JPH06230528A - Silver halide photographic product - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic product having high picture quality, good storage stability for a long time in the product state, and excellent preserving property of latent images. CONSTITUTION:The photographic product consists of a silver halide photosensitive material 3, light shielding container 4 for this photosensitive material, and light transmitting sealing container 2 which houses the light shielding container 4. The photosensitive material has a silver halide emulsion layer formed on a supporting body. This layer contains thiocyanate and silver halide emulsion sensitized with gold chalcogenide. The photosensitive material is housed in the light shielding container in such a manner that a part of the photosensitive material is out of the container. Gas can flow between the inside and outside of the light shielding container. The sealing container has a gas scavanger for hydrogen cyanide at any position of the container. At least one silver halide emulsion layer of the photosensitive material contains a specified phenol cyan coupler.

Description

Detailed Description of the Invention

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, more specifically, a silver halide photographic product in which the photographic performance is not changed even if the film is placed in a store for a long time. It is about. Further, the present invention relates to a silver halide photographic product which is excellent in latent image storability (storability of image information after photographing and before development processing).

[0002]

2. Description of the Related Art In recent years, silver halide photographic materials, particularly photographic light-sensitive materials, have high sensitivity and excellent graininess and sharpness. Sensitive materials with excellent properties are required. Then, as a cyan coupler which gives a cyan image with high sensitivity and high density, JP-A-60-237448, 61-153640 and 6
A specific naphthol-based coupler is proposed in, for example, 1-145557. Certainly, these couplers gave high-sensitivity and high-density cyan images, and the cyan image fluctuation when using a bleaching bath that was tired after running or a bleach-fixing bath was eliminated. However, it is expected that the storability of the light-sensitive material for maintaining such high performance is further improved.

As for the storability of the light-sensitive material, it is necessary to satisfy both the change in photographic property before use and the change in photographic property during aging storage after photographing and development processing. By the way, a photosensitive silver halide photographic material needs to be shielded from light before use. For example, in the case of a color film, the film is contained in a cartridge and shielded from light, the cartridge is housed in a closed case, and is packaged in a paper box, for example. 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 later. There is. However, it has recently been discovered that the performance of the film varies depending on the brightness of the place where the product is displayed for a long time on the shelves of retail stores.

As a result of further studying this point, it has been found that, especially in a color film which has been lined up in a store for a long period of time, the fog becomes large and the sensitivity is lowered among the photographic performances. When the inventors analyzed this phenomenon,
When light hits the drawer of the film through the paper box that houses the film case, a certain type of gas is generated, and this gas diffuses inside the Patrone that is blocked by the light and changes the performance of the film. I realized that 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. As a result of further studies, the present inventors applied a hydrogen cyanide gas scavenger (scavenger) to any position of the closed container of the film, for example, the coating layer of the light-sensitive material to reduce the increase of fog and reduce the sensitivity. It has been found that the decline is prevented. However, the above-mentioned JP-A-60-237448, JP-A-61-153640, and JP-A-6-153640.
When the naphthol-based cyan coupler described in 1-145557 is used, the increase in fog is certainly reduced by coating the hydrogen cyanide gas scavenger, and the reduction in sensitivity is prevented. It was found that when the image was taken after being stored for a certain period of time, the change in the photographic property during the time-lapse storage from the shooting to the development process was large, that is, the latent image storability was deteriorated.

[0005]

SUMMARY OF THE INVENTION According to the present invention, the image quality is high, the long-term storage stability in the product form is good, and the change in photographic property during the time-lapse storage after photographing is small (the latent image storability is low). Higher) silver halide photographic products.

[0006]

The present inventors have applied a hydrogen cyanide gas scavenger (scavenger) to any position of a closed container of a film, for example, a coating layer of a light-sensitive material, and further added a specific cyan coupler. By using it as a light-sensitive material, deterioration of photographic performance due to generation of hydrogen cyanide gas due to light irradiation at stores can be prevented,
Further, they have found that the storability (latent image storability) with time from development to processing after photographing is improved, and the present invention has been completed based on this finding.

That is, the present invention provides (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 thiocyanate. A light-shielding container containing the light-sensitive material and a light-transmissive sealed container containing the light-shielding container. The light-sensitive material is contained so that a part thereof is located outside the light-shielding container, and In a silver halide photographic product having a structure in which a gas can flow between the inside and the outside of a light-shielding container, a hydrogen cyanide gas scavenger is provided at any position in the sealed container, and the light-sensitive material contains at least one layer of halogen. A silver halide photographic product characterized by containing a cyan coupler represented by the following general formula (I) in the silver halide emulsion layer;

[0008]

[Chemical 2]

