenium sensitization.

(Preparation of Emulsion F) 1000 m of an aqueous solution containing 10 g of gelatin having an average molecular weight of 30,000 and 4.5 g of KBr.
1 at 70 ° C. and stirred with an aqueous solution of AgNO ₃ (7.3 g).
An aqueous solution of Br (5.3 g) was added with a double jet.
Gelatin was added to bring the temperature to 75 ° C. After adjusting the potential to 30 mV with respect to the saturated calomel electrode, AgNO
_{A 3} (139.2 g) aqueous solution and a KBr (containing 9.0 mol% KI) aqueous solution were added with a double jet while accelerating the flow rate. At this time, -30 mV against saturated calomel electrode
The silver potential was kept at. Aqueous silver nitrate solution (AgNO ₃ 6.1
g) and a KI aqueous solution (6.0 g) were added over 50 minutes, the silver potential was set to 0 mV, and a silver nitrate aqueous solution (AgNO
₃ 60 g) and was a KBr aqueous solution was added over an accelerated flow rate for 90 minutes by a double jet while. At this time, the silver potential was maintained at 0 mV with respect to the saturated calomel electrode. After desalting, add gelatin and sensitizing dye,
Sulfur and selenium sensitized.

(Manufacturing Method of Emulsion G) Emulsion G was prepared by a usual method of a double jet method using an AgNO ₃ aqueous solution and a halogen salt aqueous solution. After desalting, gelatin was added to prepare an emulsion G.

The thiocyanate used in the preparation of emulsions A to G is an aqueous solution of potassium thiocyanate, and the addition amount and the timing are as shown in the following table.

Table Emulsion Addition Amount (mol / mol Ag) Addition Timing A 8 × 10 ^{-3 During} Chemical Sensitization B 3 × 10 ^-3 〃 C 1 × 10 ^-3 〃 D 3 × 10 ^-3 〃 E 4 × 10 ^-3 〃 F 1.6 × 10 ^-3 〃 G ----- When the thiocyanate used for the preparation of emulsions A to G is added up, sample 101 contains 3 × 10 ^-3 mol / mol Ag thiocyanate. Is included.

Sample 102 was prepared in the same manner except that emulsions A to F used in sample 101 were changed to emulsions H to M, respectively. Sample 102 contains 3 × 10 ⁻³ mol / mol Ag of thiocyanate.

[0161]

[Table 2] The emulsions in Table 2 were prepared as follows.

(Production Method of Emulsion H) In the production method of Emulsion A,
It was prepared in the same manner except that hexachloroiridium (III) acid salt was added in the desalting step at 3 × 10 ⁻⁴ mol per mol of silver halide.

(Preparation of Emulsion I) In the preparation of Emulsion B, hexakis (thiocyanato) iridium (III) acid salt was chemically sensitized before 4.8 × 10 1 mol per mol of silver halide.
It was prepared in the same manner except that ^-5 mol was added.

(Production Method of Emulsion J) In the production method of Emulsion C,
Hexachloroiridium (IV) salt was used as A at the time of particle formation.
The same procedure was carried out except that 2.7 × 10 ⁻⁷ mol per mol of silver halide was added when the gNO ₃ aqueous solution was added at 71.8%.

(Production Method of Emulsion K) In the production method of Emulsion D,
Hexachloroiridium (IV) salt was used as A at the time of particle formation.
It was prepared in the same manner except that 60% of the gNO ₃ aqueous solution was added, and 8 × 10 ⁻⁸ mol was added per mol of silver halide.

(Production Method of Emulsion L) In the production method of Emulsion E,
Hexachloroiridium (IV) salt was used as A at the time of particle formation.
It was prepared in the same manner except that when the 98% gNO ₃ aqueous solution was added, 4.2 × 10 ⁻⁷ mol was added per 1 mol of silver halide.

(Production Method of Emulsion M) In the production method of Emulsion F,
Hexakis (thiocyanato) iridium (III) acid salt was prepared in the same manner except that 9 × 10 ⁻⁶ mol of hexakis (thiocyanato) iridium (III) salt was added per mol of silver halide during the chemical sensitization.

In Sample 101, sodium palladium (II) chloride was added to the sixth layer (intermediate layer) at 1 × with respect to the total silver amount.
Sample 1 was similarly prepared except that 10 ⁻⁵ mol / mol Ag was added.
03 was produced.

In Sample 102, sodium (II) chloride chloride was added to the sixth layer (intermediate layer) at 1 × with respect to the total silver amount.
Sample 1 was similarly prepared except that 10 ⁻⁵ mol / mol Ag was added.
04 was produced.

In Sample 101, the sixth layer (intermediate layer) contains sodium palladium (II) chloride at 1 × with respect to the total silver amount.
Sample 1 was similarly prepared except that 10 ⁻⁴ mol / mol Ag was added.
05 was produced.

In Sample 102, the sixth layer (intermediate layer) contains sodium palladium (II) chloride at 1 × with respect to the total amount of silver.
Sample 1 was similarly prepared except that 10 ⁻⁴ mol / mol Ag was added.
06 was produced.

Samples 101 to 106 were photographed in 135 format 24 sheets, processed into a patrone form, conditioned at a relative humidity of 60% at 25 ° C., and then stored in a transparent patrone case and a completely light-shielded patrone case in the dark.

