JPH08272059A - Package of multilayer silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a package of the multilayer silver halide color photographic sensitive material small in fluctuation of photographic performances and superior in stability against time layer by using a specified compound for at least one silver halide emulsion layer of the photosensitive material. CONSTITUTION: The package of the multilayer silver halide color photographic sensitive material has a volume of 50-140cm<3> and contains in at least one of the silver halide photosensitive layers the compounds represented by formulae I-V in which Ra1 is an alkyl or alkenyl group or the like; Ra2 is an H atom or a group same as Ra1 ; X is a heterocyclic group; Rb1 is an akyl or alkenyl or aryl group; Y is a nonmetallic atomic group necessary to form a 5-membered ring together with the -N=Cgroup; each of Rd1 and Rd2 is an alkyl or aryl group; and each of Re1 and Re2 is a hydroxylamino or hydroxyl group or the like.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a multilayer silver halide color photographic light-sensitive material package. In particular, the present invention relates to a multi-layer silver halide color photographic light-sensitive material package excellent in storage stability of a photographic light-sensitive material stored in a package.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material, especially a color light-sensitive material for photographing, is left in various environments for a long time from the manufacture of the light-sensitive material to photographing and development. There is a demand for a light-sensitive material that has little fluctuation and stable finish quality. On the other hand, in recent years, as for the color photographic material for photographing, as represented by, for example, "Shooting Run", the demand for a film unit with a lens has increased dramatically. Further, various lens-fitted photo film units have been proposed in which these mechanisms are improved, including modification of the filming area of the photo film. These lens-fitted film units use various dry batteries for stroboscopic light emission, which is used as an optical auxiliary mechanism of the camera mechanism.

However, in a lens-fitted film unit using a dry battery for stroboscopic light emission, these are hermetically sealed and packaged, and after a long period of time, the same light-sensitive material containing no dry battery is hermetically packaged under the same conditions and aged for the same period. In contrast, it was found that the photographic performance fluctuated, for example, the fog increased and the sensitivity increased, and especially when the volume of the sealed package was small, the fluctuation was large, and the film unit with lens itself was smaller than before. It was also revealed that the fluctuations were large when the volume of the packaging was reduced to a small volume. further,
It was also found that the photographic performance of the photographic light-sensitive material having a magnetic layer containing a ferromagnetic powder also fluctuates greatly, and the fluctuation becomes larger when the volume of the package is small. It is well known that a part of the compounds represented by the general formulas (AI) to (AV) of the present invention is added to the photographic photosensitive layer. For example, U.S. Patent Nos. 4,339,515 and 4,3.
No. 30,606, a light-sensitive material containing a compound similar thereto is described. However, all of these patents are for improving the image storability of the dye formed by the coupling of the coupler and the oxidized product of the developing agent, and have different constitutions and effects from the present invention. Further, in JP-A-59-162546, the latent image storability is improved by using a latent image storability in combination with a compound having an active vinyl group. It is disclosed that fog is reduced when used in combination with a silver halide emulsion. However, in a film unit with a lens in which a light-sensitive material coexists with a dry cell, fluctuations in photographic performance occur, and no suggestion has been made regarding suppressing this. Moreover, it cannot be inferred that the effect is effective.

[0004]

SUMMARY OF THE INVENTION Therefore, the present invention provides a package in which a multilayer silver halide color photographic light-sensitive material and a dry battery are hermetically packaged in the same packaging bag, and the fluctuation of photographic property during storage with time is small. It is an object to provide a multilayer silver halide color photographic light-sensitive material package having excellent stability.

[0005]

The inventor of the present invention has found that the fluctuation of photographic performance of a light-sensitive material in a package in which the light-sensitive material and a dry cell are hermetically packaged in the same packaging bag is caused by the silver halide of at least one layer of the light-sensitive material. It was found that a specific compound should be used in the photosensitive layer, and the present invention was completed based on this finding.
That is, the present invention

(1) A multi-layer silver halide color photographic light-sensitive material having at least one red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, and a dry battery in the same package. In a multi-layer silver halide color photographic light-sensitive material package sealed inside,
The following general formula (AI) is used in at least one of the silver halide-containing photosensitive layers of the multilayer silver halide color photographic light-sensitive material.
To (A-V), and the volume of the package is 50 cm ³ or more and 140 cm ³ or less, a multilayer silver halide color photographic light-sensitive material package.