(In the formula, R ²¹ represents an alkyl group, an aryl group or a heterocyclic group, R ²² represents an aryl group, and Z represents a hydrogen atom or a coupling-off group.) (2) Gold chalcogen on a support A silver halide photographic product in which a photographic light-sensitive material sensitized and containing a silver halide emulsion containing a thiocyanate compound is stored in a sealed container, wherein a part of the light-sensitive material can be exposed to light after sealing. In a silver halide photographic product in which the remaining part is arranged in a position where the remaining part is shielded from light, and the irradiated part and the shielded part have a structure in which air flows, in a sealed container of the silver halide photographic product. (1) A silver halide photographic product according to item (1), which has a halogen gas scavenger at any position, and (3) hydrogen cyanide gas or a halogen gas scavenger in the photographic light-sensitive material. The silver halide photographic product according to item (1) or (2), and (4) the hydrogen cyanide gas scavenger is Pd.
Alternatively, the silver halide photographic product according to item (1), which is an organic or inorganic compound of Pt, (5) the relative humidity in a sealed container is 55% or more at 25 ° C., according to item (1) or (2). Silver halide photographic product, (6) The silver halide photographic product according to item (3), wherein the photographic light-sensitive material is a color photographic material, (7) Hydrogen cyanide gas scavenger in the photographic product is included in the part which can be irradiated with light. 1/10 mol or more per 1 mol of thiocyanate (1), (3),
The silver halide photographic product according to item (4) or (5), and the hydrogen cyanide gas scavenger in the product (8) are 1 / mole of thiocyanate contained in a portion which can be irradiated with light. 2 mol or more (1),
This is achieved by the silver halide photographic product according to any one of (3), (4) and (5).

By the way, in JP-A-3-505263, a compound of palladium, gold and platinum (hydrogen cyanide scavenger) is provided at a position 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 prevention by including. 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. Carbon black is about 8% of the weight of paper (about 0.7
The black light-shielding paper containing g) is used, and this film also differs 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; indicates 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 needed 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.

Preferable 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 (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 in the same manner, 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 kneaded, or may be applied or kneaded and molded to parts forming a light-shielding container (eg, 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, and the hydrogen cyanide gas scavenger of the present invention is directly added to the coating solution for these layers or coated alone. 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 an aqueous solution having an appropriate concentration, and a water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, such as alcohols, glycols, ketones, esters, 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, 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, 34, 159 (19
71) Keiichi Tanaka, Journal of the Photographic Society of Japan, vol. 37, page 133 (1)
1974) Keiichi Tanaka, Journal of the Photographic Society of Japan, vol. 39, page 73 (1976) Keiichi Tanaka, Journal of Photographic Science 21: 134 (1973) Keiichi Tanaka and Journal of Photographic Science Vol. 26: 222 (1978) Tanaka 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 and 100 mol or less 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 sensitized with gold and chalcogen and containing thiocyanate on a support. The support is, for example, RD. N
28 p. 17643, 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 carried out by a conventionally known method. That is, it is usually carried out by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Selenium sensitization using the unstable selenium sensitizer described in JP-B-44-15748 is preferably used. Specific unstable selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, 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-butylselenophosphate

Preferred types of labile selenium compounds have been described above, but are not limiting. Speaking to a person skilled in the art of an unstable selenium compound as a sensitizer for a photographic emulsion, the structure of the compound is not so important as long as selenium is unstable, and the organic portion of the selenium sensitizer molecule is It is generally understood that it does not play any role other than loading selenium and making it unstable in the emulsion. 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-labile 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 when dissolved 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 type 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. It is 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.

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, etc., (b) thiourea derivatives, and (c) a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, described in JP-A No. 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 × 10 ⁻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 time. The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time.

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
Nos. 01,313, 3,656,955, German Patent 1,422,869, and Japanese Patent Publication No. 56-2.
The 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 it 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. Typical 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 captures 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 that can be used in the present invention is a compound that converts a halogen gas generated when a light-sensitive material is irradiated with light into a photographically inactive substance. The scavenger should not release substances that have a harmful effect on the silver halide light-sensitive material as a result of capturing halogen gas. Generally, it is known that gelatin acts as a halogen gas scavenger, and the 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, the following compounds are preferably present as halogen gas scavengers 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.

When these halogen gas scavengers are contained in the silver halide light-sensitive material, the position thereof is a protective layer, an intermediate layer, a non-light-sensitive layer such as a back layer opposite to the emulsion surface of the film, or Any of the silver halide emulsion layers may be used. 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.
05-1 g / m ² , more preferably 0.1-0.5 g /
m ² . In the silver halide photographic product of the present invention, the photographic light-sensitive material is stored in a hermetically sealed container, a part of the light-sensitive material is arranged at a position where light can be irradiated after sealing, and the rest is arranged at a position shielded from light. Air is circulated between the shaded portion and the shaded portion. 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. Figure 1 is a film 1 with a cartridge
The figure shows a state in which is stored in the transparent plastic container 2. Figure 2
Indicates a film 1 containing a cartridge. As shown in the figure, the silver halide photographic light-sensitive material 3 is housed in a metal cartridge 4 using a plastic spool as a mandrel, and is partially pulled out from a 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 portion 6 corresponds to a position where light can be irradiated, and the air is in a state of flowing with the light-shielded portion through the gap between the film drawing portion 5 or the cartridge.

