JPH05333485A - Silver halide photographic product - Google Patents

Abstract

PURPOSE:To suppress the deterioration in photographic performance occurring in photoirradiation. CONSTITUTION:This silver halide photographic product consists of a silver halide photosensitive material 4 constituted by providing at least one layer of silver halide emulsion layers contg. silver halide emulsions sensitized with gold chalcogen and thiocyanate on a base, a light shielding container 2 contg. the photosensitive material and light transmittable hermetic containers 5, 6 housing the light shielding container 2. The photosensitive material 4 is built into the light shielding container 2 in such a manner that a part thereof exists on the outer side of the container. In addition, the light shielding container 2 has the structure to allow the flow of gas through the inside and outside of the container. The photographic product has a gaseous hydrogen cyanide scavenger in either positions in the hermetic containers 5, 6. The photosensitive layer nearest the base of the photosensitive material 4 is red sensitive and the base and/or the coating film on the base is so dyed that the visible light entering from the side of the base opposite from the photosensitive layer attenuates to <=1/ 2 before arriving at the red sensitive layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic product in which a light-shielding container containing a silver halide photographic light-sensitive material is housed in a light-transmitting sealed container.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic materials are photosensitive. Therefore, the photosensitive portion is usually shielded from light and stored before being photographed. However, there is a case where the light-shielding portion is not sufficiently shaded due to the design control of the photographic product. .. For example, in the case of the 135 format color film, if the case where the film cartridge is stored is transparent, the inside cartridge can be seen well and the type of film can be confirmed, which is convenient for the user.
Manufacturers do not need to indicate the type of film on the storage case, which has the advantage of reducing costs. Also, the transparent case has the advantage that it can be reused as a small case.

[0003]

Recently, however, a surprising phenomenon has been discovered in which the performance of the film varies depending on the brightness of the product that has been stored for a long time on the shelves in the store of a store. Analysis of this phenomenon revealed that light hits the drawer of the film through the paper box that houses the film case, and a certain type of gas is generated, and this gas diffuses to the part that is shielded from the light. It turns out that the performance is changing. Such a phenomenon has never been known in the art.

An object of the present invention is to provide a silver halide photographic product which does not change in performance even when stored in a place where it is exposed to light.

[0005]

In the 135 format conventionally used, the drawer portion is exposed from the cartridge. This exposed portion is wound around the outer periphery of the cartridge with the base outside and the silver halide photosensitive emulsion layer inside, and light reaches the photosensitive emulsion layer mainly after passing through the base. Therefore, if the light reaching the emulsion layer is attenuated by coloring the base or by providing the antihalation layer, the above-mentioned abnormal fog will be reduced. The present inventor has paid attention to this point together with the above-mentioned intellectual test, and completed the present invention.

That is, the object of the present invention is to provide a halogen comprising (1) a gold / chalcogen-sensitized silver halide emulsion and at least one silver halide emulsion layer containing a thiocyanate on a support. A silver halide light-sensitive material, a light-shielding container containing the light-sensitive material, and a light-transmissive sealed container containing the light-shielding container. The light-sensitive material 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 gas can flow between the inside and the outside of the light-shielding container, having a hydrogen cyanide gas scavenger at any position in the sealed container,
The photosensitive layer closest to the support of the photosensitive material is red-sensitive,
Further, the support and / or the coating film on the support is colored so that visible light incident from the side opposite to the photosensitive layer of the support is attenuated to 1/2 or less before reaching the red-sensitive layer. Achieved by a silver halide photographic product. Also,
(2) A silver halide photographic scavenger containing the halogen gas scavenger, and the hydrogen cyanide gas scavenger or the halogen gas scavenger is present in the silver halide photosensitive material, and (3) the hydrogen cyanide gas scavenger. A silver halide photographic product according to (1) or (2) above, which is an organic or inorganic compound of Pd, is also within the scope of the present invention.

The photosensitive material for photographing is usually contained in an outer box on which a product name is printed, and the above-mentioned phenomenon occurs due to the light transmitted through this box. Therefore, it is possible to mitigate this phenomenon by lowering the light transmittance of the box, but for that purpose, it is necessary to select printing ink with large light absorption, that is, dark printing, and print it on the entire surface, which is eye-catching. It is impossible to adopt it as a design of a film outer box that does not become.

If the outer box is made of a composite material with a light-shielding material instead of a piece of paper, the above problem can be solved, but the cost increase cannot be avoided.

The present invention is an extremely excellent method which produces a remarkable effect at a low cost.

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

As this type of photographic product, for example,
A roll film of the 135 format, which is the mainstream at present, corresponds to this, and one mode thereof is shown in FIG. In FIG. 1, the silver halide photographic light-sensitive material is housed in a metal cartridge 2 as a light-shielding container, with a plastic spool 1 as a mandrel, and a part from a film drawing portion 3 through a light-shielding ribbon.
(4) It has been pulled out. A few cm of film is usually pulled out for the convenience of film loading.
4 corresponds to a position where light can be irradiated, and air flows between the inside and the outside through the gap between the film drawing portion 3 or the cartridge 2.

The cartridge 2 containing the silver halide photographic light-sensitive material is sealed by a cartridge case 5 and a cartridge cap 6 which are hermetically sealed containers. The hermetically sealed container is designed to block gases that are harmful to the photosensitive material and suppress the permeation of excess water vapor, but the permeability of gas and water vapor greatly affects the structure and material of the Patrone case 5 and Patrone cap 6. To be done.