[0007]

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In the general formula (AI), R _a1 is an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or aryl. It represents an oxycarbonyl group, and R _a2 represents a hydrogen atom or a group represented by R _a1 . Provided that when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group,
It is a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R _a1
And R _a2 may combine with each other to form a 5- to 7-membered ring. In formula (A-II), X represents a heterocyclic group, and R _b1 represents an alkyl group, an alkenyl group or an aryl group. X and R _b1 may combine with each other to form a 5- to 7-membered ring. In the general formula (A-III), Y is -N =
It represents a group of non-metal atoms necessary for forming a 5-membered ring with C-. Y represents a group of non-metal atoms necessary for forming a 6-membered ring together with a -N = C- group, and -N = C
The terminal of Y bonded to the carbon atom of the -group is -N (R _C1 )-, -C
(R _C2 ) (R _C3 )-, —C (R _C4 ) =, —O—, a group selected from —S— (bonded to the carbon atom of —N═C— on the left side of each group) Represents R _{C1 to} R _C4 represent a hydrogen atom or a substituent. In formula (A-IV), R _d1 and R _{d2, which} may be the same or different, each represents an alkyl group or an aryl group. However, when R _d1 and R _d2 are simultaneously an unsubstituted alkyl group and R _d1 and R _d2 are the same group, R _d1 and R _d2 are alkyl groups having 8 or more carbon atoms. In formula (A-V), R _e1 and R _e2 may be the same or different and each is a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an alkylthio group. Represents a group, an arylthio group, an alkyl group or an aryl group. However, R _e1 and R _e2 are not —NHR _e3 (R _e3 is an alkyl group or an aryl group) at the same time. R _a1 and R _a2 , and X and R _b1 may combine with each other to form a 5- to 7-membered ring.

(2) The multilayer silver halide color photographic light-sensitive material is characterized in that it has a magnetic layer containing a ferromagnetic powder on the back surface opposite the photosensitive emulsion layer and the support (1). The multi-layer silver halide color photographic light-sensitive material package according to [4].

The present inventor has found that when a multi-layered silver halide color photographic light-sensitive material and a dry battery are hermetically packaged in the same packaging bag, for example, "Shashin-run", the photographic performance varies when the aging is continued for a long time. I found that it occurred and was sensitized. On the other hand, the same light-sensitive material does not coexist with dry batteries, for example, 1
No significant change in photographic performance such as the above-mentioned sensitization does not occur even when 35 Patrone etc. are aged for a long time under the same conditions.
In addition, it was clarified that the change in photographic performance, such as sensitization, does not occur even after a long period of time when the dry battery is removed from “Sharpness Run”. Therefore, it is assumed that the photographic performance fluctuates due to the coexistence of dry batteries, and that some toxic gas is generated from the dry batteries to change the photographic performance, and the photographic performance is sensitized, so the toxic gas is reduced. As a result of various studies by presuming that it is caused by a volatile gas, it was found that the use of the compounds represented by the above general formulas (AI) to (AV) is effective.
However, the details of toxic gas are not clear yet and remain as a future research topic.

The present invention will be described in more detail below.

