JPH06167779A - Silver halide photographic product - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic product high in image quality and good in long-period storage stability in the form of the product by incorporating a gaseous hydrogen cyanide scavenger in a tightly sealed film container and a specified sensitizing dye in one of the silver halide emulsion layers of a photosensitive material. CONSTITUTION:The silver halide photographic sensitive material has the silver halide emulsion layer comprising a silver halide emulsion sensitized by a gold- calcogen sensitizer and containing thiocyanate on a support. This photosensitive material is cased in a light-shielding case so as to locate a part of the photosensitive material in the outside of the case, and the gas can pass into the inside and out of the inside, and the gaseous hydrogen cyanide scavenger is incorporated in the inside of the case. The photosensitive material contains in one silver halide emulsion layer the sensitizing dye represented by formulae I and II in which each of R11-R14 and R21-R30 is H, alkyl, or the like; each of R15, R16, R31, and R32 is alkyl; R17 is alkyl or aryl; and each of X1 and X2 is a counter ion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic product containing a silver halide photographic light-sensitive material, and more specifically, to prevent the photographic performance thereof from changing even when it is lined up at a film store for a long time. It relates to silver halide photographic products.

[0002]

2. Description of the Related Art Photosensitive silver halide photographic materials are
Must be shielded from light before use. For example, in the case of color film, the film is built into the cartridge to block light,
This patrone is stored in a closed case and is packaged in, for example, a paper box for sale.

As a case for accommodating the cartridge, a transparent plastic container is lightweight and has good airtightness.
It is used because the inside of the patrone can be seen easily and it is easy to check the contents, and it is easy to use as a small container afterwards.

Recently, however, it has been discovered that the performance of the film varies depending on the brightness of the place where the product is displayed on the shelves at the store for a long time.

[0005]

As a result of further studying this point, it was found that, especially in a color film or the like lined up in a store for a long period of time, the fog was large and the sensitivity was lowered among the photographic performances.

When the present 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.

An object of the present invention is to provide a silver halide photographic product which overcomes the above problems and has a high image quality and good long-term storage stability in a product form.

[0008]

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

That is, the present invention relates to a silver halide light-sensitive material comprising a support having at least one silver halide emulsion layer which is sensitized with gold and chalcogen and contains a thiocyanate-containing silver halide emulsion. A light-shielding container containing the light-sensitive material, and a light-transmissive sealed container containing the light-shielding container, the light-sensitive material being 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 halogen of at least one layer of the light-sensitive material is used. A silver halide photographic product characterized in that the silver halide emulsion layer contains at least one sensitizing dye represented by the following general formula (I) or (II).

[0010]

[Chemical 4] In the formula, R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ may be the same or different, and are a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an aryloxycarbonyl group, It represents an alkoxycarbonyl group, an amino group, an acyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a carboxyl group or an acyloxy group. However, R ₁₁ and R ₁₂ or R ₁₃ and R ₁₄ do not represent a hydrogen atom at the same time. R ₁₅ and R ₁₆ may be the same or different and each represents an alkyl group.

R ₁₇ is a STERIMOL parameter L, B ₁ , R ₂ , R ₃ and R ₄ are L> 4.11, B
_{1> 1.52, B 2> 1.90} , B 3> 1.90, B 4
It represents an alkyl group or an aryl group such that> 2.97.

X ₁ represents a counter anion, m is 0 or 1, and when forming an intramolecular salt, m = 0.

[0013]

[Chemical 5] In the formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R
₂₈ , R ₂₉ and R ₃₀ have the same meaning as R ₁₁ . R ₃₁ and R
₃₂ has the same meaning as R ₁₅ . Y represents a sulfur atom or a selenium atom. X ₂ has the same meaning as X ₁ . n has the same meaning as m.

In the present invention, at least one of the emulsion layer and the other emulsion layer contains at least a sensitizing dye represented by the general formula (III), the general formula (IV) or the general formula (V). The silver halide photographic product according to (1) above, which contains one type of photographic product.

By the way, in JP-A-3-505263, palladium, gold, platinum compounds and hydrogen cyanide scavenger are placed at positions where the fog caused by hydrogen cyanide gas generated from carbon black coated for light shielding can be blocked from the photosensitive emulsion. It is described that the inclusion prevents it. However, this is not related to the above reaction, that is, generation of hydrogen cyanide gas by light irradiation. Nothing is disclosed that the gas generated from the light-irradiated portion affects the photographic properties of the light-shielded portion.

Further addition of the Pd compound contained in the light-sensitive material is disclosed in US Pat. Nos. 2,566,245 and 2.
As described in Japanese Patent No. 566,263, this is a Brownie film, and a black shading paper containing carbon black at about 8% (about 0.7 g per one) based on the weight of the paper is used as the shading paper. However, this film is also different from the reaction of hydrogen cyanide gas generated by light irradiation.

The hydrogen cyanide gas scavenger used in the present invention is a compound that converts hydrogen cyanide gas generated when a light-sensitive material is irradiated with light into a photographically inactive substance. The scavenger should not release any substance that adversely affects the silver halide light-sensitive material as a result of capturing hydrogen cyanide gas. Suitable hydrogen cyanide gas scavengers can be selected from noble metal inorganic or organic compounds. Particularly preferred are palladium (II or IV; 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
Compounds of IV) and osmium (II, III or IV) are also effective, but higher amounts are required to have comparable effects.

Specific examples of useful inorganic or organic noble metal compounds include, for example, Gmelin Handbook (Gmeli Handbook).
n Handbook), and commercially available products, synthetic products and in situ synthetic products can be used in such a degree that the photographic light-sensitive material is not adversely affected.

Preferable palladium compounds include, for example, palladium (II) chloride, palladium (II) bromide, palladium (II) hydroxide, palladium (II) sulfate, palladium (II) thiocyanate, and tetrachloropalladium (I).
I) acid salt (sodium salt, potassium salt, ammonium salt), hexachloropalladium (IV) acid salt, tetrabromopalladium (II) acid salt, hexabromopalladium (I)
V) acid salt, bis (salicylato) palladium (II), acid salt, bis (dithiooxalato-S, S ′) valadium (II) acid salt, trans-dichlorobis (thioether) palladium (II), tetraamminepalladium (I)
I) salt, dichlorodiamminepalladium (II), dibromodiamminepalladium (II), oxalatodiamminepalladium (II), dinitrodiamminepalladium (I
I), bis (ethylenediamine) palladium (II) salt,
Dichloroethylenediaminepalladium (II), bis (2,2'-bipyridine) palladium (II) salt, bis (1,10-phenanthroline) palladium (II) salt,
Tetranitropalladium (II) acid salt, bis (glycinato) palladium (II), tetrakis (thiocyanato) palladium (II) acid salt, dichlorobis (phosphine) palladium (II), di-μ-chloro-bis [chloro (phosphine) Palladium (II)], di-μ-chloro-bis [chloro (arsine) palladium (II)] and dinitrobis (arsine) palladium (II).