The humidity in the sealed container is preferably kept constant, and in the present invention, the relative humidity is 55% at 25 ° C.
Above, preferably 55% to 70%, and particularly preferably 55% to 65%, the effect of the invention is remarkable. Here, that the humidity in the sealed container is kept constant means that the humidity difference between the outside air and the inside of the case is 20%, and the humidity is 12 at 25 ° C.
A change in humidity inside the case after 10 months is 10% or less.

The equilibrium humidity referred to in the present invention is a value measured at 25 ° C. and can be measured by a conventional method (equilibrium humidity is
For example, it can be measured by a capacitance type humidity measuring instrument such as a Humicap humidity sensor manufactured by VAISALA. ) In the present invention, the sealed container is light transmissive. The light-transmitting property means that the part drawn out from the film drawing-out part can be substantially exposed to external light, and its average transmittance is preferably 1% or more, more preferably 10% or more.

In the present invention, the plastic material which can be used for the sealed container is an addition polymerization of an olefin having a carbon-carbon double bond, a ring-opening polymerization of a small ring compound, a heavy chain between two or more polyfunctional compounds. Condensation (condensation polymerization), polyaddition,
And a phenol derivative, a urea derivative, or a melamine derivative and a compound having an aldehyde can be added and condensed.

The raw material of the plastics material is an olefin having a carbon-carbon double bond, for example, styrene,
α-methylstyrene, butadiene, methyl methacrylate, butyl acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinylcarbazole, N-vinylpyrrolidone, vinylidene cyanide, ethylene and propylene are typical examples. To be 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 are β-propiolactone, ethyleneimine, and tetramethylsiloxane.

Examples of polyfunctional compounds include carboxylic acids such as terephthalic acid, adipic acid and glutaric acid,
Typical examples include toluene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and other isocyanates, ethylene glycol, propylene glycol, alcohols such as glycerin, hexamethylenediamine, tetramethylenediamine, amines such as paraphenylenediamine, and epoxies. It can be cited as an example. Typical examples of the phenol derivative, urea derivative, and melamine derivative include phenol, cresol, methoxyphenol, chlorophenol, urea, and melamine. Further, typical examples of the compound having an aldehyde include formaldehyde, acetaldehyde, octanal, dodecanal, and benzaldehyde. 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.

Examples of the catalyst include (1-phenylethyl) azodiphenylmethane, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis (2-methylpropane), benzoyl peroxide and cyclohexanone peroxy. Side, radical polymerization catalysts such as potassium persulfate, sulfuric acid, toluenesulfonic acid, trifluorosulfuric acid, perchloric acid, trifluoroboron, cationic polymerization catalysts such as tin tetrachloride, n-butyllithium, sodium / naphthalene, 9- Anionic polymerization catalysts such as fluorenyllithium and phenylmagnesium bromide, triethylaluminum / tetrachlorotitanium type Ziegler-Natta type catalysts,
Sodium hydroxide, potassium hydroxide and potassium metal 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, and tetrahydrofuran.

When molding plastics as the sealed container in the present invention, a plasticizer is mixed with the plastics as needed. Examples of the plasticizer include trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sebacate, methyl amyl ketone, nitrobenzene, γ-valerolactone, di-n-octyl succinate, bromonaphthalene, and butyl palmitate. It is a thing.

In the present invention, specific examples of the plastic material used for the hermetically sealed container are shown below, but the invention is not limited thereto.

P-1 Polystyrene P-2 Polyethylene P-3 Polypropylene P-4 Polymonochlorotrifluoroethylene P-5 Vinylidene chloride resin P-6 Vinyl chloride resin P-7 Vinyl chloride-vinyl acetate copolymer resin P-8 Acrylonitrile -Butadiene-styrene copolymer resin P-9 methyl methacrylic resin P-10 vinyl formal resin P-11 vinyl butyral resin P-12 polyethylene phthalate P-13 teflon P-14 nylon P-15 phenol resin P-16 melamine resin In the invention, particularly preferable plastic materials are, for example, polystyrene, polyethylene and polypropylene.

The light-shielding container of the present invention includes a cassette for sheet film, but is typically a cartridge for roll film. Patrone for roll film
It has a spool shaft around which the silver halide photosensitive material is wound in a roll, and a film outlet for loading and unloading this photosensitive material,
And a cartridge body that stores the spool rotatably around its axis. In order to shield light, the spool has a flange, and the spool is attempted to enter the container through the gap between the spool shaft and the cap provided on the side edge of the typically cylindrical body of the cartridge body. Block the external light. Further, it is preferable that a light-shielding member is provided at the exit of the film so that the film can be pulled out and rewound smoothly. This light-shielding member has
No. 526.

The attenuation factor of visible light in the present invention is 40
It means the average value of the attenuation rate in the range of 0 nm to 700 nm. Colored organic materials such as colored couplers and dyes in the antihalation layer or an intermediate layer provided between the antihalation layer and the photosensitive emulsion layer will also contribute to the attenuation of visible light.

As a method for coloring the coating film on the support, there are a method in which an oil-soluble dye is dissolved in a high boiling point oil and emulsified and dispersed, and a method in which a water-soluble dye is fixed by using a mordant. It is disclosed in Japanese Unexamined Patent Publication No. 62-103641.