The cartridge 4 containing this silver halide photographic light-sensitive material is sealed by a transparent plastic container 2 comprising a container body 2a and a container cap 2b. The sealed transparent plastic container 2 is designed to block harmful gases to the light-sensitive material and suppress excessive permeation of water vapor.
Also, it is greatly affected by the structure and material of the cap 2b of the container. Preferably, the humidity in this sealed container is preferably kept constant, and in the present invention, the relative humidity is 25 ° C.
At 55% or more, the effect of the invention is remarkable. To keep the humidity of the sealed container constant means that the humidity change inside the container is 10% or less after 12 months at 25 ° C. when the humidity difference between the outside air and the inside of the container 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 is, for example, VAISALA Co., Ltd.).
It can be measured by a capacitance-type humidity measuring device 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 the film is kept under irradiation with light of 10000 lux for 24 hours, the increase in fog in 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 light-shielding container of the present invention includes a cassette for sheet film, but is typically a cartridge for roll film. A cartridge for a roll film has a spool shaft around which a silver halide photosensitive material is wound in a roll shape, a film outlet for taking in and out the photosensitive material, and a cartridge main body for accommodating the spool rotatably around an 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-shielding 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. 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) of two or more polyfunctional compounds, polyaddition and phenol. It can be produced by a method such as addition condensation of a 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, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl. Typical examples include carbazole, N-vinylpyrrolidone, vinylidene cyanide, ethylene and propylene. In addition, as the small ring compound, for example, ethylene oxide, propylene oxide, glycidol, 3,3-bischloromethyloxetane, 1,4-dioxane, tetrahydrofuran, trioxane, ε-caprolactam, β-propiolactone,
Representative examples include ethyleneimine and tetramethylsiloxane.

Examples of polyfunctional compounds include carboxylic acids such as terephthalic acid, adipic acid and glutaric acid,
Typical examples include 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 a plastic material is produced using these raw materials, a catalyst or a solvent may be used.
As the catalyst, (1-phenylethyl) azodiphenylmethane, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis (2-methylpropane), benzoyl peroxide, cyclohexanone peroxide, potassium persulfate Radical polymerization catalysts such as 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 Ziegler-Natta (Ziegler-Natt)
a) A system catalyst, sodium hydroxide, potassium hydroxide, potassium metal, etc. are used.

The solvent is not particularly limited as long as it does not inhibit the polymerization, but examples thereof include hexane, decalin, benzene, toluene, cyclohexane, chloroform, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran and the like. In molding the plastics of the present invention, a plasticizer is mixed with the plastics as 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 set forth below, but the present 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 made of plastic with carbon black and pigments mixed in. Next, the general formula (I) will be described.

[0037]

[Chemical 3]

(In the general formula (I), R ²¹ represents an alkyl group, an aryl group or a heterocyclic group, R ²² represents an aryl group, and Z represents a hydrogen atom or a coupling-off group.)

The phenolic cyan coupler represented by formula (I) will be described in detail below. In the general formula (I), R ²¹ is the total number of carbon atoms (hereinafter referred to as C number)
1 to 36 (preferably 4 to 30) optionally substituted, linear, branched or cyclic alkyl group, C
Number 6 to 36 (preferably 12 to 30) optionally substituted aryl group or C number 2 to 36 (preferably 12)
To 30) heterocyclic groups. Here, the heterocyclic group represents a 5 to 7-membered optionally condensed heterocyclic group having at least one hetero atom selected from N, O, S, P, Se and Te in the ring. As 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 4-pyrimidyl, 2
-Imidazolyl, 4-quinolyl and the like. Examples of the substituent of R ²¹ are halogen atom, cyano group, nitro group, carboxyl group, sulfo group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group. , Arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, imide group, amino group, ureido group, alkoxycarbonylamino group or sulfamoylamino group (Above referred to as Substituent Group E) and the like, and examples of preferable substituents include an aryl group, a heterocyclic group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group or an imide group.

