JPH05333481A - Silver halide photographic product - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic product having high image quality and good long-term perservable stability in a product form. CONSTITUTION:This photographic product consists of a silver halide photosensitive material 3 constituted by providing at least one layer of silver halide emulsion layers contg. silver halide emulsions sensitized with gold chalcogen and thiocyanate on a base, a cartridge 4 as a light shielding container contg. the photosensitive material 3 and a plastic container 2 as a light transmittable hermetic container for housing the cartridge 4. The photosensitive material 3 is built into the light shielding container 4 in such a manner that a part thereof exists on the outer side of the container. In addition, the light shielding container 4 has the structure to allow the flow of gas through the inside and outside of the container. A gaseous hydrogen cyanide scavenger is provided in either position in the hermetic container 2. At least one layer of the silver halide emulsion layers of the photosensitive material contain the sensitizing dyestuff expressed by formula. In the formula, R<1> and R<2> denote an alkyl group; R<3> denotes a hydrogen atom, etc.; X<-> denotes anion; n denotes the numerical value for adjusting the charge over the entire part of the molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic product containing a silver halide photographic light-sensitive material. The present invention relates to a silver halide photographic product.

[0002]

2. Description of the Related Art Photosensitive silver halide photographic materials are
Must be shielded from light before use. For example, in the case of color film, the film is built into the cartridge to block light,
This patrone is housed in a closed case and then packaged in, for example, a paper box for sale. As a case for storing the patrone, a transparent plastic container is used because it is lightweight and has a good airtightness, the patrone inside can be easily seen and the contents can be easily confirmed, and it is easy to use as a small container thereafter. . However, it has recently been discovered that the performance of the film varies depending on the brightness of the place where the product is placed on the shelves of retail stores for a long time.

[0003]

As a result of further studying this point, it was found that, especially in a color film or the like lined up in a store for a long period of time, the fog was large and the sensitivity was lowered in the photographic performance. When the present inventors analyzed this phenomenon, a certain kind of gas was generated by the light hitting the drawer part of the film through the paper box containing the film case, and this gas was blocked from the light. It was found that the film diffuses inside the Patrone and changes the performance of the film. Such a phenomenon has never been known in the photographic industry. 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. SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic product which overcomes such problems and has high image quality and good long-term storage stability in product form.

[0004]

Means for Solving the Problems The inventors of the present invention have made further studies in order to achieve the above-mentioned object. As a result, the hydrogen cyanide gas scavenger ( Scavenger) and by containing a specific sensitizing dye in at least one silver halide emulsion layer of the light-sensitive material, photographic performance due to generation of hydrogen cyanide gas caused by light irradiation at a store Based on this finding, the present invention has been completed.

That is, the present invention provides a silver halide light-sensitive material comprising a support and at least one silver halide emulsion layer containing a gold chalcogen-sensitized silver halide emulsion and a thiocyanate, and It comprises a light-shielding container containing a light-sensitive material and a light-transmissive hermetically-sealed container containing the light-shielding container. The light-sensitive material is incorporated so that a part thereof is located outside the light-shielding container, and A silver halide photographic product having a structure in which a gas can flow between the inside and the outside, which has a hydrogen cyanide gas scavenger at any position in the sealed container and has at least one layer of the silver halide emulsion of the light-sensitive material. The present invention provides a silver halide photographic product characterized in that the layer contains a sensitizing dye represented by the following general formula (A).

[0006]

[Chemical 2] (In the formula, R ¹ and R ² represent an alkyl group. R ³ represents a hydrogen atom, an alkyl group or an aryl group. X ⁻ represents an anion, and n controls the charge of the whole molecule (neutralizes). ), And n = 0 when forming an intramolecular salt.)

By the way, in JP-A-3-505263, palladium, gold, platinum compounds and hydrogen cyanide scavenger are provided at positions where the fog caused by hydrogen cyanide gas generated from carbon black coated for light shielding can be blocked from the photosensitive emulsion. It is described that the inclusion can prevent it. However, this is not related to the above reaction, that is, generation of hydrogen cyanide gas by light irradiation. Nothing is disclosed that the gas generated from the light-irradiated portion affects the photographic properties of the light-shielded portion. Further, the addition of a Pd compound contained in the light-sensitive material is described in US Pat. About 8% of carbon black based on the weight of paper (about 0.7g per piece)
It contains black light-shielding paper, and this film is different from the reaction of hydrogen cyanide gas generated by light irradiation.

The hydrogen cyanide gas scavenger used in the present invention is a compound that converts hydrogen cyanide gas generated when a light-sensitive material is irradiated with light into a photographically inactive substance. 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 are palladium (II or IV; shows an oxidation state. The same applies hereinafter) and platinum (II or IV) compounds. Gold (I or III) compounds are also preferred. Rhodium (III), iridium (III or I
Compounds of V) and osmium (II, III or IV) are also effective, but higher amounts are required to have comparable effects. Specific examples of useful inorganic or organic noble metal compounds include, for example, the Gmelin Handbook.
ook), commercial products, synthetic products and i.
The in situ synthetic product can be used in such a purity that it does not adversely affect the photographic light-sensitive material.