The compounds represented by formulas (A-I) to (A-V) will be described in more detail. The alkyl group referred to in the present invention is a linear, branched or cyclic alkyl group, which may have a substituent. In the general formula (AI), R
_a1 is an alkyl group (preferably an alkyl group having 1 to 36 carbon atoms such as methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl, benzyl),
Alkenyl group (preferably an alkenyl group having 2 to 36 carbon atoms such as allyl, 2-butenyl, isopropenyl,
Oleyl, vinyl), aryl groups (preferably having 6 carbon atoms)
~ 40 aryl groups such as phenyl and naphthyl, acyl groups (preferably acyl groups having 2 to 36 carbon atoms such as acetyl, benzoyl, pivaloyl, α- (2,4-di-tert-amylphenoxy) butyryl, myristoyl ,
Stearoyl, naphthoyl, m-pentadecylbenzoyl, isonicotinoyl), an alkyl or arylsulfonyl group (preferably an alkyl or arylsulfonyl group having 1 to 36 carbon atoms such as methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkyl or aryl Sulfinyl group (preferably an alkyl or aryl sulfinyl group having 1 to 40 carbon atoms such as methanesulfinyl and benzenesulfinyl), a carbamoyl group (including an N-substituted carbamoyl group, preferably a carbamoyl group having 1 to 40 carbon atoms, for example N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-butyl-N-
(Phenylcarbamoyl), sulfamoyl group (including N-substituted sulfamoyl group, preferably having 1 to 40 carbon atoms)
A sulfamoyl group of N-methylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl, N-cyclohexyl-N-phenylsulfamoyl, N-ethyl-N-dodecylsulfamoyl) , An alkoxycarbonyl group (preferably having 2 to 2 carbon atoms)
36 alkoxycarbonyl groups such as methoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyloxycarbonyl, hexadecyloxycarbonyl) or aryloxycarbonyl groups (preferably aryloxycarbonyl groups having 7 to 40 carbon atoms, such as phenoxycarbonyl). , Naphthoxycarbonyl). R _a2 represents a hydrogen atom or the group represented by R _a1 .

In the general formula (A-II), a heterocyclic group (a group which forms a 5- to 7-membered hetero ring having at least one of a nitrogen atom, a sulfur atom, an oxygen atom or a phosphorus atom as a ring-constituting atom) The bonding position of the heterocycle (position of the monovalent group) is preferably a carbon atom, for example, 1,
3,5-triazin-2-yl, 1,2,4-triazin-3-yl, pyridin-2-yl, pyrazinyl, pyrimidinyl, purinyl, quinolyl, imidazolyl, 1,
2,4-triazol-3-yl, benzimidazol-2-yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuryl, morpholinyl, phosphinolin-2-yl). R _b1 is represented by the general formula (A−
It represents an alkyl group, an alkenyl group or an aryl group having the same meaning as R _{a1 in} I).

In the general formula (A-III), Y is -N = C.
A group of non-metal atoms necessary for forming a 5-membered ring together with-(for example, the ring group formed is imidazolyl, benzimidazolyl, 1,3-thiazol-2-yl, 2-imidazolin-2-yl, purinyl, 3H -Indol-2-yl). Y is a group of non-metal atoms necessary for forming a 6-membered ring together with -N = C- group, and -N
The end of Y bonded to the carbon atom of the ═C-group is -N (R _C1 )-, -C
(R _C2 ) (R _C3 )-, —C (R _C4 ) =, —O—, a group selected from —S— (bonded to the carbon atom of —N═C— on the left side of each group) Represents R _{c1 to} R _c4 may be the same or different,
It represents a hydrogen atom or a substituent (for example, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, a halogen atom). Examples of the 6-membered ring group formed by Y include quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl, 1,3,5-triazin-5-yl, 6H-1,2,5-thiadiazin-6-yl.

In the general formula (A-IV), R _d1 and R _d
d2 is an alkyl group (preferably an alkyl group having 1 to 36 carbon atoms, such as methyl, ethyl, i-propyl, cyclopropyl, n-butyl, isobutyl, hexyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl, benzyl. ) Or an aryl group (preferably having 6 carbon atoms)
An aryl group of ˜40, for example phenyl, naphthyl). However, when R _d1 and R _d2 are simultaneously an unsubstituted alkyl group and R _d1 and R _d2 are the same group, R _d1 and R _d2 are alkyl groups having 8 or more carbon atoms.