In the general formula (I), R ²² has a C number of 6 to 36.
It represents an aryl group (preferably 6 to 15) and may be substituted with a substituent or may be a condensed ring. here,
Preferred substituents are halogen atoms (F, Cl, B
r, I), cyano group, nitro group, acyl group (eg acetyl, benzoyl), alkyl group (eg methyl, t-)
Butyl, trifluoromethyl, trichloromethyl), alkoxy group (eg methoxy, ethoxy, butoxy, trifluoromethoxy), alkylsulfonyl group (eg methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl), arylsulfonyl group (eg phenylsulfonyl) , P-tolylsulfonyl,
p-chlorophenylsulfonyl), an alkoxycarbonyl group (eg methoxycarbonyl, butoxycarbonyl), a sulfonamide group (eg methanesulfonamide, trifluoromethanesulfonamide, toluenesulfonamide), a carbamoyl group (eg N, N-dimethylcarbamoyl, N-). Phenylcarbamoyl) or a sulfamoyl group (eg, N, N-diethylsulfamoyl, N-phenylsulfamoyl). R ²²
Is preferably a phenyl group having at least one substituent selected from a halogen atom, a cyano group, a sulfonamide group, an alkylsulfonyl group, an arylsulfonyl group and a trifluoromethyl group, and more preferably 4
-Cyanophenyl, 4-cyano-3-halogenophenyl, 4-alkylsulfonylphenyl, 4-alkylsulfonyl-3-halogenophenyl, 4-alkylsulfonyl-3-alkoxyphenyl, 3-alkoxy-4-
Alkylsulfonylphenyl, 3,4-dihalogenophenyl, 4-halogenophenyl, 3,4,5-trihalogenophenyl, 3,4-dicyanophenyl, 3-cyano-
4,5-dihalogenophenyl, 4-trifluoromethylphenyl or 3-sulfonamidophenyl, particularly preferably 4-cyanophenyl, 3-cyano-4-halogenophenyl, 4-cyano-3-halogenophenyl,
It is 3,4-dicyanophenyl or 4-alkylsulfonylphenyl.

In the general formula (I), Z represents a hydrogen atom or a coupling-off group which can be eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Examples of coupling-off groups include halogen atoms, sulfo groups,
An alkoxy group having a C number of 1 to 36 (preferably 1 to 24),
An aryloxy group having a C number of 6 to 36 (preferably 6 to 24), an acyloxy group having a C number of 2 to 36 (preferably 2 to 24), an alkylsulfonyl group having a C number of 1 to 36 (preferably 1 to 24), Arylsulfonyl group having a C number of 6 to 36 (preferably 6 to 24), C number of 1 to 36 (preferably 2 to)
24) alkylthio group, C number of 6 to 36 (preferably 6)
To 24) arylthio group, C number of 4 to 36 (preferably 4 to 24) imide group, C number of 1 to 36 (preferably 1 to 36)
24) a carbamoyloxy group or a heterocyclic group bonded to the coupling active position with a nitrogen atom having a C number of 1 to 36 (preferably 2 to 24) (eg pyrazolyl, imidazolyl,
1,2,4-triazol-1-yl, tetrazolyl)
There is. Here, the alkoxy group and the following groups may be substituted with a substituent. Z is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group or a heterocyclic thio group, and particularly preferably a hydrogen atom, a chlorine atom, an alkoxy group or an aryloxy group.

Specific examples of R ²¹ , R ²² and Z in the general formula (I) are shown below. Example of R ²¹

[0043]

[Chemical 4]

[0044]

[Chemical 5]

Example of R ²²

[0046]

[Chemical 6]

[0047]

[Chemical 7]

Example of Z

[0049]

[Chemical 8]

[0050]

[Chemical 9]

[0051]

[Chemical 10]

Specific examples of the cyan coupler represented by the general formula (I) are shown below. However, A to Z and a to f are
It is a serial number of a specific example of R ²¹ in Chemical formula 3.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

[Table 4]

[0057]

[Table 5]

[0058]

[Table 6]

The cyan coupler represented by the general formula (I) is described in, for example, JP-A-56-65134 and JP-A-61-2757.
No. 63-159848, No. 63-161450.
No. 63-161451, JP-A No. 1-254956.
No. 4923791 and US Pat. No. 4,923,791. The addition amount of the cyan coupler in the present invention is usually 0.002 to 0.3 mol, preferably 0.01 per mol of the photosensitive silver halide.
To 0.2 mol, more preferably 0.03 to 0.1 mol. The total amount of the cyan couplers represented by the general formula (I) added is 30 mol% or more, preferably 70 mol% or more, and more preferably 90 mol% or more of the total cyan couplers.
It is at least mol%. The cyan coupler represented by the general formula (I) is preferably used in combination of two or more kinds. When the same color-sensitive layer is divided into two or more layers having different sensitivities, 2 equivalent cyan in the highest sensitivity layer is used. It is preferable to use a coupler and a 4-equivalent cyan coupler in the lowest sensitivity layer. It is preferable to use either or both of the same color-sensitive layers other than those.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a silver halide emulsion layer, provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer.
As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light,
In a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. 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. For the intermediate layer, JP-A-61-43748 and JP-A-5-43748 are used.
9-113438, 59-134440, 61
Nos. 20037 and 61-20038 may contain a coupler, a DIR compound and the like, and may also contain a color mixing inhibitor as commonly used. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent 1,121,470 or British Patent 923,045. A layer structure 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. Further, as described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543, a low-sensitivity emulsion layer and a support are provided on the side remote from the support. A high-sensitivity emulsion layer may be provided on the near side.
As a specific example, from the side farthest from the support, a low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH Can be installed in order.

Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually 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. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. 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 or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat. Nos. 4,663,271, 4,705,744, 4,707,436, and JP-A-62-160448.
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 preferable silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides. Particularly preferred is about 2 mol%
To silver iodobromide or silver iodochlorobromide containing up to about 10 mol% of 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 about 0.2 μm or less, but the projected area diameter is about 10 μm.
It may be a large size grain up to the above, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (R
D) No. 17643 (December 1978), 22-23
Page, "I. Emulsion preparation and type
s) ", and No. 18716 (November 1979),
Pp. 648, No. 307105 (November 1989),
Pp. 863-865 and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafkides, Chemie et P
hisique Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry (Focal P
ress, 1966)), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal P
ress, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
Monodisperse emulsions described in 655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff,
Photographic Science and Engineering), Volume 14,
248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,43
It can be easily prepared by the method described in 3,048, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform or may have different halogen compositions inside and outside,
It may have a layered structure, or silver halides having different compositions may be joined by epitaxial junction, or may be joined with a compound other than silver halide such as silver rhodanide or 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 is formed 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 types, JP-A-63-264
The core / shell internal latent image type emulsion described in No. 740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542.
The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The additives used in such a process include Research Disclosure No. 17643, No. 18716 and N.
No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion are mixed in the same layer. Can be used. Fog-coated silver halide grains described in US Pat. No. 4,082,553, US Pat.
No. 626,498 and JP-A No. 59-214852, the inside of which is covered with a silver halide grain, colloidal silver is a photosensitive silver halide emulsion layer and / or a substantially non-photosensitive hydrophilic colloid layer. Can be preferably used. 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 in which the inside or surface of the grain is fogged is described in US Pat.
-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. Examples of the silver halide having the inside or surface of the grain fogged include silver chloride,
Any of silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.75 μm, particularly 0.05 to 0.6 μm.
m is preferred. 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 the number of silver halide grains are ± 40 of the average grain size). %) Is preferable).

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. . 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 size (average value of circle-equivalent diameter of projected area) 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 by a method similar to that for 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, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. The coating amount of silver of the light-sensitive material of the present invention is 6.
It is preferably 0 g / m ² or less, and most preferably 4.5 g / m ² or less.

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 23-24 page 648 right column page 866-868 supercolor enhancement Sensitizer page 649 right column 4 Whitening agent page 24 647 right column page 868 page 5 Antifoggant, pages 24 to 25 page 649 right column 868 to 870 stabilizer 6 light absorber, page 25 to 26 page 649 right column ~ Page 873 Filter dye page 650 left column UV absorber 7 anti-stain agent page 25 right column page 650 left column ~ page 872 right column 8 Dye image stabilizer page 25 650 page left column 872 page 9 hardener 26 page 651 page Left column 874 to 875 page 10 Binder page 26 same as above 873 to 874 page 11 Plasticizer and lubricant page 27 page 650 page right column page 876 12 Coating aid, page 26 to 27 page 650 right column page 875 to 876 Surfactant 13 Static prevention Page 27 Page 650 Right column 876-877 Page 14 Stop agent 14 Matting agent 878-879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add to the photographic material a compound capable of being immobilized by reacting with formaldehyde described in No. 87 and No. 4,435,503. The light-sensitive material of the present invention can be incorporated into U.S. Pat. Nos. 4,740,454 and 4,788,132.
JP-A-62-18539, JP-A-1-28355
It is preferable that the mercapto compound described in No. 1 is contained. A compound described in JP-A No. 1-106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, to the light-sensitive material of the present invention, irrespective of the amount of developed silver produced by the development processing. Is preferably contained. In the light-sensitive material of the present invention, international publication WO88 / 04
No. 794, Dyes dispersed by the method described in JP-A-1-502912 or EP317,308A, US Pat. No. 4,420,555, JP-A-1-259358.
It is preferable to include the dyes described in No. Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 176 above.
43, VII-C to G, and No. 307105, VII-
It is described in the patents described in C to G. Examples of yellow couplers include US Pat. No. 3,933,501.
No. 4,022,620, 4,326,02
No. 4, No. 4,401,752, No. 4,248,9
No. 61, Japanese Patent Publication No. 58-10739, British Patent Nos. 1 and 4
25,020, 1,476,760, U.S. Pat. Nos. 3,973,968, 4,314,023,
No. 4,511,649, European Patent No. 249,473.
Those described in No. A, 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
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
, JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-.
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. As the cyan coupler, a compound represented by the general formula (I) of the present invention is used.
And U.S. Pat. No. 4, including those represented by (II).
No. 052,212, No. 4,146,396, No. 4,228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171,
No. 2,772,162, No. 2,895,826
No. 3, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334, 011, No. 4,327, 1
73, West German Patent Publication No. 3,329,729, European Patents 121,365A, 249,453A, U.S. Patents 3,446,622, 4,433,99.
9, No. 4,775,616, No. 4,451,5
No. 59, No. 4,427, 767, No. 4,690,
889, 4,254,212 and 4,29
Those described in JP-A No. 6,199 and JP-A No. 61-42658 are preferable. Furthermore, JP-A-64-553 and JP-A-64-553
-554, 64-555 and 64-556, and pyrazoloazole couplers described in U.S. Pat.
The imidazole couplers described in No. 18,672 can also be used. Typical examples of polymerized dye-forming couplers are disclosed in US Pat.
080,211, 4,367,282, 4,409,320, 4,576,910, British Patent 2,102,137, European Patent 341,18.
8A and the like.