Preferred platinum compounds include, for example, chloroplatinate (II) acid salt, chloroplatinum (IV) acid salt, hexafluoroplatinum (IV) acid salt, tetrachloroplatinum (II) acid salt, and hexachloroplatinum (IV) acid salt. , Trichlorotrifluoroplatinum (I
V) acid salt, tetrabromoplatinum (II) acid salt, hexabromoplatinum (IV) acid salt, dibromodichloroplatinum (II) acid salt, hexahydroxoplatinum (IV) acid salt, bis (oxalato) platinum (II) acid salt, Dichlorobis (oxalato) platinum (IV)
Acid salt, bis (thiooxalato) platinum (II) acid salt, bis (acetylacetonato) platinum (II), bis (1,1,1)
1,5,5,5-hexafluoro-2,4-pentanedionato) platinum (II), bis (1,1,1-trifluoro-2,4-pentanedionato) platinum (II), tetrakis ( Thiocyanato) platinum (II) acid salt, hexakis (thiocyanato) platinum (IV) acid salt, bis {(Z) -1,2-dicyanoethylene-1,2-dithiolato} platinum (II) acid salt,
Dichlorobis (diethylsulfide) platinum (II), tetrachlorobis (diethylsulfide) platinum (IV), bis (glycinato) platinum (II), dichloroglycinatoplatinum (II) acid salt, dichlorobis (triethylphosphine) platinum (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) can be mentioned.

Gold (I or III), Rhodium (III), Iridium (III or IV) and Osmium (II, III or
The compound of (IV) can be similarly used, and as such an example, for example, potassium tetrachloroaurate (III), rhodium (III) chloride, potassium hexachloroiridate (IV), calum tetrachloroiridate ( III) and potassium hexachloroosmate (IV).

The inorganic or organic compound of the noble metal is not limited to the above 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 of adding the hydrogen cyanide gas scavenger, a method usually used when a method of adding an additive to a photographic light-sensitive material is adopted can be applied. For example, a water-soluble compound is prepared as an aqueous solution having a suitable concentration, and a water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, such as alcohols, glycols, ketones, esters, amides, etc. Then, it can be dissolved in a solvent that does not adversely affect the photographic characteristics and added as a solution.

The back layer, emulsion layer, surface protective layer, interlayer and antihalation layer are usually binder dispersions, but useful binders include naturally occurring polymeric vehicles such as gelatin and cellulose derivatives and synthetic. Vehicles such as polyvinyl alcohol and its derivatives, acrylate or methacrylate polymers, butadiene-styrene polymers and similar substances. 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 is preferably 1 mol based on 1 mol of thiocyanate contained in the portion which can be irradiated with light. / 10 mol or more. More preferably, the amount is 1/2 mol or more and 100 mol or less with respect to 1 mol of the thiocyanate contained in the portion that can be irradiated with light.

The photographic light-sensitive material in the present invention contains a silver halide emulsion which is sensitized with gold and chalcogen and contains thiocyanate on a support. The support is, for example, RD. N
o. 17643, page 28, RD. No. 18716 of 6
Page 47 right column to page 648 left column and RD. No. 3071
05, p. 879.

Gold / chalcogen sensitization is gold / sulfur sensitization.
Selenium sensitization, gold / tellurium sensitization, gold / sulfur / selenium sensitization,
It can be used by selecting from gold / sulfur / tellurium sensitization, gold / selenium / tellurium sensitization, and gold / sulfur / selenium / tellurium sensitization. A thiocyanate is used 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 a selenium sensitizer,
It is applied by at least one of a sulfur sensitizer and a tellurium sensitizer.

Here, the selenium sensitization is carried out by a conventionally known method. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is carried out by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Selenium sensitization using the unstable selenium sensitizer described in JP-B-44-15748 is preferably used. Specific examples of unstable selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenium amides, 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 isoselenocyanate, for example, aliphatic isoselenocyanate such as allyl isoselenocyanate b selenourea (enol type Including) For example, methotre, ethyl, propyl, isopropyl, butyl, hexyl, octyl, dioctyl, tetramethyl, N- (β-carboxylethyl) -N′-N′-dimethyl, N—N-dimethyl, diethyl, dimethyl, etc. Aromatic selenoureas having one or more aromatic groups such as phenyl and tolyl; heterocyclic selenoureas having heterocyclic groups such as pyridyl and benzothiazolyl c selenoketones, for example, selenacetone, selenose Acetophenone, selenoketo having an alkyl group bonded to> C = Se , Selenobenzophenone d selenoamides, for example, selenoacetamide e selenocarboxylic acid and esters, for example, 2-selenopropionic acid, 3-selenobutyric acid, methyl 3-selenobutyrate III. Other a selenides, for example, diethyl selenide, diethyldiene Selenide,
Triphenylphosphine selenide b selenophosphates, for example, tri-p-tolylselenophosphate, tri-n-butylselenophosphate The preferred types of labile selenium compounds are described above, but these are not limiting. Absent. 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.

JP-B-46-4553 and 52-344
Selenium sensitization using the non-labile selenium sensitizers described in Nos. 92 and 52-34491 can also be used. Examples of the non-labile selenium compound include selenious acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles, diaryl selenides, diaryl diselenides,
Included are 2-thioselenazolidinediones, 2-selenooxodinthiones and their derivatives.

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

These selenium sensitizers are added at the time of chemical sensitization by dissolving them 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 the halogenation. It is 1 × 10 ^-8 mol or more per mol of silver. More preferably 1 × 10 ⁻⁷ mol or more and 1 × 10 ⁻⁴
It is less than or equal to mol. 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.

As the silver halide solvent which can be used in the present invention, US Pat. Nos. 3,271,157, 3,531,289, 3,574,628 and JP-A-54- (A) Organic thioethers described in 1019, 54-158917 and the like, JP-A-53-82.
(B) thiourea derivatives described in JP-A No. 408, 55-77737, 55-2982 and the like, JP-A-53-1.
No. 44319, (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, (d) imidazoles described in JP-A No. 54-100717, ( Examples thereof include e) sulfite and (f) thiocyanate.

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 by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time.

The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time.

For the 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 and 3,656,955 each specification,
German Patent 1,422,869, Japanese Patent Publication No. 56-249
The sulfur sensitizers described in JP-A No. 37, 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. No. 3,320,06 for the use of thiocyanate in grain formation.
9 and 4,434,226.

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 → 2Ag + Br + (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 deleterious effect on the silver halide material as a result of trapping the halogen gas.

It is generally known that zeratan acts as a halogen gas scavenger, and that its action is a function of pH and pAg of the system. However, in the present invention, the following compounds are preferably present as halogen gas scavengers at any position in the sealed container of the silver halide photographic product. Examples thereof include sulfide compounds, nitrites, semicarbazides, sulfites, hydroquinones, ethylenediamine, acetone semicarbazone, and p-hydroxyphenylglycine.

The halogen gas scavenger may be added at any position such as a protective layer, an intermediate layer, a non-photosensitive layer such as a back layer opposite to the emulsion surface of the film, or a silver halide emulsion layer. More preferably, it is added on the emulsion layer side of the support to a layer further away from the support. The addition amount is 0.
05-1 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 contained in the light-shielding container is stored in a hermetically-sealed container, but a part of the light-sensitive material is placed in a position where light can be irradiated after sealing, and the rest is left. Is shielded from light by the light shielding container,
Air is circulated between the light-irradiated portion and the light-shielded portion.

The light-shielding container of the present invention includes a cassette for 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 silver halide photographic products in which the present invention can be used include, for example, the currently prevailing 135-format roll film. One embodiment of this is shown in FIGS. FIG. 1 shows a state in which a film 1 with a cartridge is housed in a transparent plastic container 2. FIG. 2 shows a film 1 with a cartridge. 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 is in a state in which air can flow to the light-shielded portion through the gap between the film drawing portion 5 or the cartridge.