Preferred 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 (salicylat) palladium (II) acid salt, bis ( Dithiooxalato-S, S ') palladium (II) acid salt, tra
ns-Dichlorobis (thioether) palladium (I
I), tetraamminepalladium (II) salt, dichlorodiamminepalladium (II), dibromodiamminepalladium (II), oxalatodiamminepalladium (II),
Dinitrodiamminepalladium (II), bis (ethylenediamine) palladium (II) salt, dichloroethylenediaminepalladium (II), bis (2,2'-bipyridine)
Palladium (II) salt, bis (1,10-phenanthroline) palladium (II) salt, tetranitropalladium (I
I) 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)] and dinitrobis (arsine) palladium (I
I) and the like.

Preferred platinum compounds are platinum (II) chloride, platinum (IV) chloride and hexafluoroplatinum (I).
V) acid salt, tetrachloroplatinate (II) acid salt, hexachloroplatinum (IV) acid salt, trichlorotrifluoroplatinum (IV) acid salt, tetrabromoplatinum (II) acid salt, hexabromoplatinum (IV) acid salt, dibromodichloro acid salt Platinum (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) salt, hexakis (thiocyanato) platinum (IV) 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 (II) , Chlorohydridobis (triethylphosphine) platinum (II), tetraammineplatinum (II) salt, tetrachloroplatinum (II) acid salt, dichlorodiammineplatinum (I
I), trichloroammine platinum (II) salt, hexaammine platinum (IV) salt, chloropentaammine platinum (IV) salt,
Tetrachlorodiammine platinum (IV), dinitrodiammine platinum (II), dichlorotetrakis (methylamine) platinum (IV) salt, dichloro (ethylenediamine) platinum (I
I), bis (ethylenediamine) platinum (II) salt, tris (ethylenediamine) platinum (IV) salt, dichlorobis (ethylenediamine) platinum (IV) salt, dichlorodihydroxo (ethylenediamine) platinum (IV), tetrakis (pyrimidine) platinum ( II) salt, dichlorobis (pyridine) platinum (II), bis (2,2′-bipyridine) platinum (II) salt,
Tetranitroplatinate (II), chlorotrinitroplatinate (II), dichlorodinitroplatinate (II), dibromodinitroplatinate (II), hexanitroplatinate (IV), chloropentanitroplatinate (IV) ) Acid salt, dichlorotetranitroplatinate (IV) acid salt, trichlorotrinitroplatinum (IV) acid salt, tetrachlorodinitroplatinum (IV) 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) salt and dichlorodicarbonyl platinum (I
I) and the like.

Gold (I or III), Rhodium (III), Iridium (III or IV) and Osmium (II, III or IV)
The compound of can also be used similarly, but as such an example, for example, potassium tetrachloroaurate (III)
, Rhodium (III) chloride, potassium hexachloroiridate (IV), potassium tetrachloroiridate (I
II) and potassium hexachloroosmate (IV). The inorganic or organic compound of the noble metal is not limited to the above-mentioned specific examples as long as the effects of the present invention can be obtained.

In the present invention, the hydrogen cyanide gas scavenger may be located anywhere within the sealed container of the silver halide photographic product. The composition may be applied to the inner surface of the hermetically sealed container or kneaded and molded into it, or may be applied or kneaded and molded into parts forming a light-shielding container (for example, cartridge). Above all, it is preferable that a hydrogen cyanide gas scavenger is present in the photographic light-sensitive material. Specifically, photographic light-sensitive materials are usually
It comprises a support, a back layer, an emulsion layer, a surface protective layer, an intermediate layer, and an antihalation layer. It can be coated with a suitable solvent or binder. As a method for adding the hydrogen cyanide gas scavenger, a method usually used when adopting a method for 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.

The backing layer, emulsion layer, surface protective layer, intermediate layer and antihalation layer are usually binder dispersions, 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 or 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 depending on the kind and amount of the hydrogen cyanide gas scavenger used.

Generally, a noble metal compound and gelatin interact with each other, and the viscosity of the system may remarkably increase depending on conditions. For example, regarding the interaction between the palladium (II) ion and gelatin, the Journal of the Photographic Society of Japan, 34, 159 (19
71) Keiichi Tanaka, Journal of the Photographic Society of Japan, vol. 37, p. 133 (1)
974) Keiichi Tanaka, Journal of the Photographic Society of Japan, Vol. 39, page 73 (1976) Keiichi Tanaka, Journal of Photographic Science, Vol. 21, page 134 (1973) Keiichi Tanaka and Journal of Photographic Science, Vol. It is described in detail in Keiichi. 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 appropriately select and use it. The addition amount of the hydrogen cyanide gas scavenger in the present invention should be determined within the range in which the effects of the present invention are exhibited, but preferably the thiocyanate 1 contained in the portion which can be irradiated with light.
It is 1/10 mol or more with respect to mol. More preferably, the amount is 1/2 mol or more and 100 mol or less with respect to 1 mol of the thiocyanate contained in the portion that can be irradiated with light.

The photographic light-sensitive material in 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, 647
Page right column to page 648 left column and RD. No. 307105, page 879. Gold / chalcogen sensitization is gold /
Sulfur sensitization, gold / selenium sensitization, gold / tellurium sensitization, gold / sulfur / selenium sensitization, gold / sulfur / tellurium sensitization, gold / selenium / tellurium sensitization and gold / sulfur / selenium / tellurium sensitization Any one can be selected and used. A thiocyanate is used for these gold / chalcogen sensitization. As the thiocyanate, ammonium salt, potassium salt, sodium salt and the like are preferably used.