Visible light can be attenuated by incorporating a dye into the support of the silver halide light-sensitive material itself or providing an antihalation layer. For this purpose, for example, carbon black or various dyes such as oxonol dyes, azo dyes, arylidene dyes, styryl dyes, anthraquinone dyes,
Merocyanine dyes and tri- or diallylmethane dyes can be used. As the binder of the carbon black dye, cellulose acetate (di or mono), polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyvinyl formal, polymethacrylic acid ester, polyacrylic acid ester, polystyrene, styrene / maleic anhydride copolymer, poly Vinyl acetate, vinyl acetate / maleic anhydride copolymers, methyl vinyl ether / maleic anhydride copolymers, polyvinylidene chloride, and derivatives thereof can be used. A specific example of such a dye is a yellow dye having the following structural formula.

[0028]

[Chemical 1]

[0029]

[Chemical 2] The hydrogen cyanide gas scavenger 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.
Therefore, the scavenger should not release any substance that adversely affects the silver halide light-sensitive material as a result of capturing hydrogen cyanide gas. Suitable hydrogen cyanide gas scavengers can be selected from noble metal inorganic or organic compounds. Particularly preferred are palladium (II or IV) and platinum (II or IV) compounds.
Gold (I or III) compounds are also preferred. Rhodium (II
I), iridium (III or IV) and osmium (II,
Compounds of III or IV) are also effective, but higher amounts are required to achieve comparable effects.

Specific examples of useful inorganic or organic noble metal compounds include, for example, Gmelin Handbook (Gmelin).
Handbook), commercial 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.

Typical examples of useful palladium compounds include 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 (salicylat) palladium (II) acid salt,
Bis (dithiooxalato-S, S ') palladium (II)
Acid salt, trans-dichlorobis (thioether) palladium (II), tetraamminepalladium (II) salt, dichlorodiamminepalladium (II), dibromodiamminepalladium (II), oxalatodiamminepalladium (II), dinitrodiamminepalladium (II), Bis (ethylenediamine) palladium (II) salt, dichloroethylenediaminepalladium (II) salt, bis (2,2'-bipyridine) palladium (II) salt, bis (1,10-phenanthroline) palladium (II) salt, tetranitropalladium ( II) acid salt, bis (glycinato) palladium (I
I), 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) is mentioned.

Typical examples of useful platinum compounds include platinum (II) chloride, platinum (IV) chloride and hexafluoroplatinum (I
V) acid salt, tetrachloroplatinate (II) acid salt, hexachloroplatinum (IV) acid salt, trichlorotrifluoroplatinum (IV) acid salt, tetrabromoplatinum (II) acid salt, hexabromoplatinum (IV) acid salt, dibromodichloro acid salt Platinum (II) acid salt, hexahydroxoplatinum (IV) acid salt, bis (oxalato) platinum (II) acid salt, dichlorobis (oxalato) platinum (IV) acid salt, bis (thiooxalato) platinum (II) acid salt, bis (Acetylacetonato) platinum (II), bis (1,1,1,
5,5,5-hexafluoro-2,4-pentanedionato) platinum (II), bis (1,1,1-trifluoro-)
2,4-pentanedionato) platinum (II), tetrakis (thiocyanato) platinum (II) salt, hexakis (thiocyanato) platinum (IV) salt, bis {(Z) -1,2-dicyanoethylene-1, 2-dithiolato} platinum (II) acid salt,
Dichlorobis (diethylsulfide) platinum (II), tetrachlorobis (diethylsulfide) platinum (IV), bis (glycinato) platinum (II), dichloroglycinatoplatinum (II) acid salt, dichlorobis (triethylphosphine) platinum (II) , Chlorohydridobis (triethylphosphine) platinum (II), tetraammineplatinum (II) salt, tetrachloroplatinum (II) salt, dichlorodiammineplatinum (I
I), trichloroammine platinum (II) salt, hexaammine platinum (IV) salt, chloropentammine 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 (pyridine) platinum ( II) salt, dichlorobis (pyridine) platinum (I
I), bis (2,2′-bipyridine) platinum (II) salt, tetranitroplatinate (II) salt, chlorotrinitroplatinum (I)
I) acid salt, dichlorodinitroplatinum (II) acid salt, dibromodinitroplatinum (II) acid salt, hexanitroplatinum (IV) acid salt, chloropentanitroplatinum (IV) acid salt, dichlorotetranitroplatinum (IV) acid salt , Trichlorotrinitroplatinate (IV), tetrachlorodinitroplatinate (IV), dibromodichlorodinitroplatinate (IV), trichloro (ethylene) platinum (II), di-μ-chloro-bis { Chloro (ethylene) platinum (II)}, trans-dichloro (ethylene) (pyridine) platinum (II), bis [bis (β-mercaptoethylamine) nickel (II) -S,
S ″-] platinum (II) salts, and dichlorodicarbonyl platinum (II).

Gold (I or III), Rhodium (III), Iridium (III or IV) and Osmium (II, III or
The compounds of (III) can also be mentioned in the same manner.
Chloride, potassium hexachloroiridate (IV),
Included are potassium tetrachloroiridate (III) and potassium hexachloroosmate (IV).

The inorganic or organic compound of the noble metal is not limited to the above-mentioned specific examples as long as the effects of the present invention can be obtained.

In the present invention, the hydrogen cyanide gas scavenger may be located anywhere within the sealed container of the photographic product. It may be formed by coating or kneading on the inner surface of the sealed container, or may be formed by coating or kneading on the parts forming the light-shielding container. Particularly preferably, the hydrogen cyanide gas scavenger is present in the photographic light-sensitive material. The photographic light-sensitive material usually comprises a support, a back layer, an emulsion layer, a surface protective layer, an intermediate layer and an antihalation layer. In the present invention, a hydrogen cyanide gas scavenger is directly added to these layers for coating. Alternatively, it may be applied alone with a suitable solvent or binder.