The cartridge 4 containing the silver halide photographic light-sensitive material has a container body 2a and a container cap 2b.
It is sealed by a transparent plastic container 2 made of. The sealed transparent plastic container 2 is designed to block harmful gases for the photosensitive material and suppress excessive permeation of water vapor, but the permeability of gas and water vapor is the main body 2 of the container.
It is greatly influenced by the structure and material of a and the cap 2b of the container.

It is preferable that the humidity in the sealed container is kept constant. In the present invention, the effect of the present invention is remarkable when the relative humidity is 25% or more at 25 ° C. To keep the humidity of the sealed container constant means that the humidity change inside the case is 10% or less when 12 months have passed at 25 ° C. when the humidity difference between the outside air and the inside of the case is 20%.

It is preferable for the present invention to keep the inside of the sealed container near normal humidity. Specifically, at 25 ° C., the relative humidity in the sealed container is preferably 50% or more and 70% or less, more preferably 55% or more and 68% or less.

The relative humidity referred to in the present invention is a value measured at 25 ° C., and can be measured by a conventional method (relative humidity is
For example, it can be measured by a capacitance type humidity measuring device such as a Humicap humidity sensor manufactured by VAISALA. In the present invention, as shown in FIG. 1, the body 2a of the transparent plastic container or the cap 2b of the container is light transmissive. The light-transmissive property means that the portion pulled out from the film pull-out portion can be substantially exposed to external light. More specifically, 2 under the irradiation of light of 10000 lux.
When held for 4 hours, the increase in fogging of the part drawn out from the film drawing part is 0.1 or more, preferably 0.5.
Or more, more preferably 1.0 or more. -Addition polymerization of olefins having carbon double bonds, ring-opening polymerization of small ring compounds, polycondensation (condensation polymerization) of two or more polyfunctional compounds, polyaddition and phenol derivatives, urea derivatives, melamine derivatives and aldehydes It can be produced by a method such as addition condensation with a compound having

The raw material of the plastic material is an olefin having a carbon-carbon double bond, such as styrene or α.
-Methyl styrene, butadiene, methyl methacrylate,
Representative examples include butyl acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl carbazole, N-vinyl pyrrolidone, vinylidene cyanide, ethylene, propylene and the like. In addition, as the small ring compound, for example, ethylene oxide, propylene oxide, glycidol, 3,3-bischloromethyloxetane, 1,4-dioxane, tetrahydrofuran, trioxane, ε-caprolactam,
Typical examples include β-propiolactone, ethyleneimine, tetramethylsiloxane and the like.

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, peroxide Radical polymerization catalyst such as potassium sulfate, sulfuric acid, toluenesulfonic acid, trifluorosulfuric acid, perchloric acid, trifluoroboron, cationic polymerization catalyst such as tin tetrachloride, n-butyllithium, sodium / naphthalene, 9-fluorenyllithium, Anionic polymerization catalysts such as phenylmagnesium bromide, triethylaluminum / tetrachlorotitanium type Ziegler-Natta type catalysts, sodium hydroxide, potassium hydroxide, potassium metal and the like are used.

The solvent is not particularly limited as long as it does not inhibit the polymerization, but examples thereof include hexane, decalin, benzene, toluene, cyclohexane, chloroform, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran and the like.

For molding the plastics of the present invention, a plasticizer is mixed with the plastics if necessary. As the plasticizer, for example, trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sebacate, methyl amyl ketone, nitrobenzene, γ-valerocratone, di-n-octyl succinate, bromonaphthalene, butyl palmitate, etc. are typical. It is a thing.

Specific examples of the plastic material used in the present invention are given 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 phenol resin P-16 melamine resin Particularly preferred plastic materials for the invention are polystyrene, polyethylene, polypropylene and the like.

Next, the sensitizing dyes represented by the general formulas (I) and (II) will be further described.

[0068]

[Chemical 6] In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ may be the same or different and each represents a hydrogen atom, an alkyl group (including one having an alkyl group as a substituent), an aryl group (here And aryl groups include those having a substituent), alkoxy groups (wherein the alkoxy group includes those having a substituent), aryloxy groups (where the aryloxy group includes those having a substituent), halogen Atoms, alkoxycarbonyl groups (wherein the alkoxycarbonyl group includes those having a substituent), aryloxycarbonyl groups (where the aryloxycarbonyl group includes those having a substituent), acylamino groups (wherein the acylamino group is (Including those having a substituent), acyl groups (wherein the acyl group includes those having a substituent), cyano groups, carbamoyl groups (herein Moyl groups include those having a substituent), sulfamoyl groups (wherein the sulfamoyl group includes those having a substituent), carboxyl groups, or acyloxy groups (wherein the acyloxy group includes those having a substituent). Represent.

However, R ₁₁ and R ₁₂ and R ₁₃ and R ₁₄ do not represent hydrogen atoms at the same time. R ₁₅ and R ₁₆ may be the same or different and each represents a substituted or unsubstituted alkyl group.

R ₁₇ is L> 4.11, B ₁ > 1.52,
Alkyl groups (including substituted alkyl) and aryl groups having L, B ₁ , B ₂ , B ₃ and B ₄ such that B ₂ > 1.90, B ₃ > 1.90, B ₄ > 2.97 (Including substituted aryl).

Where L, B ₁ , B ₂ , B ₃ and B ₄
Is, for example, Bear Rope, W. Hogenstraten, J. Tipcar, Volume 7 of Drug Design (E.
J. Academic Press, Academic Press, New York (1976), pages 180-185 (A. Verlo)
op, W.W. Hoogenstratten, J .; Tip
ker: “Drug Design, Vol. VII”
(E.J. Ariens Ed.) Academic P
less, New York (1976). pp. 18
The values of L, B ₁ , B ₂ , B ₃ , and B ₄ of the STERIMOL parameters described in Nos. 0 to 185 are shown (unit is angstrom).

Specifically, propyl, isopropyl, cyclopropyl, butyl, isobutyl, chloromethyl, 2-
Mention may be made of chloroethyl, 3-chloropropyl, phenyl and benzyl, most preferably propyl, phenyl and benzyl.

X ₁ represents a counter anion, m is 0 or 1, and when forming an intramolecular salt, m = 0.

[0074]

[Chemical 7] In the formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R
₂₈ , R ₂₉ and R ₃₀ have the same meaning as R ₁₁ . R ₃₁ and R
₃₂ has the same meaning as R ₁₅ . Y represents a sulfur atom or a selenium atom. X ₂ has the same meaning as X ₁ . n has the same meaning as m.

In the general formula (I) or (II) of the present invention, when the specific partial structure is an alkyl group or an aryl group, these may have a usual substituent.