The gold chalcogen sensitization in the present invention will be described in detail. 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 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 examples of unstable selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenium amides,
There are selenocarboxylic acids and esters, and selenophosphates. 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 compounds such as allyl isoselenocyanate Isoselenocyanate b selenoureas (including enol type) For example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, dioctyl, tetramethyl, N- (β-carboxyethyl) -N′-N′-dimethyl. , N-N-Dimethyl, diethyl, dimethyl, etc., aliphatic selenoureas; Aromatic selenourea having one or more aromatic groups such as phenyl, tolyl, etc .; Heterocycles having heterocyclic groups such as pyridyl, benzothiazolyl, etc. Selenoureas c selenoketones, for example, selenoacetone, selenoacetophenone, alkyne Selenoketones having groups bound to> C = Se, selenobenzophenones d selenoamides, for example selenoacetamide e selenocarboxylic acids and esters, for example 2-selenopropionic acid, 3-selenobutyric acid, methyl 3-selenobutyrate III. Others a Selenides For example, diethyl selenide, diethyl diselenide,
Triphenylphosphine selenide b selenophosphates, for example, tri p-tolylselenophosphate, tri-n-butyl selenophosphate

Preferred types of labile selenium compounds have been described above, but are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, so long as selenium is unstable, the structure of the compounds is not so important, and the organic portion of the selenium sensitizer molecule is It is generally understood that it has no role except to carry selenium and make it present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used. Japanese Examined Sho 46-
4553, 52-34492 and 52-344.
Selenium sensitization using the non-labile selenium sensitizer described in No. 91 is also used. Examples of the non-unstable selenium compound include selenious acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles, diaryl selenides, diaryl diselenides, 2-thioselenazolidinediones, and 2-selenooxazines. Thiones and their derivatives are included.

The non-labile selenium sensitizer and thioselenazolidinedione compound described in JP-B-52-38408 are also effective. These selenium sensitizers are added at the time of chemical sensitization by dissolving in water or an organic solvent such as methanol and ethanol alone or in a mixed solvent. It is 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. 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 the activity of the selenium sensitizer used, the kind and size of silver halide, the temperature and time of ripening, and preferably 1 mol of silver halide. 1 x 10
^-8 mol or more. More preferably, it is 1 × 10 ⁻⁷ mol or more and 1 × 10 ⁻⁴ mol or less. The temperature of chemical ripening when the 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 pH range of 4 to 9.

The selenium sensitization of the present invention is more effective when carried out in the presence of a silver halide solvent. The silver halide solvent that can be used in the present invention includes U.S. Pat. Nos. 3,271,157 and 3,531,289.
No. 3,574,628, JP-A-54-1019.
(A) Organic thioethers described in JP-A Nos. 54-158917, JP-A-53-82408, 55-55
No. 77737, No. 55-2982 and the like (b) thiourea derivatives, and (c) a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom as described in JP-A-53-144319. A silver halide solvent having
Examples thereof include (d) imidazoles, (e) sulfite, (f) thiocyanate, etc. described in JP-A No. 54-100717. Particularly preferred solvents are thiocyanate and tetramethylthiourea. The amount of the solvent used varies depending on the type, but in the case of thiocyanate, the preferable amount is 1 × per mol of silver halide.
It is 10 ⁻⁴ mol or more and 1 × 20 ⁻² mol or less. Sulfur sensitization is usually carried out at a high temperature, preferably 4 by adding a sulfur sensitizer.
It is carried out by stirring the emulsion at 0 ° 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 above-mentioned sulfur sensitization, known sulfur sensitizers can be used. Examples thereof include thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other US Pat. No. 1,574,
No. 944, No. 2,410,689, No. 2,27
No. 8,947, No. 2,728,668, No. 3,5
No. 01,313, No. 3,656,955, German Patent 1,422,869, Japanese Patent Publication No. 56-2
Sulfur sensitizers described in JP-A-4937, JP-A-55-45016 and the like can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but is 1 × 10 ^-7 mol or more per 1 mol of silver halide and 1 × 10 ^-4. It is preferably not more than mol. As the gold sensitizer for gold sensitization of the present invention, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like. The addition of the gold sensitizer varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 1 × 10 ⁻⁴ mol per mol of silver halide.

The thiocyanate may be used alone for 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.

According to the research conducted by the present inventors, it is considered that the following reaction occurs under light irradiation in the silver halide emulsion layer. 2AgBr (+ hν; light irradiation) → 2Ag + Br ₂ (printout) 2AgSCN + Br ₂ → 2AgBr + (SCN) ₂ (SCN) ₂ (hydrolysis) → 2HCN According to the present invention, the scavenger traps the hydrogen cyanide gas. From this reaction formula, it will be understood that the halogen gas scavenger described below is also effective.

The above-mentioned halogen gas scavenger which can be used in the present invention is a compound which converts a halogen gas generated when a light-sensitive material is irradiated with light into a photographically inactive substance. The scavenger should not release any substance that has a harmful effect on 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 its action depends on the pH and pA of the system.
It is also known to be a function of g. However, in the present invention, it is preferable that the following compound is present as a halogen gas scavenger at any position in the sealed container of the silver halide photographic product. For example, sulfide compound, nitrite, semicarbazide, sulfite,
Hydroquinones, ethylenediamine, acetone semicarbazone, p-hydroxyphenylglycine and the like.