In the general formula (A-V), R _e1 and R _e
e2 is a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group (preferably an alkylamino group having 1 to 50 carbon atoms, such as methylamino, ethylamino, diethylamino, methylethylamino, propylamino, dibutylamino, cyclohexyl). Amino, t-octylamino, dodecylamino, hexadecylamino,
Benzylamino, benzylbutylamino), an arylamino group (preferably an arylamino group having 6 to 50 carbon atoms, for example, phenylamino, phenylmethylamino, diphenylamino, naphthylamino), an alkoxy group (preferably having 1 to 36 carbon atoms). An alkoxy group of, for example, methoxy, ethoxy, butoxy, t-butoxy, cyclohexyloxy, benzyloxy, octyloxy, tridecyloxy, hexadecyloxy), an aryloxy group (preferably an aryloxy group having 6 to 40 carbon atoms). , For example, phenoxy, naphthoxy), an alkylthio group (preferably an alkylthio group having 1 to 36 carbon atoms, such as methylthio, ethylthio, i-propylthio, butylthio,
Cyclohexylthio, benzylthio, t-octylthio, dodecylthio), an arylthio group (preferably an arylthio group having 6 to 40 carbon atoms, for example, phenylthio,
Naphthylthio), alkyl group (preferably having 1 to 3 carbon atoms)
6 alkyl groups such as methyl, ethyl, propyl,
Butyl, cyclohexyl, i-amyl, sec-hexyl, t-octyl, dodecyl, hexadecyl) and an aryl group (preferably an aryl group having 6 to 40 carbon atoms, for example, phenyl or naphthyl). However, R _e1 and R _e2
Are not simultaneously -NHR (R is an alkyl group or an aryl group).

R _a1 and R _a2 , X and R _b1 are bonded to each other to form 5
~ 7-membered ring may be formed, for example, a succinimide ring,
Examples thereof include a phthalimide ring, a triazole ring, a urazole ring, a hydantoin ring, and a 2-oxo-4-oxazolidinone ring. Each group of the compounds represented by formulas (AI) to (AV) may be further substituted with a substituent.
Examples of these substituents include alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, hydroxy groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, amino groups, acylamino groups, sulfonamide groups,
Alkylamino group, arylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, halogen atom, cyano group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, hydroxyamino group And so on.

In formula (AI), R _a2 is a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and R _a1 is an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group or an alkoxycarbonyl group. Group, an aryloxycarbonyl group, and more preferably, R _a2 is an alkyl group or an alkenyl group, and R _a1 is an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. A compound that is a group.
Most preferably, R _a2 is an alkyl group and R _a1 is an acyl group.

In the general formula (A-II), R _b1 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. On the other hand, the general formula (A-II) is preferably represented by the following general formula (A-II-1), more preferably X is 1,3,5-triazin-2-yl, and the following general formula (A-II) Most preferably, it is the compound represented by A-II-2).

[0020]

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[0021] In formula (A-II-1), R b1 represents R _b1 of the general formula (A-II), a non-metallic atomic group necessary for X ₁ to form a 5- or 6-membered ring Represent. General formula (A-
Of the compounds represented by II-1), it is more preferable that X ₁ forms a 5- or 6-membered heteroaromatic ring.

[0022]

[Chemical 4]

[0023] In formula (A-II-2), R b1 represents a R _b1 in formula (A-II). R _b2 and R _{b3, which} may be the same or different, each represents a hydrogen atom or a substituent. In the compound represented by formula (A-II-2), R _b2 and R _b3 are hydroxyamino group, hydroxyl group, amino group, alkylamino group, arylamino group, alkoxy group, aryloxy group, alkylthio group, Particularly preferred is an arylthio group, an alkyl group or an aryl group.

Of the compounds represented by the general formula (A-III), Y is preferably a group of non-metal atoms necessary for forming a 5-membered ring, and is bonded to a carbon atom of -N = C- group. It is more preferable that the terminal atom of Y is a nitrogen atom. Y
Most preferably forms an imidazoline ring. This imidazoline ring may be condensed with a benzene ring.

Of the compounds represented by formula (A-IV), those in which R _d1 and R _d2 are alkyl groups are preferable. On the other hand, in the general formula ( _AV ), R _e1 and R _e2 are preferably a group selected from a hydroxyamino group, an alkylamino group and an alkoxy group. Particularly preferably, R _e1 is a hydroxylamino group and R _e2 is an alkylamino group.