Preferred examples of each substituent in the compound represented by the general formula (I) or the general formula (II) used in the present invention are shown below. That is, R ₁₁ , R ₁₂ , R ₁₃ ,
R ₁₄ is an alkyl group (for example, methyl, ethyl, propyl,
Isopropyl, butyl, branched butyl groups (eg isobutyl, t-butyl), pentyl groups, branched pentyl groups (eg isopentyl, t-pentyl), vinylmethyl groups, cyclohexyl groups}, aryl groups having 10 or less carbon atoms (eg phenyl , 4-methylphenyl, 4-chlorophenyl, naphthyl), an aralkyl group having 10 or less carbon atoms (for example, benzyl, phenethyl, 3-phenylpropyl), an alkoxy group having 10 or less carbon atoms (for example, methoxy, ethoxy, propyloxy, butyloxy, Pentyloxy,
Benzyloxy, phenethyloxy), an aryloxy group having 10 or less carbon atoms (for example, phenoxy, 4-methylphenoxy, 4-chlorophenoxy, naphthyloxy),
Halogen atoms (eg fluorine, chlorine, bromine, iodine),
Haloalkyl group (eg trifluoromethyl), alkoxycarbonyl group having 10 or less carbon atoms (eg methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, aryloxycarbonyl group having 10 or less carbon atoms (eg phenyloxycarbonyl, 4-methylphenyloxycarbonyl) , 4-chlorophenyloxycarbonyl, naphthyloxycarbonyl), an acylamino group having 8 or less carbon atoms (eg acetylamino, propionylamino, benzoylamino), an acyl group having 10 or less carbon atoms (eg acetyl, propionyl, benzoyl, mesyl), cyano Group, a carbamoyl group having 6 or less carbon atoms (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbamoyl), a sulfamoyl group having 6 or less carbon atoms (eg, sulfamoyl) Le, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), a carboxyl group or a C 10 an acyloxy group (e.g. acetyloxy, propionyloxy, benzoyloxy) are preferred.

Most preferably, R ₁₁ and R ₁₃ are hydrogen atoms, R ₁₂ is a chlorine atom or a phenyl group, and R ₁₄ is a chlorine atom or a phenyl group.

R ₁₅ and R ₁₆ are an alkyl group having 8 or less carbon atoms (eg, methyl, ethyl, propyl, vinylmethyl, butyl, pentyl, hexyl, heptyl, octyl), an aralkyl group having 10 or less carbon atoms (eg, benzyl). , Phenethyl, 3-phenylpropyl). The substituents of R ₁₅ and R ₁₆ include a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, fluorine, chlorine and chlorine), an alkoxycarbonyl group having 8 or less carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, Benzyloxycarbonyl), an alkoxy group having 8 or less carbon atoms (eg, methoxy, ethoxy, butyloxy, benzyloxy, phenethyloxy), 8 carbon atoms
The following aryloxy groups (eg, phenoxy, p-tolyloxy), acyloxy groups having 8 or less carbon atoms (eg, acetyloxy, propionyloxy, benzoyloxy), acyl groups having 8 or less carbon atoms (eg, acetyl, propionyl, benzoyl, 4-). Fluorobenzoyl), a carbamoyl group having 6 or less carbon atoms (for example, carbamoyl,
N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, methanesulfonylaminocarbonyl), sulfamoyl group having 6 or less carbon atoms (for example, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl, acetyl) Aminosulfonyl), and an aryl group having 10 or less carbon atoms (eg, phenyl, p-fluorophenyl-p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl).

Preferred as R ₁₅ and R ₁₆ are sulfoethyl, sulfopropyl, sulfobutyl, 1-methylsulfopropyl, carboxymethyl and carboxyethyl, with sulfopropyl and sulfobutyl being most preferred.

R ₁₇ is an alkyl group having 8 or less carbon atoms (eg propyl, isopropyl, cyclopropyl, butyl, branched butyl group (eg isobutyl, t-butyl), pentyl, branched pentyl group (eg isopentyl, t -Pentyl), cyclohexyl, an aryl group having 10 or less carbon atoms (eg, phenyl, p-tolyl),
Aralkyl groups having 10 or less carbon atoms (eg, benzyl, phenethyl, 3-phenylpropyl) are preferred.

Particularly preferred as R ₁₇ is propyl,
Phenyl and benzyl.

R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R
₂₇ , R ₂₈ , R ₂₉ and R ₃₀ have the same meaning as R 11.

The combination of the substituents R _{21 to} R ₃₀ is preferably a case where R ₂₄ and / or R ₂₅ is an alkyl group, R ₂₉ is a halogen atom or an alkyl group, and the rest are all hydrogen atoms.

General formula (I) and general formula (II) of the present invention
The compound represented by F.M.Harmer (F.
M. Hamer) "Heterocyclic Compounds-Cyanine Soybean and Relative Compounds (Heterocyclic Compound)
s-Cyanine Dyes and Relate
d Compounds, John Wiley & Sons-
New York, London, 1964), D.M. Sturmer, "Heterocyclic Compounds-Special Topics."
In Heterocyclic Chemistry- (Hete
local Compounds-Specia
l topics in heterocycle
Chemistry-) ", page 18, section 14, fourth
82-515, John Wiley & Sons, Inc., New York, London, (1977), "Rods Chemistry of Carbon Compounds (Rodds.
Chemistry of Carbon Compo
unds) ", (2nd. Ed. Vol. IV, part.
B, 1977), Chapter 15, 369-422.
Page; (2nd. Ed. Vol. IV, part B, 19
1985), Chapter 15, pp. 267-296, Els Buyer, Science Public Company, Inc. (Elsvier Science Publishing).
ng Company Inc. ) It can be synthesized based on the method described in New York, published by the company.

Specific examples of the compounds represented by formula (I) and formula (II) of the present invention are shown below, but the scope of the present invention is not limited to these.

[0086]

[Chemical 8]

[0087]

[Chemical 9]

[0088]

[Chemical 10]

[0089]

[Chemical 11]

[0090]

[Chemical 12]

[0091]

[Chemical 13] At least one layer of the silver halide photographic light-sensitive material of the present invention preferably contains a compound represented by the following general formula (III) or (IV) or (V).

[0092]

[Chemical 14] The sensitizing dye represented by formula (III) or (IV) or (V) will be further described.

The optionally substituted alkyl group represented by R ³ and R ⁴ is an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms (unsubstituted alkyl group (for example, , Methyl, ethyl, propyl,
Isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups such as aralkyl groups (eg, benzyl, 2-phenylethyl), hydroxyalkyl groups (eg, 2-hydroxyethyl, 3-hydroxypropyl), Carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), sulfoalkyl group (For example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-
[3-sulfopropoxy] ethyl, 2-hydroxy-3
-Sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl group (for example, 3-sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1) -Yl) ethyl, tetrahydrofurfuryl), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl) or allyl group.

Either R ³ or R ⁴ is preferably a sulfoalkyl group or a carboxyalkyl group.

R ⁵ is a hydrogen atom, an optionally substituted alkyl group (eg, methyl, ethyl, benzyl), an optionally substituted aryl group (eg, phenyl, p
-Tolyl). Particularly preferred is ethyl.

X ⁻ is an inorganic or organic anion (eg,
Chloride, bromide, iodide, p-toluenesulfonate, p-nitrobenzenesulfonate, methanesulfonate, methylsulfate, ethylsulfate, perchlorade, 1,5-naphthalenedisulfonate).

N represents a numerical value for controlling the charge of the whole molecule, and is 0 when forming an intramolecular salt.

The sensitizing dyes represented by the general formula (III), (IV) or (V) represented by the general formula used in the present invention include F.I. M. By Hammer,
"Heterocyclic Compounds-Cyanine Soybean and Relayed Compounds (Heter
ocyclic Compounds-Cyanine
Dyes and Related Compound
s) "Chapter 4, Chapter 5, Chapter 6, pages 86-119,
John Wiley and Sons (John Wile
y and Sons) (1964), D.Y. M.
Heterocyclic Compounds Special Topics in Heterocyclic Chemistry by DM Sturmer
cylic Compounds-Special T
Opics in Heterocyclic Che
can be easily synthesized based on the method described in "Johnson Wiley &Size" (1977), Chapter 8, pp. 482-515.