As a method for adding the hydrogen cyanide gas scavenger, a method usually used when adding an additive to a photographic light-sensitive material can be applied. For example, the water-soluble compound is an aqueous solution having a suitable concentration, and the water-insoluble or sparingly soluble compound is a suitable organic solvent miscible with water, for example,
Alcohols, glycols, ketones, esters,
Among the amides, they can be dissolved in a solvent that does not adversely affect the photographic properties and added as a solution.

The back layer, emulsion layer, surface protective layer, intermediate layer and antihalation layer are usually dispersions with binders, but useful binders include naturally occurring polymeric vehicles such as gelatin and cellulose derivatives. And synthetic vehicles such as polyvinyl alcohol and its derivatives, acrylate and methacrylate polymers, butadiene-styrene polymers and similar materials. When the hydrogen cyanide gas scavenger is directly added to these layers, it is necessary to carefully select the conditions such as the concentration and pH of the binder according to the type 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 increase remarkably depending on the conditions. For example, regarding the interaction between palladium (II) ions and gelatin, the Journal of the Photographic Society of Japan, Vol. 34, page 159 (1971) Keiichi Tanaka, The Photographic Society of Japan, Volume 37, page 133 (1974) Keiichi Tanaka, The Photographic Society of Japan, Volume 39. 73
Page (1976) Keiichi Tanaka, Journal of Photographic Science Volume 21 Page 134 (197)
3) Keiichi Tanaka and Journal of Photographic Science Vol. 26, page 222 (1978) Keiichi Tanaka. Since the palladium (II) ion has a strong bond with the amide bond and the amino acid residue of gelatin, it may form a lumpy foreign substance of gelatin under some conditions. It is preferable to select and use.

The addition amount of the hydrogen cyanide gas scavenger in the present invention should be determined within a range in which the effect of the present invention is remarkably exhibited, but preferably 1 / mol of thiocyanate contained in a portion which can be irradiated with light. 10
More than a mole. More preferably 1/2 mole or more and 10 per mole of thiocyanate contained in the portion that can be irradiated with light.
It is 0 mol or less, particularly preferably 1 mol to 10 mol.

The halogen gas scavenger in the present invention is a compound that converts the halogen gas generated when the photosensitive material is irradiated with light into a photographically inactive substance. Therefore, the scavenger should not release a substance that adversely affects the silver halide light-sensitive material as a result of capturing the halogen gas.

It is generally known that gelatin acts as a halogen gas scavenger, and that its action is also a function of system pH and pAg. However, in the present invention, it is preferable that the following compound is present as a halogen gas scavenger at any position in the sealed container of the photographic product.
That is, preferred compounds as the halogen gas scavenger in the present invention include, for example, sulfide compounds, nitrites, semicarbazides, sulfites, hydroquinones, ethylenediamine, acetone semicarbazone,
It is p-hydroxyphenylglycine. Particularly preferred compounds include compounds represented by the following general formula (H).

[0041]

[Chemical 3] In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a group capable of substituting for a benzene nucleus.

In the general formula (H), the substituent is
A halogen atom (for example, fluorine, chlorine, bromine), an alkyl group (for example, methyl, ethyl, n-propyl, t-butyl, n-amyl, i-amyl, n-octyl, n-dodecyl, n-octadecyl, Particularly preferably having 1 to 32 carbon atoms), alkenyl group, aryl group, acyl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylacylamino group,
Arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group,
An arylsulfonamide group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylacyloxy group and an arylacyloxy group are preferable.

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

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

[0045]

[Chemical 4]

[0046]

[Chemical 5]

[0047]

[Chemical 6]

[0048]

[Chemical 7]

[0049]

[Chemical 8] A halogen gas scavenger such as hydroquinone may be added at any position of a protective layer, an intermediate layer, a non-photosensitive layer such as a back layer provided on the side opposite to the emulsion surface of the film, or a silver halide emulsion layer. .. More preferably, it is added to a layer more distant from the support on the emulsion layer side of the support.

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

Examples of the compound capable of generating hydrogen cyanide gas directly or indirectly by irradiating the photographic product with light include inorganic compounds such as selenocyanate, cyano complex salt and selenocyano complex salt and organic compounds having a cyano group. ..

Examples of the organic compound having a cyano group include the following.

[0053]

[Chemical 9]

[0054]

[Chemical 10]

[0055]

[Chemical 11]

[0056]

[Chemical formula 12]

[0057]

[Chemical 13]

[0058]

[Chemical 14]

[0059]

[Chemical 15]

[0060]

[Chemical 16]

[0061]

[Chemical 17]

[0062]

[Chemical 18]

[0063]

[Chemical 19]

[0064]

[Chemical 20]

[0065]

[Chemical 21]

[0066]

[Chemical formula 22]

[0067]

[Chemical formula 23]

[0068]

[Chemical formula 24]

[0069]

[Chemical 25] The photographic light-sensitive material in the present invention has a silver halide emulsion containing a gold / chalcogen sensitized silver halide emulsion and a thiocyanate-containing silver halide emulsion layer on a support. The support is, for example, Research Disclosure (RD) No. 17
643, page 28, R.M. D. No. 18716 of 64
Page 7, right column to page 648, left column, and R. D. N
o. 307105, page 879.