The ratio of the area of the film filled with the light shielded from the film in the cartridge and the area of the film drawn out from the film drawing portion corresponds to 1: 0.05.

These were subjected to light irradiation for 24 hours for 10,000 lux, then stored together with those not irradiated for 3 days at 60 ° C., and processed under the following conditions using an automatic processor.

The processing steps and processing liquid compositions are shown below. (Processing step) Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 600 ml 17 liters Bleach 50 seconds 38.0 ° C 140 ml 5 liters Bleach fixing 50 seconds 38.0 ° C-5 liters Fixed 50 seconds 38.0 ℃ 420 ml 5 liters Water wash 30 seconds 38.0 ℃ 980 ml 3 liters Stable (1) 20 seconds 38.0 ℃ -3 liters Stable (2) 20 seconds 38.0 ℃ 560 ml 3 liters Dry 1 minute 60 ℃ Amount per 1 m ² The stabilizing solution was a countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath. To replenish the bleach-fixing bath, a switch is provided at the top of the bleaching tank of the automatic processor and at the top of the fixing tank. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the water washing process are respectively per 1 m ² of the light-sensitive material. 65m
1, 50 ml, 50 ml, 50 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

As the replenishing liquid, the same liquid as the tank liquid was replenished.

The composition of the treatment liquid is shown below. (Inventive developer) (Unit g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 1.4 Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 2-Methyl-4 -(N-Ethyl-N- (β-hydroxyethyl) amino) aniline sulfate 4.5 Water was added to 1.0 liter pH 10.05 (bleaching solution) (unit g) 1,3-Diaminopropaneferric acid ferric ammonium ammonium monohydrate Salt 130 Ammonium bromide 80 Ammonium nitrate 15 Hydroxyacetic acid 50 Acetic acid 40 Water is added to 1.0 liter pH (adjusted with ammonia water) 4.4 (bleach-fixing solution) A 15:85 (volume ratio) mixture of the above bleaching solution and the following fixing solution. (PH 7.0) (fixing solution) (Unit: g) Ammonium sulfite 19 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml imidazole 15 Ethylenediaminetetraacetic acid 15 Water was added to 1.0 l pH (adjusted with ammonia water and acetic acid) 7.4 (Washing) Water) Tap water is used as an H-type strongly acidic kaothine exchange resin (Amberlite IR-120B manufactured by Rohm and Haas)
And an OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through the column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by isocyanuric dichloride. Sodium acid 20mg / liter and sodium sulfate 150mg /
1 liter was added. The pH of this liquid was in the range of 6.5 to 7.5. (Stabilizing liquid) (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 and 1.0 liter pH 8.5 The results are shown in Table 3.

[0178]

[Table 3] The following are clear from Table 3. Irradiation of light in a transparent cartridge case causes abnormal fogging, and the degree of fogging is remarkable when silver halide grains containing an iridium salt are used. 1/1 th mol of thiocyanate contained in the portion of the sixth layer (intermediate layer) that can be irradiated with Pd salt.
In the case of the sample 104 containing 5 mol, the fogging by light irradiation in the transparent cartridge case was not significantly improved.
It is remarkably improved in the sample 106 with / 3 mol added. The effect of the Pd salt on the occurrence of fog on irradiation with light in the transparent cartridge case is remarkable in the silver halide grains containing the iridium salt. Further, in the silver halide grains containing no iridium salt, the occurrence of abnormal fogging due to light irradiation in the transparent cartridge case is small. P
Although the addition of the d salt improves abnormal fog even in silver halide grains containing no iridium salt,
The present invention does not reach the present invention in terms of reciprocity law characteristics.

Example 2 Sample 107 is a sample obtained by making the following changes to sample 106. 11th, 12th, 13th
Cpd-3 was added to the layers at 0.07, 0.015, 0.
02 g / m ^{2 was} added. The same processing as in Example 1 was performed, and the same experiment and treatment were performed. The results are shown in Table 4.

[0180]

[Table 4] It can be seen from Table 4 that the hydroquinone derivative known as a halogen gas scavenger contributes to the reduction of abnormal fog. (Example 3) The humidity and conditioning conditions of the sample 102 were changed, and the same experiment and treatment as in Example 1 were performed. The results are shown in Table 5.

[0181]

[Table 5] From Table 5, when the humidity in the cartridge case is low, abnormal fogging is unlikely to occur, and therefore the effect of the present invention is that the humidity is 55%.
It can be seen that the above is remarkable.

[Brief description of drawings]

FIG. 1 is a perspective view showing a specific example of a silver halide photographic product according to the present invention with a sealed container open.

Claims (1)

[Claims] 1. A support having at least one silver halide emulsion layer containing a thiocyanate salt and a gold / chalcogen-sensitized silver halide emulsion containing silver halide grains containing an iridium salt. 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, a part of the light-sensitive material being outside the light-shielding container. In a silver halide photographic product which is built in so as to be positioned and has a structure in which a gas can flow between the inside and outside of the light-shielding container, it is possible to have a hydrogen cyanide gas scavenger at any position in the sealed container. A characteristic silver halide photographic product.