As couplers in which the color forming dye has an appropriate diffusibility, US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, West German Patent (Publication) No. 3 , 234,533 are preferred. 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 releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers releasing a development inhibitor are disclosed in the above-mentioned RD17643, VII-F and No. 307105, VII-F patents, JP-A-57-151944 and 57-15423.
No. 4, No. 60-184248, No. 63-37346.
No. 63-37350, U.S. Pat. No. 4,248,9.
Those described in No. 62 and No. 4,782, 012 are preferable. R. D. No. 11449, No. 24241, and the bleaching accelerator releasing coupler described in JP-A No. 61-201247 are effective for shortening the processing time having a bleaching ability. The effect is great when it is added to a light-sensitive material using silver particles.
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.
Further, 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. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. , A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Examples thereof include releasing couplers.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent 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 can be mentioned. 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, dimethylformamide and the like. The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,5.
41, 230 and the like.

In the light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272 are used.
No. 248, and 1, 2 described in JP-A No. 1-80941.
-Benzisothiazolin-3-one, n-butyl p-
Hydroxybenzoate, phenol, 4-chloro-
It is preferable to add various antiseptics or antifungal agents such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.
The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports that can be used in the present invention are, for example, those described in 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. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, and 23 μm.
The following is more preferable, and 18 μm or less is further preferable,
16 μm or less is particularly preferable. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and 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. Eng.), 19 vol., No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. in a color developing solution, 3 Minute 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 until the saturated film thickness reaches 1/2. The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The photosensitive material 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. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is preferably 150 to 500%.

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 to 881 of The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-
4-amino-N, N-diethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Methanesulfonamidoethylaniline, 3-methyl-
4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates, etc. may be mentioned. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more of these compounds can be used in combination depending on the purpose.

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

When reversal processing is carried out, black and white development is usually carried out before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone. , Or in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented 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, More preferably, it is 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 surface of the photographic processing liquid in the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit developing treatment method described in No. 63-216050 can be mentioned. Reducing the aperture ratio is preferably applied not only in both the color development and black-and-white development steps but also in the subsequent steps, for example, all steps such as bleaching, bleach-fixing, fixing, washing and stabilizing. Further, the amount of replenishment can be reduced by using 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 can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III), such as aminoamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Among these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetate iron (III) complex salt are used from the viewpoint of rapid treatment and prevention of environmental pollution. preferable. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution.
The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8.0, but it may be processed at a lower pH in order to speed up the processing. it can.

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 No. 50-140129; -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 and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and in particular, US Pat.
Compounds described in US Pat. Furthermore, US Pat.
The compounds described in No. 552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (pka) of 2 to 5, specifically, acetic acid,
Propionic acid, 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 EP 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 of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved,
In addition, the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, Japanese Patent Laid-Open No.
2-183460, a method of causing a jet of a processing solution to collide with the emulsion surface of a light-sensitive material, and JP-A-62-183461.
The stirring effect is improved by using the rotating means of No. No., and the stirring effect is further improved by moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent. And a method of increasing the circulation flow rate of the entire processing liquid. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the agitation 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 for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in Nos. 1258 and 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, 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 of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of washing water in the washing process is
It can be set in a wide range depending on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), the purpose of use, the washing water temperature, the number of washing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other 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 Soc.
society of Motion Picture and Television Engineers Volume 64, p. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the document, the amount of washing water can be significantly reduced,
The increase in the residence time of water in the tank causes problems such as bacteria breeding and the produced floating substances adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, JP-A-62-28
The method of reducing calcium ion and magnesium ion described in No. 8838 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 Shuppan, Hygiene Society, edited by "Microbial sterilization, sterilization, and fungicide technology" (1982), Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) A bactericide can also be used. The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time may be variously set depending on the characteristics and intended use of the light-sensitive material, but generally 15 to 45 ° C. and 20 seconds to
A range of 10 minutes, preferably 30-40 seconds at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543
All known methods described in Nos. 58-14834 and 60-220345 can be used. Also,
The washing treatment may be followed by a further stabilizing treatment, and examples thereof include 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. it can. Aldehydes such as formalin and glutaraldehyde, N
-Methylol compounds, hexamethylenetetramine, aldehyde sulfite adducts, etc. may be mentioned.
Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution resulting from the above washing with water and / or replenishment 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 compounds described in No. 15159, 139
Aldol compounds described in No. 24, US Pat. No. 3,71
Metal salt complexes described in JP-A No. 9,492, JP-A-53-1356.
The urethane compound described in No. 28 can be mentioned.
The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438. Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard,
It is possible to accelerate the treatment to shorten the treatment time by raising the temperature to a higher temperature, and conversely to lower the temperature to improve the image quality and the stability of the treatment liquid. The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
-133449, 59-218443, 61-
It is also applicable to the photothermographic materials described in 238056 and European Patent 210,660A2.