General formulas (III) and (IV) used in the present invention
And specific examples of the sensitizing dyes represented by (V),
Although shown in Table 1, Table 2 and Table 3 below, the present invention is not limited thereto.

[0100]

[Table 1]

[0101]

[Table 2]

[0102]

[Table 3] The sensitizing dyes represented by formulas (III), (IV) and (V) used in the present invention may be contained in any step of the process for producing a silver halide photographic light-sensitive material.

General formulas (I) and (I
In order to incorporate the compounds represented by I), (III), (IV) and (V) into silver halide, they may be dispersed directly in the emulsion, or they may be dispersed in water, methanol, ethanol. It may be added to the emulsion by dissolving it in a solvent such as acetone, methyl cellosolve, and fluoroalcohol alone or in a mixed solvent. When it is added to the silver halide emulsion, it may be added during the process of forming the silver halide grains or may be added afterwards to the silver halide grains produced in advance. When added in the process of forming silver halide grains, it may be added immediately before the process of reacting silver and halogen, the physical ripening process, the chemical ripening (post ripening) process, during the chemical ripening process, or immediately after the chemical ripening process. However, it is preferably added just before the physical ripening process to the chemical ripening (post-ripening) process.

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

General formulas (I) and (I used in the present invention
The addition amount of the sensitizing dyes represented by I), (III), (IV) and (V) varies remarkably depending on the type of silver halide emulsion, but is usually 4 × 10 ⁻⁶ to 8 × per mol of silver halide.
It is 10 ^-3 mol.

The light-sensitive material used in the silver halide photographic product of the present invention has at least one silver halide emulsion layer of blue-sensitive layer, green-sensitive layer and red-sensitive layer on the support. Is provided, and the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed 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, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The array is, in order from the support side, a red color-sensitive layer, a green color-sensitive layer,
They are installed in order of blue color sensitivity. 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 in the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as usual.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Further, JP-A-57-112751, JP-A-62-20035.
No. 0, No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

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

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 the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Further, an arrangement in which a silver halide emulsion layer having a lower photosensitivity is disposed and three layers having different sensitivities in which the sensitivities are sequentially lowered toward the support are provided can be mentioned. 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, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
Nos. 63-89850 and BL, G
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer.

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

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

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

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), page 648, ibid. Thirty
7105 (Nov. 1989), pp. 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemieet.
Phisique Photographique, P
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff).
in, Photographic Emulsion
Chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
otographic Emulsion, Focal
Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 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 in Gutoff, Photographic Science and Engineering (Gutoff, Photograph).
ic Science and Engineering
g), 14: 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157, and the like.

The crystal structure is uniform, and the inside and the outside may have different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

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

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and the same No. No. 307105, and the relevant parts are summarized in the table below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

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

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but is 0.01 to 0.75 as an average grain size.
μm, and particularly preferably 0.05 to 0.6 μm. 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 a 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 development process, and it is preferable that it is not covered in advance. preferable.

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferably silver iodide is 0.
5 to 10 mol% is contained.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. However, 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.

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 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, page 649, right column, 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Antifoggants, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizer 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter dyes, to page 650, left column, ultraviolet absorbers 7. Stain page 25 right column page 650 left column page 872 Inhibitor to right column 8. Dye image Page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder page 26 page 651 left column 873 to page 874 11. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27 page 650 right column 876 to 877 inhibitor 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, fixing is performed by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being converted into a light-sensitive material.

Photosensitive materials used in the silver halide photographic products of the present invention include US Pat. Nos. 4,740,454, 4,788,132, JP-A-62-18539 and JP-A-1-283551. It is preferable to include the mercapto compound described in No.

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

The light-sensitive material used in the silver halide photographic product of the present invention contains a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or EP317,308A, US Pat. Number 4, 42
It is preferable to incorporate the dyes described in JP-A No. 0,555 and JP-A-1-259358.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure (RD) No. 17643, VII-C to G,
And the same No. 307105, VII-C to G.

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

As the magenta coupler, 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)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in US Pat. No. 8,5951, US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat. No. 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Further, JP-A 64-553 and 64-5.
No. 54, No. 64-555 and No. 64-556, and pyrazoloazole couplers described in US Pat.
The imidazole couplers described in No. 8,672 can also be used.

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

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

Colored couplers for correcting unwanted absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. Of 307105
Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD1 above.
7643, Item VII-F and No. 307105, VII
Patents described in section F, JP-A-57-151944
No. 57-154234, No. 60-184248.
No. 63-37346, No. 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012.
Those described in No. 10 are preferable.

RD No. The bleaching accelerator releasing couplers described in 11149, 24241 and JP-A-61-201247 are effective in shortening the processing time having a bleaching ability, and particularly, the tabular silver halide grains described above. The effect is great when it is added to a photosensitive material using.
Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,140,
No. 2,131,188, JP-A-59-157638.
Nos. 59-170840 and No. 59-170840 are preferable.
Further, JP-A-60-107029 and JP-A-60-2523.
No. 40, JP-A Nos. 1-44940 and 1-45687, and compounds which release a fog, a development accelerator, a silver halide solvent and the like by a redox reaction with an oxidized product of a developing agent 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 photographic 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. 2,322,027. The boiling point at atmospheric pressure used in oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate,
Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphone Acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate,
Tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (eg 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg N, N-). Diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-t-amylphenol), aliphatic carboxylic acid esters (eg Screw (2-
Ethylhexyl) sebacate, dioctyl azelate,
Glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-butoxy-5-t-octylaniline), hydrocarbons (eg paraffin, dodecylbenzene, diisopropylnaphthalene) And so on. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate and butyl acetate.
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
3, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

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

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

Suitable supports which can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

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

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

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

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
18716, page 651, left column to right column, and the same No. 307
Development processing can be carried out by a usual method described on page 880-881.

The color developer used for processing the silver halide photographic product of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3- Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Examples thereof include amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. 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 developing solution includes, for example, pH buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles,
A development inhibitor such as benzothiazoles or mercapto compounds or an antifoggant is generally contained. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvent such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salt,
Development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos. Various chelating agents represented by carboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo. -N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N,
Representative examples include N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In the black-and-white developing solution, known developing agents, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used. They can be used alone or in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. 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, the contact area with the air in the processing tank is reduced to evaporate the liquid,
It is preferable to prevent air oxidation.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² ) ÷ volume of treatment liquid (cm ³ )] The above aperture ratio (cm ⁻¹ ) is preferably 0.1 or less, 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 photographic processing liquid surface of the processing tank,
The method using a movable lid described in JP-A-1-82033 and the slit development processing method described in JP-A-63-216050 can be mentioned. Reducing the aperture ratio is not limited to both color development and black and white development,
Subsequent steps, such as bleaching, bleach-fixing, fixing, washing,
It is preferably applied in all steps such as stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

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

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. As a typical bleaching agent, an organic complex salt of iron (III), for example, aminopolyamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Carboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: 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. Compounds having a mercapto group or a disulfide group described in 17129 (July 1978) and the like;
Thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5.
Thiourea derivatives described in No. 61; West German Patent No. 1,12
No. 7,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30; Japanese Patent Publication No. 4
Polyamine compounds described in JP-A-5-8836; Others, JP-A-49-40,943, JP-A-49-59644 and JP-A-53
-94927, 54-57727, 55-26.
Compounds described in Nos. 506 and 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable because of its large accelerating effect, and particularly, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630.
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 and hydroxyacetic acid are preferred.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Use of thiosulfates is preferred. It is common and in particular ammonium thiosulfate can be used most widely. 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, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution contains p for adjusting the pH.
It is preferable to add 0.1 to 10 mol / liter of a compound having a Ka of 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.