Among the compounds represented by the general formulas (AI) to (AV), compounds having a total carbon number of 15 or less are preferable in that they act on layers other than the additive layer, and vice versa. A compound having a total carbon number of 16 or more is preferable for the purpose of acting only on the additive layer. General formula (AI)-(A-
V) among the compounds represented by the general formula (AI),
Those represented by (A-II), (A-IV) and (A-V) are preferable, more preferably general formulas (A-I) and (A-).
IV) and (A-V), more preferably those represented by the general formulas (AI) and (A-V). The general formulas (A-I) to (A-V) of the present invention are shown below.
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0027]

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[0028]

[Chemical 6]

[0029]

[Chemical 7]

[0030]

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[0031]

[Chemical 9]

These compounds and the above-mentioned general formula (AI)
Correspondence with ~ (A-V) is as follows. General formula (AI): A-33 to A-55. General formula (A-II): A-5 to A-7, A-10, A-2
0, A-30. General formula (A-III): A-21 to A-29, A-31, A
-32. General formula (A-IV): A-8, A-11, A-19. General formula (AV): A-1 to A-4, A-9, A-12
~ A-18. These compounds of the present invention are described in J. Org. Chem., 27, 405.
4 ('62), J. Amer. Chem. Soc., 73,2981 ('51), Japanese Patent Publication No. 4
It can be easily synthesized by the method described in 9-10692 or the like or a method similar thereto. In the present invention, the compounds represented by the general formulas (A-I) to (A-V) are emulsified even if they are dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. It may be added by dispersion. Further, it may be added in advance when preparing the emulsion. When it dissolves in water, the higher or lower the pH, the higher the solubility, the pH
It may be added by dissolving it by raising or lowering.
In the present invention, two or more kinds of the compounds represented by the general formulas (AI) to (AV) may be used in combination. For example, using both water-soluble and oil-soluble
It is advantageous in photographic performance. Compounds (A-I) to (A-V)
The coating amount of 0.01 to 0.01
100 mg / m ² is preferred. 0.1 to 50 mg / m ² is more preferable, and 1 to 20 mg / m ² is even more preferable. These compounds are used in at least one layer of the silver halide photosensitive layer, but the same compound may be used in a plurality of layers.
Different compounds may be used in each photosensitive layer.
Further, at the same time as the photosensitive layer, a non-photosensitive layer, for example, an intermediate layer,
It can also be used in a colloidal silver-containing yellow filter layer, an AH layer and a protective layer. Any water-soluble compound can be used in any of the layers constituting the photographic photosensitive layer.
In the case of an oil-soluble compound, it is preferably used in the silver halide photosensitive layer. It is also preferable to use a water-soluble compound and an oil-soluble compound in combination.

Next, the hermetically sealed packaging according to the present invention will be described. The hermetically sealed package is a moisture-proof package that is well known in the field of normal packaging. Examples of packaging materials include metals such as aluminum plate, tin plate, aluminum foil, metal foil, glass or polyethylene, polyvinyl chloride, polystyrene, polyvinylidene chloride, polypropylene, polycarbonate, polyamide and other polymers, various polymers and cellophane, paper , A composite laminated material made of a material such as aluminum foil (a laminated material in the packaging term) is used.
As a sealing method for sealing, a bonding method using various adhesives, a heat fusion method such as heat sealing, or the like can be used.
Details of these sealing methods are described in "Handbook of Food Packaging Technology" (edited by Japan Packaging Technology Association), pages 573 to 609.

In the package in which the light-sensitive material of the present invention and the dry battery are combined and hermetically packaged in the same packaging, it is preferable to use a composite laminated material of aluminum foil whose surface is processed with various polymers. These hermetically sealed packages may be doubled.
At this time, the volume of 50 cm ³ or more and 140 cm ³ of the hermetically sealed package means the volume of the package body in which the innermost direct photosensitive material and the dry battery are hermetically packaged.