The halogen gas scavenger may be added at either a protective layer, an intermediate layer, a non-photosensitive layer such as a back layer opposite to the emulsion surface of the film, or a silver halide emulsion layer. More preferably, it is added on the emulsion layer side of the support to a layer further away from the support. The addition amount is 0.
05 to 1 g / m ² , more preferably 0.1 to 0.5 g / m ² .
m ² . In the silver halide photographic product of the present invention, a photographic light-sensitive material contained in a light-shielding container is stored in a hermetically-sealed container. A part of the light-sensitive material is placed at a position where light can be irradiated after sealing, and the rest is the light-shielding material. It is protected from light by the container,
Air is circulated between the light-irradiated portion and the light-shielded portion.

The light-shielding container of the present invention includes a cassette for a sheet film, but a cartridge for a roll film is typical. A cartridge for a roll film has a spool shaft around which a silver halide light-sensitive material is wound in a roll shape, a film outlet for loading and unloading the light-sensitive material, and a cartridge body for rotatably storing the spool around its axis. .. In order to shield light, the spool has a flange, and external light that is incident on the inside of the container through a gap between the spool shaft and a cap provided on a side edge of a typically cylindrical body of the cartridge body. Shut off. Also,
A light blocking member is preferably 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. Silver halide photographic products in which the present invention can be used include, for example, currently popular 135-format roll film. One embodiment of this is shown in FIGS. FIG. 1 shows a state in which a film 1 with a cartridge is housed in a transparent plastic container 2. FIG. 2 shows a film 1 with a cartridge. Silver halide photographic light sensitive material 3 as shown
Is housed in a metal cartridge 4 using a plastic spool as a mandrel, and is partially pulled out from the film pull-out portion 5 via a light-shielding ribbon. Reference numeral 6 indicates a pulled-out portion of the film. A few cm of film is usually pulled out for the convenience of film loading. This part 6
Corresponds to a position where light can be irradiated, and air is allowed to flow to the light-shielded portion through the gap between the film drawing portion 5 or the cartridge.

The cartridge 4 containing the silver halide photographic light-sensitive material comprises a container body 2a and a container cap 2b.
It is sealed by a transparent plastic container 2. This sealed transparent plastic container 2 is designed to block harmful gases to the photosensitive material and suppress excessive permeation of water vapor, but the permeability of gas and water vapor is the main body 2 of the container.
It is greatly influenced by the structure and material of the container a and the cap 2b of the container. The humidity in the sealed container is preferably kept constant, and in the present invention, the relative humidity is 25%.
The effect of the invention is remarkable when the temperature is 55% or higher. That the humidity of the sealed container is kept constant means that the humidity change inside the case is 10% or less when 12 months have passed at 25 ° C. when the humidity difference between the outside air and the inside of the case is 20%.

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 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, FIG.
As shown in, the body 2a of the transparent plastic container or the cap 2b of the container is transparent or translucent. The term "transparent" or "translucent" means that the portion pulled out from the film pull-out portion can be substantially exposed to external light. More specifically, when it is kept under irradiation with light of 10000 lux for 24 hours, the increase in fogging of the part drawn out from the film drawing part is 0.1 or more, preferably 0.5 or more, more preferably 1.0 or more. Is.

The plastic material used in the present invention includes addition polymerization of an olefin having a carbon / carbon double bond, ring-opening polymerization of a small ring compound, polycondensation (condensation polymerization) between two or more polyfunctional compounds, and polycondensation. It can be produced by a method such as addition and condensation of a phenol derivative, a urea derivative or a melamine derivative with a compound having an aldehyde. The raw material of the plastic material is an olefin having a carbon-carbon double bond, for example, styrene, α-methylstyrene,
Butadiene, methyl methacrylate, butyl acrylate,
Representative examples thereof include acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl carbazole, N-vinyl pyrrolidone, vinylidene cyanide, ethylene and propylene. Further, as the small ring compound, for example, ethylene oxide, propylene oxide, glycidol, 3,3-bischloromethyl oxetane, 1,4-dioxane, tetrahydrofuran, trioxane, ε-caprolactam, β-propiolactone, ethyleneimine, tetra Typical examples include methyl siloxane and the like.

Examples of polyfunctional compounds include carboxylic acids such as terephthalic acid, adipic acid and glutaric acid,
Representative examples are toluene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and other isocyanates, ethylene glycol, propylene glycol, glycerin, and other alcohols, hexamethylenediamine, tetramethylenediamine, paraphenylenediamine, and other amines, and epoxies. It is mentioned as a thing. Examples of the phenol derivative, urea derivative, and melamine derivative include phenol, cresol, methoxyphenol, chlorophenol, urea,
Representative examples include melamine. Further, as a compound having an aldehyde, formaldehyde,
Representative examples include acetaldehyde, octanal, dodecanal, benzaldehyde and the like. These raw materials may be used alone or in combination of two or more, depending on the target performance. When manufacturing a plastic material 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-
Radical polymerization catalysts such as methyl propane), benzoyl peroxide, cyclohexanone peroxide, potassium persulfate, etc., cationic polymerization catalysts such as sulfuric acid, toluenesulfonic acid, trifluorosulfuric acid, perchloric acid, trifluoroboron, tin chloride, n-butyl. Anionic polymerization catalysts such as lithium, sodium / naphthalene, 9-fluorenyllithium and phenylmagnesium bromide, triethylaluminum / tetrachlorotitanium meter Ziegler-Natta 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, and 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 needed. 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 plastic 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 Phenolic resin P-16 Melamine resin

Particularly preferred plastic materials for the present invention are polystyrene, polyethylene, polypropylene and the like. In order to provide light-shielding properties, it is manufactured using plastic in which carbon black, pigment, etc. are kneaded.