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 step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, there is a method described in JP-A-62-183460, in which a jet stream of a processing solution is made to collide with the emulsion surface of a light-sensitive material, and JP-A-6-63.
No. 2-183461, a method of enhancing the stirring effect, and further moving the light-sensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface to make the emulsion surface turbulent, thereby further stirring. There are a method of improving the effect and a method of increasing the circulation flow rate of the whole treatment liquid. Such a stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

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

The silver halide color photographic light-sensitive material used in the present invention is generally washed with water and / or stabilized after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the material used such as coupler), the purpose of use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent and forward flow, and various other methods. It can be set in a wide range depending on the conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is as follows.
f the Society of MotionPi
movie and Television Engi
neers Vol. 64, p. 248-253 (1955
May issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and benzotriazole are also described by Hiroshi Horiguchi in "Bacterial and Antifungal Agents". Chemistry (1986) Sankyo Publishing, edited by Sanitary Technology, "Microbial sterilization, sterilization and antifungal technology" (1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal "Encyclopedia of Antibacterial and Antifungal Agents" (1986) It is also possible to use the bactericide described in (4).

The pH of washing water in the processing of the light-sensitive material used in the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but are generally in the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. To be selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water.
In such stabilization treatment, Japanese Patent Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

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

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

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

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

The silver halide color light-sensitive material used in the present invention is, if necessary, for the purpose of accelerating color development.
Various 1-phenyl-3-pyrazolidones may be incorporated. Typical compounds are, for example, JP-A-56-64339.
No. 57-144547 and No. 58-11543.
No. 8.

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

[0177]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a film 101 which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ⁻³ HBS-1 0.20 Second layer (intermediate) Layer) Emulsion G1 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-10 .10 HBS-2 0.020 gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A1 Silver 0.10 Emulsion B1 Silver 0.40 ExS-1 6.9 × 10 ^-5 ExS-2 1. 8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0. 010 Cpd-2 0.025 H S-1 0.10 Gelatin 0.87 Fourth Layer (medium-sensitivity red-sensitive emulsion layer) Emulsion D1 silver ^{0.60 ExS-1 3.5 × 10 -4} ExS-2 1.6 × 10 -5 ExS-3 5.1 × 10 ⁻⁴ ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.08 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd -2 0.023 HBS-1 0.10 Gelatin 0.75 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E1 Silver 1.10 ExS-1 2.4x10 ^-4 ExS-2 1.0x10 ^-4 ExS-3 3.4x10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS- 2 0.10 Gelatin 1.20 6th layer (intermediate layer) Cp -1 0.10 HBS-1 0.50 Gelatin 1.10 7th layer (low sensitivity green-sensitive emulsion layer) Emulsion C1 silver ^{0.35 I-2 4.8 × 10 -4} ExS-4 3.0 × 10 ^-5 ExS-5 2.1x10 ^-4 ExS-6 4.0x10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-10 .30 HBS-3 0.010 Gelatin 0.73 Eighth layer (medium sensitivity green emulsion layer) Emulsion D1 Silver 0.80 I-2 5.0 × 10 ⁻⁴ ExS-4 3.2 × 10 ⁻⁵ ExS -5 2.2 x 10 ^-4 ExS-6 4.2 x 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0x 10 ^-3 Gelatin 0.90 9th layer (high-sensitivity green-sensitive emulsion layer) Emulsion E1 Silver 1.25 I-2 2.0 × 10 ^-4 E xS-4 3.7 × 10 ⁻⁵ ExS-5 8.1 × 10 ⁻⁵ ExS-6 1.6 × 10 ⁻⁴ ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM− 5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44 10th layer (yellow filter layer) Yellow colloidal silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60 11th layer (low-sensitivity blue emulsion layer) Emulsion C1 Silver 0.18 ExS-7 8.6 × 10 ⁻⁴ ExY-1 0.020 ExY-2 0.22 ExY-30 .50 ExY-4 0.020 Cpd-3 0.01 HBS-1 0.28 Gelatin 1.10 12th layer (medium-sensitivity blue-sensitive emulsion layer) Emulsion D1 Silver 0.40 ExS-7 7.4 × 10 ^{− 4 ExC-7 7.0 × 10 -3} ExY 2 0.050 ExY-3 0.10 Cpd-3 0.005 HBS-1 0.050 Gelatin 0.78 13th layer (high-sensitivity blue emulsion layer) Emulsion F1 Silver 0.80 ExS-7 4.0x 10 ^-4 ExY-2 0.10 ExY-3 0.10 Cpd-3 0.004 HBS-1 0.070 gelatin 0.86 14th layer (first protective layer) Emulsion G1 Silver 0.20 UV-40 .11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00 Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 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 Furthermore, storability, processability, pressure resistance, and antifungal properties are appropriately applied to each layer.
To improve antibacterial property, antistatic property and coating property W-
1 to W-3, B-4 to B-6, F-1 to F
-17 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained.

[0178]

[Table 4] In Table 4, (1) Emulsions A1 to F1 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 A1 to F1 are described in JP-A-3-237.
According to the Example of No. 450, gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate.

(3) Preparation of tabular grains is described in JP-A-1-1.
Low molecular weight gelatin is used according to the Example of 58426.

(4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

[0182]

[Chemical 15]

[0183]

[Chemical 16]

[0184]

[Chemical 17]

[0185]

[Chemical 18]

[0186]

[Chemical 19]

[0187]

[Chemical 20]

[0188]

[Chemical 21]

[0189]

[Chemical formula 22]

[0190]

[Chemical formula 23]

[0191]

[Chemical formula 24]

[0192]

[Chemical 25]

[0193]

[Chemical formula 26]

[0194]

[Chemical 27]

[0195]

[Chemical 28]

[0196]

[Chemical 29]

[0197]

[Chemical 30] (Film 102) Film 1 except that the sensitizing dye I-2 in the seventh, eighth and ninth layers was replaced with equimolar II-1.
A film 102 was prepared in the same manner as 01. (Film 103) Film 103 was prepared in the same manner as Film 101, except that ² mg of tetrachloropalladium (II) potassium was added to the 6th layer per m ² (0.533 mol was added to 1 mol of thiocyanate). Was produced. (Films 104 to 106) Potassium tetrachloropalladium (II) was added to the sixth layer in an amount of ² mg and 1 m, respectively, per m ^2.
g, 0.5 mg (0.533 mol, 0.267 mol, 0.1.
Films 104, 105 and 106 were produced in the same manner as the film 102 except that the addition amount was 133 mol). (Film 107) A film 107 was produced in the same manner as the film 103 except that the sensitizing dye I-2 of the seventh layer, the eighth layer, and the ninth layer was replaced with equimolar amounts of ExS-8. (Film 108) A film 108 was prepared in the same manner as the film 102 except that the sensitizing dye ExS-5 in the seventh layer, the eighth layer, and the ninth layer was replaced with equimolar amount ExS-6.

Films 101-108 in the dark 135
Format 24 shots Processed into a patrone form. At this time, the ratio of the area of the film filled in the inside of the cartridge and the area of the film drawn out from the film drawing portion was set to correspond to 1: 0.05. This one at 25 ℃
After adjusting the humidity to 60% relative humidity for 4 days, the silver halide photographic products 1 to 12 shown in Table 5 were placed in a transparent plastic sealed container shown in FIG. It was made.