The gold / chalcogen sensitization is performed with gold and at least one of a selenium sensitizer, a sulfur sensitizer and a tellurium sensitizer. That is, gold / sulfur sensitization, gold / selenium sensitization, gold / tellurium sensitization, gold / sulfur / selenium sensitization, gold / sulfur / tellurium sensitization, gold / selenium / tellurium sensitization and gold / sulfur / selenium sensitization. It can be selected from among the tellurium sensitizations.

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

I. Colloidal metal selenium II. Organic selenium compound (selenium atom double-bonded to carbon atom of organic compound by covalent bond) a. Isoselenocyanates Aliphatic isoselenocyanates such as allyl isoselenocyanates b. Selenoureas (including enol type) For example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, dioctyl, tetraoctyl, N- (β-carboxyethyl) -N ', N'-dimethyl, N,
Aliphatic selenoureas such as N-dimethyl, diethyl and dimethyl; aromatic selenoureas having one or more aromatic groups such as phenyl and tolyl; heterocycles having heterocyclic groups such as pyridyl and benzothiazolyl Formula selenourea c. Selenoketones, for example, selenoacetone, selenoacetophenone, selenoketone having an alkyl group bonded to> C = Se, selenobenzophenone d. Selenoamides For example, selenoacetamide e. Selenocarboxylic acids and esters For example, 2-selenopropionic acid, 3-selenobutyric acid, methyl
3-Selenobutyrate III. Other a. Selenides For example, diethyl selenide, diethyl diselenide,
Triphenylphosphine selenide b. Selenophosphates For example, tri -p-tolyl selenophosphate, tri -n-
Butylselenophosphate Unstable selenium compounds have been described above in terms of preferred types.
These are not limiting. Speaking of those skilled in the art as unstable selenium compounds as sensitizers for photographic emulsions,
The structure of the compound is not so important as long as selenium is unstable, and the organic part of the selenium sensitizer molecule carries selenium and has no role except that it is present in the emulsion in an unstable form. Is generally understood. In the present invention, the unstable selenium compound having such a broad concept is advantageously used.

Japanese Patent Publication No. 46-4553, Japanese Patent Publication No. 52-3
Selenium sensitization using the non-labile selenium sensitizers described in JP-B No. 4491 and JP-B-52-34492 can also be used. Examples of the non-labile selenium compound include selenious acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles, diaryl selenides, diaryl diselenides, 2-thioselenazolidinediones, and 2-selenooxo. Included are ginthion and their derivatives.

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

These selenium sensitizers are added at the time of chemical sensitization by dissolving them in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, but preferably added before the start of chemical sensitization. To be done. The selenium sensitizer used is not limited to one kind, and two or more kinds of the above selenium sensitizers can be used in combination. Particularly, the combined use of an unstable selenium compound and a non-unstable selenium compound is preferable.

The addition amount of the selenium sensitizer used in the present invention varies depending on, for example, the activity of the selenium sensitizer used, the kind and size of silver halide, the temperature and time of ripening, and preferably, 1 x 1 per mol of silver halide
It is 0 ^-8 mol or more, and more preferably 1 × 10 ^-7 mol or more and 1 × 10 ^-4 mol or less. When the selenium sensitizer is used, the temperature of chemical ripening is preferably 45 ° C. or higher,
It is more preferably 50 ° C. or higher and 80 ° C. or lower. pAg
And pH are arbitrary. For example, the effect of the present invention can be obtained in a wide range of pH from 4 to 9.

In the present invention, selenium sensitization is more effective when carried out in the presence of a silver halide solvent.

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

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

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

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

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

As the gold sensitizer for gold sensitization in the present invention, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, and pyridyl trichlorogold.

The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is 1 × 10 1 per mol of silver halide.
^It is preferably ^-7 mol or more and 1 x 10 ^-4 mol or less.

In the light-sensitive material of the present invention, thiocyanate is used in combination during the sensitization of gold and chalcogen. As the thiocyanate, for example, ammonium salt, potassium salt and sodium salt are preferably used.

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 gold.
It is more preferably used not only during chalcogen sensitization but also during grain formation or during the desalting step. For the use of thiocyanate in grain formation, see US Pat. No. 3,320,
069 and 4,434,226.

The silver halide light-sensitive material of the present invention comprises
The ISO sensitivity is preferably 100 to 3200,
It is more preferably 400 to 3200.

The light-sensitive material of the present invention may have at least one blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer on a support. The number of emulsion layers and non-photosensitive layers is not particularly limited. A typical example is that at least one photosensitive layer having color sensitivity to blue light, green light, and red light, respectively, is provided on a support, and the color sensitivity is substantially the same. It is a silver halide photographic light-sensitive material having a plurality of silver halide emulsion layers with different degrees. In the silver halide color photographic light-sensitive material of the present invention, the light-sensitive layer closest to the support is red-sensitive.

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 is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the sensitivities are gradually decreased toward the support, and a non-photosensitive layer may be provided between each silver halide emulsion layer. Further, JP-A-57-112751, JP-A-62-20035.
No. 0, No. 62-206541, No. 62-206543
As described in the publications, 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, a low-sensitivity blue photosensitive layer (BL) / a high-sensitivity blue photosensitive layer (B
H) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH
/ RL, or BH / BL / GH / GL / RL / R
It can be installed in the order of H or the like.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order 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, a silver halide emulsion layer having the highest photosensitivity in the upper layer, a silver halide emulsion layer having a lower photosensitivity in the middle layer, and a middle layer in the lower layer. An arrangement in which a silver halide emulsion layer having a lower photosensitivity is disposed and three layers having different sensitivities are sequentially lowered toward the support 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. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer.