The sensitizing dye represented by the general formula (A) used in the present invention is F.I. M. Hamer
Written by "Heterocyclic Compounds-Cyanine
Soybean and relayed compounds (Hetero
cyclic Compounds-Cyanine Dyes and Related Compound
s) ”, Chapters 4, 5, 6 and 86-119,
John Wiley and S
ons) (1964), D.I. M. Starmer (D.
M. Sturmur), Heterocyclic Compounds-Special Top
ics in Heterocyclic Chemistry) ”, Chapter 8, 48
It can be easily synthesized based on the method described in pages 2 to 515, published by John Wiley and Sons (1977), and the like. Specific examples of the sensitizing dye represented by formula (A) used in the present invention are shown in Table 1 below, but the present invention is not limited thereto.

[0035]

[Table 1]

The sensitizing dye represented by the general formula (A) used in the present invention may be contained in any step of the production process of the silver halide photographic light-sensitive material. In order to incorporate the compound represented by the general formula (A) used in the present invention into silver halide, they may be directly dispersed in an emulsion,
Alternatively, they may be dissolved in a solvent such as water, methanol, ethanol, acetone, methyl cellosolve, or fluorinated alcohol alone or in a mixed solvent and added to the emulsion. 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 of reacting silver and halogen, physical ripening process, chemical ripening (post heat)
It can be added immediately before the process, during the chemical ripening process, or immediately after the chemical ripening process.

Further, these are singly or dissolved in a solvent which is substantially immiscible with water such as phenoxyethanol and then dispersed in water or a hydrophilic colloid directly or by using a surfactant, and this dispersion is dispersed in an emulsion. May be added to. The addition amount of the sensitizing dye represented by the general formula (A) used in the present invention varies remarkably depending on the kind of silver halide emulsion, but is usually 4 × 10 ^-6 mol to 8 × 10 ^-3 mol per mol of silver halide. Is.

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

The intermediate layer has a layer of JP-A-61-43748.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is usually 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 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,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order. In addition, Japanese Examined Japanese Patent Publication 55-349
As described in Japanese Patent No. 32,32, it is also possible to arrange in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, JP-A-56-25738,
As described in the specification of No. 62-63936,
Blue-sensitive layer / GL / RL / G from the side farthest from the support
It is also possible to arrange them in the order of H / RH.

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 low photosensitivity is arranged 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 from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer. In addition, they 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, in the case of four layers or more, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
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 configurations and arrangements can be selected according to the purpose of each light-sensitive material. The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. .. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is
The projected area diameter is about 1 even for fine particles of about 0.2 microns or less.
Large size particles up to 0 micron may be used, and polydisperse emulsion or monodisperse emulsion may be used.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23, "
I. Emulsion preparation and types ",
And No. 18716 (November 1979), 648.
Pp. 307105 (November 1989), 863.
-865 and Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P.Glafkides, Chemie et Phisique
Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff
in, Photographic Emulsion Chemistry (Focal Press, 1
966)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et al., Making
and Coating Photographic Emulsion, Focal Press, 19
It can be prepared using the method described in 64).
US Pat. Nos. 3,574,628 and 3,655,39
Monodisperse emulsions described in, for example, No. 4 and British Patent No. 1,413,748 are 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 emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which forms a latent image inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is
It is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process, etc.
-40 nm is preferable, and 5-20 nm is particularly preferable.
As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The additives used in such a process are the above-mentioned Research Disclosure N.
No. 17643, No. 18716 and No. 30710
It is described in No. 5, and 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 kinds of light-sensitive silver halide emulsions having at least one characteristic of grain size, grain size distribution, halogen composition, grain shape, and sensitivity. The above emulsion,
It can be mixed and used in the same layer. Fogging silver halide grains described in U.S. Pat. No. 4,082,553 and halogens fogged inside the grains described in U.S. Pat. No. 4,626,498 and JP-A-59-214852. 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 grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed portion and exposed portion of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
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 a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment. preferable. The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain diameter (average value of circle-equivalent diameters of projected areas) of 0.01 to 0.5 μm, and 0.02 to
0.2 μm is more preferable. 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 nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. 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 right column 3 Spectral sensitizer, page 23 to page 648 right column page to 866 to 868 page Supersensitizer page 649 Right column 4 Whitening agent page 24 647 Page right column 868 Page 5 Antifoggant, pages 24 to 25 page 649 Right column 868 to 870 Stabilizer 6 Light absorber, page 25 to 26 649 Page right column to page 873 filter dye page 650 left column UV absorber 7 anti-staining agent page 25 right column page 650 left column to page 872 right column 8 dye image stabilizer page 25 650 page left column page 872 9 hardener 26 Page 651 page left column 874 to 875 page 10 binder 26 page same as above page 873 to 874 page 11 plasticizer, lubricant page 27 page 650 page right column page 876 12 coating aid, page 26 to page 650 right column page 875 to 876 surface Activator 13 Static protection page 27 page 650 right column 876 to 877 stop agent 14 matting agent page 878 to 879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add a compound capable of being immobilized by reacting with formaldehyde described in No. 87 and No. 4,435,503 to the light-sensitive material. The light-sensitive material used in the silver halide photographic product of the present invention is described in US Pat.
No. 454, No. 4,788,132, JP-A-62-1.
It is preferable to incorporate the mercapto compounds described in JP-A No. 8539 and JP-A No. 1-283551. The light-sensitive material used in the silver halide photographic product of the present invention is disclosed in JP-A-1-
It is preferable to include a compound described in No. 106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing. The light-sensitive material used in the silver halide photographic product of the present invention is disclosed in International Publication WO88 / 0479.
4, a dye dispersed by the method described in JP-A-1-502912 or the dyes described in EP317,308A, US Pat. No. 4,420,555, and JP-A-1-259358. Is preferred.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure (RD) No. 17643, VII-C to G, and No. 307105, VII-C. To the patents listed in G. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501 and 4,022,6.
No. 20, No. 4,326,024, No. 4,401,
752, 4,248,961 and Japanese Examined Patent Publication 58-1
0739, British Patents 1,425,020, 1,476,760, U.S. Patent 3,973,968.
No. 4,314,023, No. 4,511,64
Those described in No. 9, European Patent No. 249,473A, etc. are preferable. As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
1,432, 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-72238, and JP-A 60-32.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 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, JP-A-61-42658 and the like are preferable. Further, JP-A 64-553 and 64-5.
54, 64-555 and 64-556, and pyrazoloazole couplers described in US Pat. No. 4,811.
The imidazole couplers described in No. 8,672 can also be used. Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820 and 4,0.
No. 80,211, No. 4,367,282, No. 4,
409,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A.
No. etc.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) No. 3 , 234,533 are preferable. Researched Disclosure No. 1 is a colored coupler for correcting unwanted absorption of color forming dyes.
7643, Item VII-G, No. 307105, Item VII-G
, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-3
9413, 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 releasing a development inhibitor are disclosed in RD17643, VII-F and JP-A No. 307105, VII-F, JP-A-57-151944 and 57-15423.
No. 4, No. 60-184248, No. 63-37346.
63-37350, U.S. Pat. No. 4,248,9.
Those described in No. 62 and No. 4,782, 012 are preferable.