[0199]

[Table 5] As shown in Table 6, silver halide photographic products 1 to 12 were produced with and without light irradiation at 10,000 lux for 24 hours (samples 1001 to 1024 in Table 6).
Samples 1001 to 1024 in the dark at 60 ° C. 60% relative humidity
It was stored under an atmosphere of RH for 3 days. After that, open the sealed container, pull out the film in the dark, and in the unexposed area,
1/100 through continuous wedge at color temperature 4800 ° K
Exposed for 2 seconds. Further, the silver halide photographic products 1 to 12 which were not subjected to the above treatment were similarly exposed.

[0200]

[Table 6] After exposing the color photographic light-sensitive material as described above, it was processed by the method described below. (Processing process) Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ℃ Bleaching 3 minutes 00 seconds 38 ℃ Washing with water 30 seconds 24 ℃ Settling 3 minutes 00 seconds 38 ℃ Washing with water (1) 30 seconds 24 ℃ Water Washing (2) 30 seconds 24 ° C Stability 30 seconds 38 ° C Drying 4 minutes 20 seconds 58 ° C Next, the composition of the treatment liquid is described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 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 added 1.0 liter pH (to potassium hydroxide and sulfuric acid 10.05 (bleaching solution) (unit g) ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 ethylenediaminetetraacetic acid disodium salt 10.0 3-mercapto-1,2,4-triazole 0.03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Add water 1.0 liter pH (adjusted with ammonia water and nitric acid) 6.0 (fixing solution) (unit g) ethylenediaminetetraacetic acid disodium salt 0.5 ammonium sulfite 20.0 ammonium thiosulfate aqueous solution (700 g / liter) 295.0 Milliliter acetic acid (90%) 3.3 Add water 1.0 liter pH (adjusted with ammonia water and acetic acid) 6.7 (stabilizing liquid) (unit g) sodium p-toluenesulfinate 0.03 polyoxyethylene -P-Monononyl phenyl ether (average degree of polymerization: 10) 0.2 ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazole-1) -Ilmethyl) piperazine 0.75 Add water to 1.0 liter pH 8.5 Treated sample with green filter The density was measured at 60 ° C., and the increase in fog and the change in sensitivity of the film stored at 60 ° C. and 60% RH in relative humidity for 3 days were calculated.
The results are shown in Table 6. At this time, the change in sensitivity is indicated by the difference in logarithm of the exposure amount required to increase the fog density by 0.15.

From Table 6, the films 101 and 102 in the transparent sealed plastic containers are 60 ° C. and 60% RH.
If it is exposed to light before being stored for 3 days (Sample 10
It is understood that abnormal fog occurs only in No. 01, 1005). On the other hand, in the silver halide photographic products 5, 7, 9, 10, and 12, which are the silver halide photographic products of the present invention, this fogging change is small and the effect of the present invention is remarkable.

Example 2 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a film 201 which is a multilayer color light-sensitive material. (Photosensitive layer composition) The materials used for each layer are classified as follows; ExC: Cyan coupler HBS: High boiling point organic solvent ExM: Magenta coupler ExO: Color mixture inhibitor ExY: Yellow coupler W: Surfactant ExS: Sensitizing dye H: Gelatin hardening agent UV: Ultraviolet absorber B: Polymer S: Formalin scavenger or antifoggant F: Additive (stabilizer, antifoggant, etc.) The number corresponding to each component is g / m ² unit The coating amount represented by is shown, and for silver halide, the coating amount in terms of silver is shown. 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 0.090 Dispersion A of organic solid disperse dye 10.0 Dispersion B of organic solid disperse dye 5.0 Gelatin 1.4 Second layer (intermediate) Layer) 2,5-di-t-pentadecylhydroquinone 0.18 ExM-1 0.070 ExC-2 0.020 ExF-1 0.0020 UV-1 0.060 UV-2 0.080 UV-30 .10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.0 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A2 Silver 0.10 Emulsion B2 Silver 0.40 ExS-1 1.5 × 10 ^{− 4} ExS-2 1.8 × 10 ⁻⁵ ExS-3 2.5 × 10 ⁻⁴ ExC-7 0.020 ExC-1 0.17 ExC-4 0.17 ExC-9 0.020 ExM-3 0. 020 UV-1 0.070 U -2 0.050 UV-3 0.070 HBS- 1 0.060 Gelatin 0.87 Fourth Layer (medium-sensitivity red-sensitive emulsion layer) Emulsion D2 silver ^{1.60 ExS-1 1.0 × 10 -4} ExS- 2 1.4 × 10 ⁻⁵ ExS-3 2.0 × 10 ⁻⁴ ExC-2 0.010 ExC-7 0.010 ExC-1 0.050 ExC-4 0.04 ExC-3 0.080 Gelatin 0 .70 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion G2 Silver 0.8 ExS-1 1.0 × 10 ^-4 ExS-2 1.4 × 10 ^-5 ExS-3 2.0 × 10 ^-4 ExC -0.050 ExC-7 0.015 ExC-1 0.20 ExC-4 0.20 ExC-10 0.20 ExC-11 0.020 UV-1 0.070 UV-2 0.050 UV-3 0.070 HBS-1 0.22 HBS-2 0.10 Gelatin 1.6 Sixth Layer (Intermediate Layer) ExO-1 0.040 ExM-11 0.050 HBS-1 0.020 Gelatin 0.80 Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion A2 Silver 0.15 Emulsion B2 silver 0.15 emulsion C2 silver 0.10 ExS-9 5.0 × 10 ⁻⁵ ExS-4 3.0 × 10 ⁻⁵ ExS-5 1.0 × 10 ⁻⁴ ExS-6 3.8 × 10 ^{− 4} ExM-1 0.021 ExM-3 0.030 ExM-2 0.20 ExY-1 0.0050 ExM-7 0.10 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63 Eighth layer (Medium speed green sensitive emulsion layer) ExM-4 0.018 ExC-11 0.040 HBS-1 0.16 HBS-3 0.0080 Gelatin 0.50 9th layer (high sensitive green sensitive emulsion layer) Emulsion E2 Silver ^{1.4 ExS-9 0.50 × 10 -5} ExS-4 ^{.5 × 10 -5 ExS-5 8.0} × 10 -5 ExS-6 3.0 × 10 -4 ExM-3 0.025 ExM-8 0.015 ExM-9 0.50 ExY-5 0.020 HBS-1 0.25 HBS-2 0.10 Gelatin 1.5 10th layer (intermediate layer) ExO-1 0.040 HBS-1 0.020 Gelatin 0.80 11th layer (of the multi-layer effect on the red-sensitive layer) Donor layer) Emulsion J2 Silver 1.4 Emulsion K2 Silver 1.8 I-2 4.0 × 10 ^-4 ExC-7 0.10 ExM-10 0.10 HBS-1 0.10 HBS-2 0.10 Gelatin 0.80 12th layer (yellow filter layer) Yellow colloidal silver Silver 0.050 Dispersion of organic solid disperse dye B 15.0 ExO-1 0.080 HBS-1 0.030 Gelatin 0.95 13th layer (low) Sensitivity blue-sensitive emulsion layer) Emulsion 2 silver 0.080 Emulsion B2 silver 0.070 Emulsion F2 silver ^{0.070 ExS-7 3.5 × 10 -4} ExC-1 0.042 ExY-2 0.72 ExY-6 0.020 HBS-1 0. 28 Gelatin 1.1 Fourteenth layer (medium-speed blue-sensitive emulsion layer) Emulsion G2 Silver 0.45 ExS-7 2.1 × 10 ^-4 ExY-2 0.15 ExC-7 0.0070 HBS-1 0.050 Gelatin 0.78 Fifteenth layer (high-sensitivity blue-sensitive emulsion layer) Emulsion H2 Silver 0.77 ExS-7 2.2 × 10 ⁻⁴ ExY-5 0.010 ExY-2 0.60 ExY-6 0.010 HBS -1 0.070 Gelatin 0.69 16th layer (protective layer) Emulsion I2 Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 0.050 Dispersion A of organic solid disperse dye A 0. 50 Dispersion B of organic solid disperse dye 0.50 W-1 0.020 H-1 0.40 B-1 (diameter about 1.5 μm) 0.10 B-2 (diameter about 1.5 μm) 0.10 B-3 0.020 S-1 0.20 Gelatin 1.8 In addition to the above, 1,2-benzisothiazolin-3-one (on average 2 g
00 ppm), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm). Further, W-2, W-3, B-4 to B-6, F-1 to F-17, iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained. Preparation of Dispersion A of Organic Solid Disperse Dye ExF-3 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethane sulfonate and 0.5 g of 5% aqueous solution of P-octylphenoxypolyoxyethylene ether (polymerization degree 10) and 700 g were put in a 700 ml pot mill. , Dye ExF
-3 5.0 g and zirconium oxide beads (diameter 1 m
m) 500 ml was added and the contents were dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out and added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion A of a dye. Preparation of Dispersion B of Organic Solid Disperse Dye ExF-2 below was replaced with ExF-3 of Dispersion A above. The following was prepared in the same manner as Dispersion A.