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

In order to improve the color reproducibility, US Pat.
No. 63-89850, 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 layers such as L and RL, adjacent to or close 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 preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or iodochloroodor containing about 30 mol% or less of silver iodide. It is silver oxide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in a photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having 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 silver halide may be fine grains of about 0.2 μm or less, 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.
716 (November 1979), page 648, ibid. Thirty
7105 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemie et.
Phisique Photographique,
Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duf).
fin, Photographic Emulsion
Chemistry (Focal Press, 19
66)), "Production and Coating of Photographic Emulsions" by Zelikmann et al.,
Published by Focal Press, Inc. (VL Zelikman e
tal. , Making and Coating P
photographicEmulsion, Focal
It can be prepared using the method described in Press, 1964).

For example, US Pat. No. 3,574,628.
No. 3,655,394 and British Patent No. 1,41
The monodisperse emulsion described in 3,748 is 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), Vol. 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 may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside the grain, or a type having a latent image both on the surface and inside. It must be a negative emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-
No. 133542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

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

In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion in the same layer. Can be mixed and used.

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

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
It is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are within ± 40% of the average grain size). It is preferable that the particles have a particle size of

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

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

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 0.2 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 need not be chemically 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, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains.

[0115] In the present invention, the coating amount of silver in the light-sensitive material is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above-mentioned 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. Fogging prevention pages 24 to 25 pages 649 right column 868 to 870 pages agents and stabilizers 6. Light absorber, page 25-26, page 649, right column, page 873, filter dye, ~ page 650, left column, ultraviolet absorber 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 left column 874-875 pages 10. Binder page 26 page 651 left column 873 to 874 page 11. Plasticizers and 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 876-877 Page 14 Inhibitor 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is immobilized 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 added to the light-sensitive material.

The light-sensitive material of the present invention contains the mercapto compounds described in US Pat. Nos. 4,740,454, 4,788,132, JP-A-62-18539 and JP-A-1-283551. It is preferable to contain it.

The light-sensitive material of the present invention is described in JP-A-1-
It is preferable to include a compound described in No. 106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

The light-sensitive material of the present invention includes the international publication W.
O88 / 04794, Dyes or EP317,30 dispersed by the method described in JP-A-1-502912
8A, U.S. Pat. No. 4,420,555, JP-A 1-2
It is preferable to incorporate the dye described in No. 59358.

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

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

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and examples thereof include US Pat. Nos. 4,310,619 and 4,35.
No. 1,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432, 3,725,067, Research Disclosure No. 24220 (198
June 4), JP-A-60-33552, Research Disclosure No. 24230 (June 1984)
Mon), JP-A-60-43659, JP-A 61-72238.
No. 60-35730, No. 55-118034,
No. 60-185951, U.S. Pat. No. 4,500,63.
No. 0, No. 4,540, 654, No. 4,556, 6
No. 30, those described in International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers. Examples thereof include US Pat. Nos. 4,052,212 and 4,146,396.
No. 4,228,233, No. 4,296,200
No. 2, No. 2,369,929, No. 2,801,17
No. 1, No. 2,772, 162, No. 2, 895, 8
No. 26, No. 3,772,002, No. 3,758,
No. 308, No. 4,334, 011 and No. 4,32
7,173, West German Patent Publication No. 3,329,729,
European Patent Nos. 121,365A and 249,453A
U.S. Pat. Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,775,616, No. 4,4
No. 51,559, No. 4,427,767, No. 4,
Those described in 690,889, 4,254,212, 4,296,199 and JP-A-61-42658 are preferable. Further, JP-A-64-553,
No. 64-554, No. 64-555, and No. 64-556.
The pyrazoloazole couplers described in US Pat. No. 4,818,672 and the imidazole couplers described in US Pat. No. 4,818,672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
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.

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

Colored couplers for correcting unwanted absorption of color-forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. 30710
5, section VII-G, U.S. Pat. No. 4,163,670,
Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,9
29, 4,138,258, British Patent 1,1.
Those described in No. 46,368 are preferable. Further, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are RD1 described above.
7643, Item VII-F and No. 307105, V
Patents described in paragraph II-F, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184248.
Nos. 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

For example, R. D. No. 11449 and 2
The bleaching accelerator releasing couplers described in JP-A No. 4241 and JP-A No. 61-201247 are effective in shortening the processing time having a bleaching ability, and particularly, the light-sensitive material using the tabular silver halide grains described above. The effect is great when it is added to. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59.
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
The compounds described in JP-A-45687, which release a fogging agent, 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 which can be used in the light-sensitive material of the present invention include US Pat.
Competitive couplers described in U.S. Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60
No. 185950, JP-A No. 62-24252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A, 313, 313. No. 308A, a coupler releasing a dye that undergoes color recovery after release, a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, Examples thereof include couplers releasing a fluorescent dye described in US Pat. No. 4,774,181.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl)). Phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2
-Ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2
-Ethylhexyl-p-hydroxybenzoate), amides (e.g., N, N-diethyldodecane amide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert)
-Amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples thereof include aniline derivatives (for example, N, N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C or higher and about 1
An organic solvent at 60 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

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

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

Various color light-sensitive materials can be applied to the invention. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

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

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less,
18 μm or less is more preferable, and 16 μm or less is particularly preferable. The film swelling speed T _1/2 is preferably 30 seconds or less,
20 seconds or less is more preferable. The film thickness is 25 ° C and relative humidity is 5
Means the film thickness measured under 5% humidity control (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A. Green (A.
Green) et al., Photographic Science and Engineering (Photogr. Sc)
i. Eng. ), Vol. 19, No. 2, pp. 124-129, and can be measured by using a swellometer (swelling meter) of the type. T _1/2 was treated with a color developing solution at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness that reaches at times is defined as the saturated film thickness, and is defined as the time until it reaches 1/2 of the saturated film thickness.