The bleaching accelerator releasing couplers described in RD No. 11449, No. 24241, JP-A No. 61-201247 and the like are effective for shortening the time of the processing step having a bleaching ability, and particularly, the above-mentioned flat plate. The effect is great when it is added to a light-sensitive material using a silver halide grain.
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-59-157638.
Nos. 59-170840 and No. 59-170840 are preferable.
Also, JP-A-60-107029 and JP-A-60-2523.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent, etc. by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A No. 40, JP-A-1-44940 and JP-A-1-45687 are also preferable. Other compounds that can be used in the light-sensitive material of the present invention include US Pat.
Competitive couplers described in U.S. Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60
No. 185950, JP-A No. 62-24252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A, 313, 313. No. 308A, a coupler releasing a dye that undergoes color recovery after release, 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, Examples thereof include couplers releasing a fluorescent dye described in US Pat. No. 4,774,181.

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. 2,322,222.
No. 027 and the like. 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 (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-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (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 (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (for example, N, N-diethyldodecane amide, N, N-diethyllaurylamide,
N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4
-Di-t-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-t-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 or higher and about 16 ° C.
An organic solvent at 0 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
In the light-sensitive material used in the silver halide photographic product of the present invention, phenethyl alcohol and JP-A-63-25774 are used.
No. 7, 62-272248, and JP-A-1-809.
1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-
It is preferable to add various preservatives or antifungal agents such as phenoxyethanol and 2- (4-thiazolyl) benzimidazole. The present invention is preferably applied to various color photographic materials. Color negative film for general use,
A typical example is a color reversal film for slides.

Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, No. 18
716, right column, page 647 to left column, page 648, and No. 3 of the same.
07105, page 879. Film swelling rate T of a light-sensitive material used in the silver halide photographic product of the present invention
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film swelling rate T _1/2 can be measured according to a method known in the art. For example, A. Green et al. Photographic Science and Engineering (Photogr. Sci. En
g.), Vol. 19, No. 2, pp. 124-129, and can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is a color developing solution at 30 ° C. for 3 minutes 15 90% of the maximum swollen film thickness reached when the second treatment is performed is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. 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 150
~ 400% is preferred. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness)
/ Can be calculated according to the film thickness. The light-sensitive material used in the silver halide photographic product of the present invention is preferably 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. .
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surface active agent and the like. The swelling ratio of this back layer is 150-
500% is preferable.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, No. 18;
716, page 651, left column to right column, and No. 307105.
It can be developed by a usual method described on pages 880-881. The color developing solution used for processing 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-
Examples thereof include N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these,
3-Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developer contains, for example, a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound,
It is common to include a development inhibitor such as benzothiazoles or mercapto compounds or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvent such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salt,
Development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos. Various chelating agents represented by carboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo. -N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N,
Representative examples include N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal processing is carried out, black and white development is usually carried out before color development. In the black-and-white developing solution, known developing agents, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used. They 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. Further, the replenishing amount of these developing solutions is generally 3 liters or less per 1 square meter of the light-sensitive material, though it depends on the color photographic light-sensitive material to be processed, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, the contact area with air in the processing tank is reduced to evaporate the liquid,
It is preferable to prevent air oxidation.