[0203]

[Table 7] In Table 7, (1) Emulsions A2 to K2 are described in JP-A 2-1
According to the example of No. 91938, reduction sensitization was carried out at the time of grain preparation using thiourea dioxide and thiosulfonic acid.

(2) Emulsions A2 to K2 are described in JP-A-3-237.
According to the examples of No. 450, gold sensitization, sulfur sensitization, selenium sensitization and tellurium sensitization are performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer.

(3) Preparation of tabular grains is described in JP-A-1-1.
Low molecular weight gelatin is used according to the Example of 58426.

(4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains and the normal crystal grains having a grain structure by using a high voltage electron microscope.

[0207]

[Chemical 31]

[0208]

[Chemical 32]

[0209]

[Chemical 33]

[0210]

[Chemical 34]

[0211]

[Chemical 35] (Film 202) A film 202 was prepared in the same manner as the film 201 except that the sensitizing dye I-2 of the 11th layer was replaced with an equimolar amount of II-1. (Films 203, 204) Films 203, 204 are the same as Films 201, 202 except that 2 mg of tetrachloropalladium (II) potassium is added to the sixth layer per m ² .
204 was produced. (Film 205) A film 205 was prepared in the same manner as the film 203 except that the sensitizing dye I-2 of the 11th layer was replaced with equimolar amount of ExS-8.

Films 201-205 in the dark 135
Format 24 shots Patrone processed into the same form as in Example 1 and adjusted in humidity, then stored in the transparent plastic hermetic container shown in FIG. 1 or a completely light-shielded hermetic container, capped, and shown in Table 8. Silver halide photographic product 13 ~
21 was produced.

[0213]

[Table 8] As shown in Table 9, silver halide photographic products 13 to 21 were produced with and without light irradiation at 10,000 lux for 24 hours (samples 2001 to 2018 in Table 9). Samples 2001-2018 in the dark at 60 ° C. relative humidity 6
It was stored for 3 days in an atmosphere of 0% RH. Then, the sealed container was opened, the film was taken out in a dark place, and the unexposed portion was exposed in the same manner as in Example 1. Further, the silver halide photographic products 13 to 21 which were not subjected to the above treatment were similarly exposed.

[0214]

[Table 9] Further, the same treatment as in Example 1 was performed.

The density was measured in the same manner as in Example 1, and the changes in film sensitivity and fogging were determined and are shown in Table 9. At this time, the change in sensitivity is indicated by the difference in logarithm of the exposure amount required to increase the fog density by 0.15.

From Table 9, the films 201 and 202 contained in the transparent hermetically sealed plastic containers are 60 ° C. and 60% RH.
If it was exposed to light before being stored for 3 days (Sample 20
01, 2005), it is understood that abnormal fog occurs. On the other hand, the silver halide photographic product 1 of the present invention
In Nos. 7 and 19, this fogging change is small and the effect of the present invention is remarkable.

[Brief description of drawings]

FIG. 1 shows an embodiment of the present invention, and is a view showing a state in which a film with a cartridge is housed in a transparent plastic container.

FIG. 2 is a diagram showing the film with a cartridge of FIG.

[Explanation of symbols]

1 ... Film with cartridge, 2 ... Sealed transparent plastic container, 3 ... Silver halide photographic light-sensitive material, 4 ... Patrone.

Claims (2)

[Claims] 1. A silver halide light-sensitive material comprising a support and at least one silver halide emulsion layer containing a silver halide emulsion sensitized with gold / chalcogen and containing thiocyanate, and said light-sensitive material. A light-shielding container containing a material, and a light-transmissive hermetically-sealed container for housing the light-shielding container. The photosensitive material is incorporated so that a part thereof is located outside the light-shielding container, and A silver halide photographic product having a structure in which a gas can flow between the inside and the outside, wherein a hydrogen cyanide gas scavenger is provided at any position in the sealed container, and a silver halide emulsion of at least one layer of the light-sensitive material The layer has the following general formula (I) or (II)
A silver halide photographic product containing at least one sensitizing dye represented by [Chemical 1] In the formula, R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ may be the same or different, and are a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an aryloxycarbonyl group, It represents an alkoxycarbonyl group, an amino group, an acyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a carboxyl group or an acyloxy group. However, R ₁₁ and R ₁₂ or R ₁₃ and R ₁₄ do not represent a hydrogen atom at the same time. R ₁₅ and R ₁₆ may be the same or different and each represents an alkyl group. R ₁₇ is ST
ERIMOL parameters L, B ₁ , R ₂ , R ₃
And R ₄ is L> 4.11, B ₁ > 1.52, B ₂ >.
It represents an alkyl group or an aryl group such that 1.90, B ₃ > 1.90 and B ₄ > 2.97. X ₁ represents a counter anion, m is 0 or 1, and when forming an intramolecular salt, m = 0. [Chemical 2] In the formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R
₂₈ , R ₂₉ and R ₃₀ have the same meaning as R ₁₁ . R ₃₁ and R
₃₂ has the same meaning as R ₁₅ . Y represents a sulfur atom or a selenium atom. X ₂ has the same meaning as X ₁ . n has the same meaning as m. 2. An emulsion layer or at least one of the other emulsion layers contains at least one sensitizing dye represented by the following general formula (III), general formula (IV) or general formula (V). 1. A silver halide photographic product as described in 1. [Chemical 3] In the above three formulas, R ³ and R ⁴ represent an alkyl group. R
⁵ represents a hydrogen atom, an alkyl group or an aryl group.
X ⁻ represents an anion, n represents an integer for controlling the charge of the entire molecule, and n = when forming an intramolecular salt.
It is 0.