In the present invention, the volume of the package is 50 cm ³ or more and 140 cm ³ or less. This volume is limited by the size of the lens-fitted film unit, but is preferably 70
cm ³ or more 130cm ³ or less. A more preferable range is 90 cm ³ or more and 120 cm ³ or less. Originally, in order to reduce the influence of the toxic gas in the package, it is desirable to increase the volume of the hermetically sealed package, but the above general formula (A-
By finding the compounds represented by I) to (A-V), the volume of the package can be made smaller than in the conventional case, and the volume range can be made within the above range.

Next, the dry battery of the present invention will be described.
The dry battery used in the present invention is a dry battery used for a lens-fitted film unit such as "Sharp Run" as described above. Therefore, it is not a special dry battery but a so-called commercially available dry battery. The shape includes various types such as a single type to a single type 5 cylindrical rod type, a rectangular type, a button type and a coin type. In the present invention, the shape is preferably AA type.
The classification based on the electromotive force of dry batteries includes so-called alkali, manganese, silver oxide, lithium dry batteries and the like. Among them, the alkaline dry battery is preferable in the present invention because of its short strobe charge time and economical efficiency. Therefore, in the present invention, it is particularly preferable to use the AA cylindrical rod type alkaline dry battery in the lens-fitted film unit.

The fluctuations in photographic performance that occur in the package in which the photographic light-sensitive material of the present invention and the dry battery are hermetically packaged in the same package also occur in the use of any of the dry batteries. Therefore, the fluctuations in photographic performance, the increase in fog, and the increase in sensitivity were attributed to the toxic gas as described above, but from the appearance and property inspection before and after using the dry cell, it is probably not a problem for hydrogen gas. It is thought that there is. In this regard,
As will be shown in Examples described later, it is considered that this can be supported also by the similar behavior in the presence of hydrogen gas.

The photosensitive material of the present invention may have at least one photosensitive layer provided on a support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. 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, the arrangement of the unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer is DE 1,121,470 or GB 923,0.
As described in No. 45, it is preferable to arrange two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer so that the sensitivities become lower toward the support. In addition, JP-A-57-1127
51, the same 62-200350, the same 62-206541,
As described in JP-A-62-206543, 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 farthest side 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 (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH It can be installed in the order of. Further, as described in JP-B-55-34932, from the side farthest from the support, the blue-sensitive layer / GH / RH
It can also be arranged in the order of / GL / RL. In addition, JP-A-56
No. 25738, No. 62-63936, the blue-sensitive layer / GL / RL / from the side farthest from the support.
It can also be arranged in the order of GH / RH. In addition,
No. 15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the lower sensitive silver halide emulsion layer, and the lower layer is the lower sensitive silver halide emulsion. An example is an arrangement in which layers are arranged and three layers having different sensitivities are sequentially lowered toward the support, and the sensitivities are different from each other. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. Other, high sensitivity emulsion layer /
Low-speed emulsion layer, medium-speed emulsion layer, or low-speed emulsion layer /
The medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, US Pat.
271, the same 4,705,744, the same 4,707,43
6. Adjacent to the main photosensitive layer is a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL and RL described in JP-A-62-160448 and 63-89850. Alternatively, it is preferable to arrange them in close proximity.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, which contains about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide 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 (hereinafter abbreviated as RD) No. 17643 (197).
Dec. 8), pp. 22-23, "I. Emulsion production (Emulsi
on preparation and types) ", and the same No.18716
(November, 1979), pp. 648, No. 307105.
(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 Duffin, Photographic Emul)
sion Chemistry, Focal Press, 1966), "Production and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (V.
L. Zelikman, et al., Making and Coating Photographi
c Emulsion, Focal Press, 1964) and the like.