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 (cm ⁻¹ ) is preferably 0.1 or less, It is more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in No. 60-216050 can be mentioned. Reducing the aperture ratio is preferably applied not only in both the color developing step and the black and white developing step but also in the subsequent steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilizing. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. 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 may 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. Typical bleaching agents are organic complex salts of iron (III), such as aminopolyamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Carboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Among these, aminopolycarboxylic acid irons such as ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III) complex salt
(III) 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 iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH 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: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978), and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45. -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,12
No. 7,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30; Japanese Patent Publication No. 4
Polyamine compounds described in JP-A-5-8836; Others, JP-A-49-40943, JP-A-49-59644, and JP-A-53-
94927, 54-35727, 55-265.
Compounds described in No. 06 and No. 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 particularly described in U.S. Pat. Compounds are preferred. Further, US Pat. No. 4,55
The compounds described in No. 2,834 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 photographing.

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, hydroxyacetic acid and the like are preferred. As a fixing agent used in a fixing solution or a bleach-fixing solution, thiosulfate,
Thiocyanates, thioether compounds, thioureas,
Although a large amount of iodide salt and the like can be mentioned, thiosulfate is generally used, and ammonium thiosulfate is 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, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids 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 has a pKa of 6.0 to adjust the pH.
It is preferable to add a compound of 9.0, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole in an amount of 0.1 to 10 mol / liter.

The total time for 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 preferred temperature range, the desilvering rate is improved,
In addition, the occurrence of stains after the treatment is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, Japanese Patent Laid-Open No. 62-62160
No. 183460, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material, a method of improving the stirring effect by using a rotating means of JP-A No. 62-183461, and a wiper provided in the solution. Examples include a method of moving the light-sensitive material while bringing the blade into contact with the emulsion surface to make the emulsion surface turbulent, thereby further improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. The improvement of stirring is due to the bleaching agent in the emulsion film,
It is considered that the supply of the fixing agent is accelerated, and as a result, the desilvering rate is increased. 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 and 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 washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the material used such as couplers), 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 water volume in the multi-stage countercurrent system is described in the Journal of the
Society of Motion Picture and Television Engineer
s Vol. 64, p. 248-253 (May 1955 issue)
It can be determined by the method described in. According to the multi-stage counter-current method described in the above literature, 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, etc. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, JP-A-62-2
The method for reducing calcium ion and magnesium ion described in No. 88838 can be used very effectively. Further, isothiazolone compounds, thiabendazoles, chlorine-based bactericides such as chlorinated sodium isocyanurate described in JP-A-57-8542, and benzotriazole, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986).
Sankyo Publishing, Sanitary Technology Society, "Sterilization, Sterilization, and Antifungal Technology of Microorganisms" (1982), Industrial Technology Association, Japan Society for Antibacterial and Antifungal, Encyclopedia of Antibacterial and Antifungal Agents (1986) A bactericide can also be used.

The pH of the washing water in the processing of the light-sensitive material used in the present invention is 4 to 9, preferably 5 to 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. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. 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 that accompanies the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. 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. 14850 and N.
Schiff base type compound described in No. 15159, No. 1
Aldol compounds described in 3924, US Pat. No. 3,7
Metal salt complexes described in JP-A-53-135.
The urethane compound described in No. 628 can be mentioned. The silver halide color light-sensitive material used in the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of promoting color development.
Typical compounds are JP-A Nos. 56-64339 and 57-57.
Nos. 144547 and 58-115438. Various treatment liquids in the present invention are 10 ° C to 50 ° C.
Used in. 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.

[0069]

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 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 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 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 0.010 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 0.010 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 0.010 HBS-1 0.50 gelatin 1.10

Seventh Layer (Low-Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ⁻⁵ A-11 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 A-11 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

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ⁻⁵ A-11 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 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive 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

Thirteenth 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 14th layer (first protective layer) UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00 15th 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 order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6,
It contains F-1 to F-17, iron salt and lead salt.

[0079]

[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 gold-sensitized and sulfur-sensitized under the conditions shown in Table 3 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. And selenium sensitization is applied. (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 are observed in the tabular grains and the normal crystal grains having a grain structure by using a high voltage electron microscope.

[0081]

[Table 3]

[0082]

[Chemical 3]

[0083]

[Chemical 4]

[0084]

[Chemical 5]

[0085]

[Chemical 6]

[0086]

[Chemical 7]

[0087]

[Chemical 8]

[0088]

[Chemical 9]

[0089]

[Chemical 10]

[0090]

[Chemical 11]

[0091]

[Chemical formula 12]

[0092]

[Chemical 13]

[0093]

[Chemical 14]

[0094]

[Chemical 15]

[0095]

[Chemical 16]

[0096]

[Chemical 17]

(Films 102-104) Tetrachloropalladium (II) potassium was added to the sixth layer in an amount of ² per m 2.
mg, 1 mg, 0.5 mg are added (thiocyanate 1
The film 10 except for the addition of 0.533 mol, 0.267 mol, and 0.133 mol, respectively, with respect to mol.
Films 102, 103 and 104 were produced in the same manner as in 1. (Film 105) Film 101 except that 2 mg of tetrachloropalladium (II) potassium was added to the 14th layer
A film 105 was produced in the same manner as in. (Film 106) A film 106 was prepared in the same manner as the film 102 except that the sensitizing dye A-11 in the seventh layer, the eighth layer, and the ninth layer was replaced with equimolar ExS-8.