[0081]

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 sample film 11 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 C Silver 0.25 ExS-1 4.5 × 10 ⁻⁴ ExS-2 1.5 × 10 ⁻⁵ ExS-3 4 .5 × 10 ⁻⁴ ExC-1 0.17 ExC-3 0.01 ExC-4 0.10 ExC-5 0.0050 ExC-7 0.0050 ExC-8 0.020 Cpd-2 0.025 HBS- 1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-1 3.0 × 10 ⁻⁴ ExS-2 1.2 × 10 ⁻⁵ ExS-3 4.0 × 10 ⁻⁴ ExC-1 0.15 ExC-2 0.01 ExC-4 0.11 ExC-7 0.0010 ExC-8 0.025 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 2.0 × 10 ⁻⁴ ExS-2 1.0 × 10 ⁻⁵ ExS-3 3.0 × 10 ⁻⁴ ExC-1 0.15 ExC-3 0.02 ExC-6 0.020 ExC-8 0.007 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20 6th layer ( Intermediate layer) Cpd-1 0.10 HBS-1 0.50 gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion A Silver 0.17 Emulsion B Silver 0.17 ExS-4 4.0 × 10 ⁻⁵ ExS-5 1.8 × 10 ⁻⁴ ExS-6 6 .5 × 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 ( Mid-Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.16 ExM -3 0.045 ExY-1 0.01 ExY-5 0.030 HBS-1 0.16 HBS-3 8.0x10 ^-3 gelatin 0.90

Ninth 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 0.015 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.020 HBS-1 0.25 HBS-2 0.10 Gelatin 1.20 10th layer ( Yellow filter layer) Yellow colloidal silver 0.010 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.25 Emulsion D Silver 0.40 ExS-7 8.0 × 10 ⁻⁴ ExY-1 0.030 ExY-2 0.55 ExY− 3 0.25 ExY-4 0.020 ExC-7 0.01 HBS-1 0.35 Gelatin 1.30 12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.38 ExS-7 3.0x 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

Thirteenth 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 14th Layer (Second Layer) Protective layer) 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,
F-1 to F-17 and iron salt, lead salt, gold salt, platinum salt, iridium salt, palladium salt and rhodium salt are contained.

[0091]

[Table 7]

In Table 7, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. (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 by using a high voltage electron microscope.

[0093]

[Chemical 11]

[0094]

[Chemical 12]

[0095]

[Chemical 13]

[0096]

[Chemical 14]

[0097]

[Chemical 15]

[0098]

[Chemical 16]

[0099]

[Chemical 17]

[0100]

[Chemical 18]

[0101]

[Chemical 19]

[0102]

[Chemical 20]

[0103]

[Chemical 21]

[0104]

[Chemical formula 22]

[0105]

[Chemical formula 23]

[0106]

[Chemical formula 24]

[0107]

[Chemical 25]

(Samples 101 to 109) Sample film 11
In the sixth layer of the above, sodium palladium (II) chloride was added to 2 × 10 ⁻⁴ mol / mol Ag (based on thiocyanate, about equimolar palladium (II) chloride was added) with respect to the total silver amount. A sample film 12 was prepared in the same manner except that it was added as described above. Next, the cyan coupler ExC- added to the third and fourth layers of the sample film 12
Sample films 13 to 18 were prepared by replacing ExC-4 with the cyan coupler of the present invention as shown in Table 8. In addition,
An attempt was made to triple the amount of sodium palladium (II) chloride added to the sixth layer, but the sample film could not be prepared because the viscosity of the coating solution increased. Each of these sample films 11 to 18 was processed into a Patrone form by taking 24 35 sheets of 135 format. At this time, the ratio of the area of the film stored inside the patrone to the area of the film left outside the patrone was set to 1: 0.05, and then 25 ° C 6
Samples 102 to 109 were prepared by controlling the humidity to 0% for 3 days and storing in a transparent sealed container in the dark. In addition, a sample 101 was prepared in which the sample film 11 was housed in a completely light-tight sealed container. 10000lu for these samples 101-109
x After irradiating light for 24 hours, 25 ℃ and 60 ℃ humidity 60%
Under the conditions of 3 days, the film portion stored in the cartridge was subjected to imagewise exposure for sensitometry, and the color development treatment shown below was performed. Although it was stored for a day, the increase in fog density and the change in relative sensitivity were measured and used as a measure of storage stability. The results are shown in Table 8.

Next, samples 101 to 109 were subjected to 10000 lux.
After irradiating with light for 24 hours, the sample was stored under the condition of 60 ° C. and 60% for 3 days, and image-wise exposed for sensitometry using the film portion stored in the cartridge.
The difference in relative sensitivity between the samples subjected to the color development treatment described below after being stored under the condition of 30 ° C. for 3 days and the samples 101 to 109 produced and subjected to the exposure development process without giving the above-mentioned aging was measured. This value is used as a measure of the latent image storability of a sample stored in a product form to some extent, and the smaller the value, the better the storability. The results are also shown in Table 8.