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

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 1
50 to 500% is preferable.

The color photographic light-sensitive material of the present invention is the same as RD. No. 17643, pages 28-29, ibid.
18716, page 651, left column to right column, and the same No. Thirty
The development processing can be carried out by a usual method described in 7105, pages 880 to 881.

The color developing solution used for the development processing of the light-sensitive material in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3- Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline, 4-amino-3-methyl-N- Methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-
Amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-
Ethyl-N- (3-hydroxypropyl) aniline, 4
-Amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl -N-methyl-N- (4-
Hydroxybutyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4
-Hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-
Bis (4-hydroxybutyl) aniline, 4-amino-
3-methyl-N, N-bis (5-hydroxypentyl)
Aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4
-Hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates , Hydrochloride or p-toluenesulfonate. Among these, especially 3-methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4
-Hydroxybutyl) aniline and their hydrochlorides,
P-toluenesulfonate or sulfate is preferred.
These compounds may be used in combination of two or more depending on the purpose.

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

When the reversal process is carried out, the black and white development is usually carried out before the color development. This black and white developer contains dihydroxybenzenes such as hydroquinone,
Known black-and-white developing agents such as 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol 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 L (liter) or less per 1 square meter of the light-sensitive material, and it is possible to reduce the bromide ion concentration in the replenishing solution by 50%.
It can be 0 ml or less. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

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

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

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, for example, polyvalent metal compounds such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents are iron (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid,
Complex salts of aminopolycarboxylic acids such as glycol ether diamine tetraacetic acid, citric acid, tartaric acid, or malic acid 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 iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but 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 prebaths.
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 Declosure No. 17129 (July 1978) and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506 and JP-A-52-208.
32, No. 53-32735, U.S. Pat. No. 3,70.
Thiourea derivatives described in 6,561; West German Patent No. 1,
127,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410, and 2,74.
No. 8,430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40, 943 and 49-59, 644.
No. 53-94, 927, 54-35, 727.
No. 55, No. 55-26, 506, No. 58-163, 940.
Compounds described in No. 1; bromide ions and the like can be used. Of these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and particularly, US Pat.
893,858, West German Patent 1,290,812,
The compounds described in JP-A-53-95630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 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 photographing.

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

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Is most commonly used, with ammonium thiosulfate being the most widely used. It is also preferable to use a thiosulfuric acid solution in combination with a thiocyanate, a thioether compound, thiourea or the like. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids or 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 fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2- It is preferable to add 0.1 to 10 mol / L of an imidazole such as 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 preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

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

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in Nos. 1258 and 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide photographic light-sensitive material in the present invention is generally subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range.
Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society
y of Motion Picture and T
Elevision Engineers, Volume 64,
It can be determined by the method described on pages 248-253 (May 1955 issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but bacteria are propagated due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. The problem arises. In the processing of the light-sensitive material in the present invention, as a solution to such a problem, JP-A-62-288,838 has been proposed.
The method of reducing calcium ion and magnesium ion described in No. 10 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and benzotriazole are also described by Hiroshi Horiguchi in "Bacterial and Antifungal Agents". Chemistry "(1986)
Sankyo Publishing Co., Ltd., Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Antibacterial and Antifungal Encyclopedia" (1986). Can also be used.

In the present invention, the pH of the washing water in the processing of the light-sensitive material is 4-9, preferably 5-8. The washing water temperature and washing time may be variously set depending on the characteristics and intended use of the light-sensitive material, but generally 15 to 45 ° C. and 20 seconds to
A range of 10 minutes, preferably 30-40 seconds at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, Japanese Patent Laid-Open No. 57-8
No. 543, No. 58-14834, No. 60-22034.
All known methods described in No. 5 can be used.

In some cases, the washing treatment may be followed by further stabilizing treatment. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as the final bath of a color light-sensitive material for photographing, may be used. Can be mentioned. 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 resulting from the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

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

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, No. 3,342,599, Research Disclosure No. 14, 850 and the same No. 15,159
Examples thereof include the Schiff base type compounds described in JP-A No. 13-324, the aldol compounds described in JP-A No. 13,924, the metal salt complexes described in US Pat. No. 3,719,492, and the urethane compounds described in JP-A-53-135628. ..

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
Typical compounds are JP-A Nos. 56-64339 and 57-57.
144447 and 58-115438.