[0098]

[Chemical 18]

(Film 107) 7th layer, 8th layer, 9th layer
A film 107 was prepared in the same manner as the film 102 except that the sensitizing dye A-11 in the layer was replaced with equimolar ExS-4. (Film 108) C in the 11th, 12th and 13th layers
Film 108 was prepared in the same manner as film 102 except that pd-3 was added in an amount of 10 mg, 5 mg and 4 mg, respectively, per m ^2.
Was produced.

Films 101-108 in the dark 135
Format 24 shots Processed into a patrone form. At this time, the ratio of the area of the film filled in the inside of the cartridge and the area of the film drawn out from the film drawing portion was set to correspond to 1: 0.05. This one at 25 ℃
After adjusting the humidity to 60% RH for 4 days, the silver halide photographic products 1 to 10 shown in Table 4 were placed in a transparent plastic airtight container shown in FIG. It was made.

[0101]

[Table 4]

For silver halide photographic products 1-10,
As shown in Table 4, those with and without light irradiation at 10,000 lux for 24 hours were prepared (Samples 1001 to 10 in Table 5).
19) was done. Samples 1001 to 1019 were stored in the dark at 60 ° C. and a relative humidity of 60% RH for 3 days. Thereafter, the closed container was opened, the film was pulled out in the dark, and the unexposed portion was exposed at a color temperature of 4800 ° K through a continuous wedge for 1/100 seconds. Further, silver halide photographic products 1 to 10 which were not subjected to the above treatment were similarly exposed.

[0103]

[Table 5]

After exposing the color photographic light-sensitive material as described above, it was processed by the following method. (Processing method) Process 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 Wash (2) 30 seconds 24 ℃ Stability 30 seconds 38 ℃ Dry 4 minutes 20 seconds 55 ℃

Next, the composition of the treatment liquid is shown. (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

(Bleach) (Unit: g) Ethylenediaminetetraacetic acid sodium ferric 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

(Fixer) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / liter) 290.0 ml Water was added to 1.0 liter pH 6.7

(Stabilizing 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

The density of the treated sample was measured with a green filter, and the relative humidity was 60% at 60 ° C. with respect to the untreated film.
The increase in fog and the change in sensitivity of the film stored in RH for 3 days were determined and are shown in Table 5. At this time, the change in sensitivity is indicated by the difference in logarithm of the exposure amount required to increase the fog density by 0.15.

From Table 5, when the film 101 in the transparent closed plastic container was exposed to light before being stored at 60 ° C. and 60% RH for 3 days (Sample 1001).
It can be seen that only abnormal fog occurs. On the other hand, in the silver halide photographic products 3, 5, 6, 7, and 10 which are the silver halide photographic products of the present invention, this fogging change is small and the effect of the present invention is remarkable. This effect is remarkable especially in the silver halide photographic product 10 to which a halogen scavenger is added.

Example 2 Films 101 and 102 were formed in the same manner as in Example 1
24 shots in 5 formats were taken and processed into a patrone form.
By changing the humidity control conditions of these samples as shown in Table 6, 4
After humidity control for a day, it was placed in a transparent closed plastic container as shown in FIG. 1 and a cap was attached to produce silver halide photographic products 11 to 20 shown in Table 6.

[0112]

[Table 6]

10,000 l for silver halide photographic products 11-20
After irradiating with ux for 24 hours, the same treatment as in Example 1 was performed, and the fog of the green-sensitive layer and the change in sensitivity were determined. The results are shown in Table 6. From Table 6, it can be seen that when the humidity in the closed plastic container is low, abnormal fogging hardly occurs, and therefore the effect of the present invention is remarkable at a relative humidity of 55% or more.

[0114]

The silver halide photographic product of the present invention has high image quality and excellent long-term storage stability in product form. Therefore, even if it is placed in a bright place like a store in a film store for a long time, deterioration of photographic performance, especially fogging,
The change in sensitivity is suppressed.

[Brief description of drawings]

FIG. 1 is a perspective view showing an embodiment of a silver halide photographic product.

FIG. 2 is a front view of a film with a cartridge used in the embodiment of FIG.

[Explanation of symbols]

 1 Film with Patrone 2 Transparent Plastic Container 3 Silver Halide Photosensitive Material 4 Patrone 5 Film Drawout 6 Film Drawout 2a Body of Sealed Plastic Container 2b Cap of Sealed Plastic Container

Claims (1)

[Claims] 1. A silver halide light-sensitive material comprising a support and at least one silver halide emulsion layer containing a gold chalcogen-sensitized silver halide emulsion and a thiocyanate, and the light-sensitive material. It comprises a light-shielding container incorporated therein and a light-transmissive hermetically-sealed container accommodating the light-shielding container. The photosensitive material is incorporated so that a part thereof is located outside the light-shielding container, and inside and outside the light-shielding container. Is a silver halide photographic product having a structure through which a gas can flow, and has a hydrogen cyanide gas scavenger at any position in the sealed container, and at least one silver halide emulsion layer of the light-sensitive material is A silver halide photographic product containing a sensitizing dye represented by formula (A). [Chemical 1] (In the formula, R ¹ and R ² represent an alkyl group. R ³ represents a hydrogen atom, an alkyl group or an aryl group. X ⁻ represents an anion, and n is adjusted to neutralize the charge of the whole molecule. (In the case of forming an intramolecular salt, n = 0.)