[0110]

[Table 8]

From these results, it can be seen that the use of the constitution of the present invention improves the storage stability of the product form and the storage stability over time from the photographing to the development processing.

(Processing method) Process processing time processing temperature color development 3 minutes 15 seconds 38 ° C bleaching 6 minutes 30 seconds 38 ° C water washing 2 minutes 10 seconds 24 ° C fixing 4 minutes 20 seconds 38 ° C water washing (1) 1 minute 05 seconds 24 ℃ Washing with water (2) 1 minute 00 seconds 24 ℃ Stability 1 minute 05 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 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6 Add 0.5 ml water 1.0 liter pH 6.0 (fixing solution) (unit: g) Disodium salt of ethylenediaminetetraacetic acid 0.5 Sodium sulfite 7.0 Ammonium thiosulfate aqueous solution (70%) 170.0 ml Add water 1.0 liter pH 6.7

(Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added. 1.0 liter pH 8.5-8.0

Example 2 Cpd-3 was added to each of the eleventh, twelfth, and thirteenth layers in an amount of 0.01.
A sample film 27 was produced in exactly the same manner as the sample film 17 of Example 1 except that g / m ² , 0.015 g / m ² , and 0.01 g / m ^{2 were} added. The same experiment as in Example 1 was conducted using these sample films. The results are shown in Table 9.

[0117]

[Table 9]

From the above, it is understood that the hydroquinone derivative as a halogen gas scavenger further contributes to the reduction of fog.

Reference Example 1 The humidity control conditions of the sample film 11 of Example 1 were changed as shown in Table 10 and the same test as in Example 1 was conducted. The results are shown in Table 10.

[0120]

[Table 10]

From the above, when the humidity in the sealed container is low, abnormal fogging hardly occurs. Therefore, the effect of the present invention is that the humidity is 55%.
It can be seen that it is remarkable when it is above%.

Reference Example 2 The same test as in Example 1 was carried out by changing only the development processing of the experiment of Reference Example 1 to the black and white development processing described later. The results are shown in Table 11.

[0123]

[Table 11]

From the above, it is understood that no remarkable abnormal fog occurs in the black and white development processing. (Black-and-white development treatment) After development with a developing solution having the following formulation at 20 ° C. for 7 minutes, stopping, fixing, washing with water and drying are carried out by a usual method. Developer Metol 2g Sodium sulfite 100g Hydroquinone 5g Borax.10H ₂ O 2g Water added 1 liter

[0125]

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. In addition, the stability with time from the photographing to the development processing is improved.

[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 Extraction Part 6 Film Extraction Part 2a Body of Sealed Plastic Container 2b Cap of Sealed Plastic Container

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 3/00 AN 7/34

Claims (8)

[Claims] 1. A silver halide photosensitive 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 photosensitive material. The light-shielding container comprises a light-shielding container and a light-transmissive hermetically-sealed container for housing 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 hermetically sealed container, and the light-sensitive material has at least one silver halide emulsion layer having the following structure. A silver halide photographic product characterized by containing a cyan coupler represented by formula (I). General formula (I) (In the formula, R ²¹ represents an alkyl group, an aryl group or a heterocyclic group, R ²² represents an aryl group, and Z represents a hydrogen atom or a coupling-off group.) 2. A silver halide photographic product, in which a photographic light-sensitive material sensitized with gold chalcogen on a support and containing a silver halide emulsion containing a thiocyanate compound is stored in a sealed container. A silver halide photographic product in which a part of the material is placed in a position where light can be radiated after sealing and the rest is placed in a position where light is shielded, and air is allowed to flow between the irradiated portion and the light shielded portion. The silver halide photographic product according to claim 1, which has a halogen gas scavenger at any position in the sealed container of the silver halide photographic product. 3. The silver halide photographic product according to claim 1, wherein a hydrogen cyanide gas or a halogen gas scavenger is present in the photographic light-sensitive material. 4. The hydrogen cyanide gas scavenger is P
An organic or inorganic compound of d or Pt.
The described silver halide photographic products. 5. Relative humidity in a sealed container is 55% at 25 ° C.
The above is the silver halide photographic product according to claim 1 or 2. 6. The silver halide photographic product according to claim 3, wherein the photographic light-sensitive material is a color photographic material. 7. A scavenger of hydrogen cyanide gas in a photographic product is 1/10 mol or more per 1 mol of thiocyanate contained in a portion which can be irradiated with light.
The silver halide photographic product according to any one of 3, 4, and 5. 8. The hydrogen cyanide gas scavenger in the photographic product is 1/2 mol or more per 1 mol of thiocyanate contained in the part which can be irradiated with light.
4. A silver halide photographic product as described in 4 or 5.