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

[0162]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

On the undercoated cellulose triacetate film support, each layer having the composition shown below was coated in multiple layers,
Sample 11, which is a multilayer color photographic material, was prepared. (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.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20 Second Layer (Intermediate Layer) Emulsion G Silver 0.065 2,5-di -T-Pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87 4th layer (medium sensitivity red emulsion layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC -1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC- 4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20 6th layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10 7th layer (low-sensitivity green emulsion layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM -1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 Eighth layer (medium sensitivity green emulsion layer) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS- ^{5 2.2 × 10 -4 ExS-6} 8.4 × 10 -4 ExM-2 0.13 ExM-3 0.030 xY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 -3 Gelatin 0.90 9th layer (high sensitivity green-sensitive emulsion layer) Emulsion E silver ^{1.25 ExS-4 3.7 × 10 -5} ExS-5 8.1 × 10 -5 ExS -6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44 10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60 11th layer (low sensitivity blue-sensitive emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS -1 0.28 Gelatin 1.10 12th layer (medium speed blue emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78 13th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86 14th layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00 Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 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, anti-mold
To improve antibacterial property, antistatic property and coating property, W-
1 to W-3, B-4 to B-6, F-1 to F
-17, iron salt, and lead salt are contained.

Emulsions A to G used in the above composition
Are emulsions shown in Table 1 below.

[0166]

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

[0167]

[Table 2]

[0168]

[Chemical formula 26]

[0169]

[Chemical 27]

[0170]

[Chemical 28]

[0171]

[Chemical 29]

[0172]

[Chemical 30]

[0173]

[Chemical 31]

[0174]

[Chemical 32]

[0175]

[Chemical 33]

[0176]

[Chemical 34]

[0177]

[Chemical 35]

[0178]

[Chemical 36]

[0179]

[Chemical 37]

[0180]

[Chemical 38]

[0181]

[Chemical Formula 39]

[0182]

[Chemical 40]

[0183]

[Chemical 41]

[0184]

[Chemical 42] Samples 12 to 15 in which the coating amount of the first layer of black colloidal silver was changed as shown in Table 3 with respect to Sample 11 were prepared. Further, samples 16 to 20 were prepared by adding 2 mg / m ² of hydrogen cyanide gas scavenger to the intermediate layer of the sixth layer with respect to samples 11 to 15.

The above film samples 11 to 20 were photographed in 135 format 24 sheets and processed into patrone form, respectively, to obtain photographic product samples 101 to 110. After humidity adjustment to 25 ° C.-60%, in a dark place in a transparent patrone case. Stowed.

The ratio of the area of the light-shielded portion housed in the cartridge to the area of the film drawing portion is 1:
It is 0.05.

These photographic product samples 101 to 110 were irradiated with light at 10,000 lux for 24 hours, and then at 60 ° C.-6.
The film was stored under a condition of 0% for 3 days, and the film in the light-shielded portion contained in the cartridge was cut out and subjected to sensitometry. The treatment of each film after light irradiation was in accordance with the treatment method described later. The results are shown in Table 3.

Table 3 Photographs Used CN gas Colloid product for green layer of light Film Scavenging Silver coating amount Attenuation rate Fog Sample name Jar increase 101 11 None 0.18 1/10 0.35 102 12 None None 0.06 1/5 0.50 103 13 None 0.03 1/2 0.65 104 14 None 0.006 1 / 1.5 0.80 105 15 None None 0 1/1 1.06 106 16 Pd 0.18 1/10 0. 06 107 17 Pd 0.06 1/5 0.06 108 18 Pd 0.03 1/2 0.06 109 19 Pd 0.006 1 / 1.5 0.08 110 20 Pd 0 1/1 0.10 or more From the above, it can be seen that the effect is remarkable when the attenuation rate is 1/2 or more.

In this example, the processing performed on the photographic product sample after irradiation with light was as follows.

[0190] Next, the composition of the treatment liquid will be described.

(Color Developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-3.0 diphosphonic acid Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Iodination Potassium 1.5 mg Hydroxylamine sulfate 2.4 4- [N-ethyl-N-β-hydroxyethyl 4.5 amino] -2-methylaniline sulfate Add water 1.0 liter pH 10.05 (bleach Liquid) (Unit: g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 3-Mercapto-1,2,4-triazole 0.08 Ammonium bromide 140.0 Ammonium nitrate 30 0.0 Ammonia water (27%) 6.5 ml Water was added to 1.0 liter pH 0.0 (fixing solution) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution 290.0 ml (700 g / liter) Water was added to 1.0 liter pH 6.7 (Stable Liquid) (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl 0.2 ether (Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazole-1-0.75 ylmethyl) piperazine Water was added to 1.0 liter pH 8.5

[0192]

As described above, the silver halide photographic product according to the present invention does not show deterioration of photographic performance such as increase in fog even when stored in a place where light is irradiated.

[Brief description of drawings]

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

[Explanation of symbols]

1 ... Spool, 2 ... Patrone, 3 ... Film drawer,
5… Patrone case, 6… Patrone cap.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 1/825

Claims (2)

[Claims] 1. A silver halide light-sensitive material comprising a support and at least one silver halide emulsion layer containing a gold / chalcogen-sensitized silver halide emulsion and a thiocyanate, and the light-sensitive material. And a light-transmissive sealed container that houses the light-shielding container. The photosensitive material is built in so that a part of the light-sensitive material is located outside the light-shielding container, and inside the light-shielding container. In a silver halide photographic product having a structure in which a gas can flow to the outside, a hydrogen cyanide gas scavenger is provided at any position in the sealed container, and the light-sensitive layer closest to the support of the light-sensitive material is red-sensitive. And on the support and / or on the support such that visible light incident from the side opposite to the side on which the photosensitive layer is provided of the support is attenuated to 1/2 or less before reaching the red-sensitive layer. Application of Silver halide photographic product but characterized in that it is colored. 2. A photographic product according to claim 1, wherein a hydrogen cyanide gas or a halogen gas scavenger is present in the silver halide light-sensitive material.