US 3,574,628, US 3,655,655
The monodisperse emulsions described in 394 and GB 1,413,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering.
and Engineering), Vol. 14, pp. 248-257 (1
970); US 4,434,226; 4,414,14.
310, 4,433,048, 4,439,520
And GB 2,112,157 can be easily prepared. Even if the crystal structure is uniform,
The inside and the outside may have different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image types, JP-A-63-264740
The core / shell type internal latent image type emulsion described in JP-A-59-133542 may be used. The shell thickness 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 additive used in such a process is RD No. 17643,
It is described in No. 18716 and No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US 4,082,
553, the surface of which is covered with a silver halide grain, US Pat. No. 4,626,498, and JP-A-59-21485.
It is preferable to apply the internally fogged silver halide grains and colloidal silver described in 2 to the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. A silver halide grain having a fog inside or on the surface thereof is irrespective of the unexposed portion and exposed portion of the light-sensitive material,
It refers to silver halide grains that can be uniformly (non-imagewisely) developed, and its preparation method is described in US Pat.
8 and JP-A-59-214852. The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition. 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 average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape may be regular grains or polydisperse emulsions, but monodispersity (at least 95% of the weight of silver halide grains or the number of grains is ± 4 of the average grain size).
Those having a particle size of 0% or less) are preferable.

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain size (average value of circle-equivalent diameter of projected area) of 0.01 to 0.5 μm, and 0.02 to
0.2 μm is more preferable. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. 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 contained in the fine silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 page right column page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, page 866 to 868, supersensitizer, page 649, right column, 4. Whitening agent Page 24 Page 647 Page right column Page 868 5. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter to page 650, left column, dyes, ultraviolet absorbers 6. Binder 26 pages 651 pages left column 873 to 874 pages 7. Plasticizer, page 27, page 650, right column, page 876, lubricant 8. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 9. Static page 27 page 650 page right column 876-877 page inhibitor 10. Matting agent page 878-879

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferable. Yellow coupler: Formula (I) of EP502,424A,
A coupler represented by formula (II); a coupler represented by formulas (1) and (2) of EP513, 496A (particularly Y on page 18);
-28); couplers represented by formula (I) of claim 1 of EP 568,037A; US Pat. No. 5,066,576;
Column 1, lines 45 to 55, a coupler represented by formula (I); coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; EP498,381.
The coupler described in Claim 1 on page 40 of A1 (especially 18
Page D-35); couplers represented by formula (Y) on page 4 of EP 447,969 A1 (especially Y-1 (page 17),
Y-54 (page 41)); couplers represented by formulas (II) to (IV) in columns 7, lines 36 to 58 of US Pat. No. 4,476,219 (particularly II-17, 19 (column 17), II-24).
(Column 19)). Magenta coupler: JP-A-3-39737 (L-57)
(Page 11, lower right), L-68 (Page 12, lower right), L-77
(Page 13, lower right); [A-4] -6 of EP 456,257.
3 (page 134), [A-4] -73, -75 (139).
Page); M-4, -6 (page 26) of EP486,965,
M-7 (page 27); EP-571,959A, M-45.
(Page 19); (M-1) (6) of JP-A-5-204106.
Page); M-2 in paragraph 0237 of JP-A-4-362631
2. Cyan coupler: CX-1, JP-A-4-204843,
3, 4, 5, 11, 12, 14, 15 (14-16
Page); C-7, 10 (35) of JP-A-4-43345.
Page), 34, 35 (page 37), (I-1), (I-1)
7) (pages 42 to 43); a coupler represented by formula (Ia) or (Ib) of claim 1 of JP-A-6-67385. Polymer coupler: P-1, P of JP-A-2-44345
-5 (p. 11).

Examples of couplers in which the coloring dye has an appropriate diffusibility include US 4,366,237, GB 2,125,
570, EP96,873B, DE3,234,533
Those described in are preferable. A coupler for correcting unnecessary absorption of a color forming dye is a yellow colored cyan coupler represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP456,257A1 (especially on page 84). YC-86), the yellow colored magenta coupler ExM-7 (page 202) and EX-1 (24
9), EX-7 (251), US 4,833,06
Magenta colored cyan coupler CC-9 according to Item 9.
(Column 8), CC-13 (Column 10), US 4,8
37, 136 (2) (column 8), WO92 / 115
The colorless masking couplers represented by formula (A) in claim 1 of 75 (in particular, the exemplified compounds on pages 36 to 45) are preferable. Examples of the compound (including a coupler) which reacts with an oxidized product of a developing agent to release a photographically useful compound residue include the following. Development inhibitor releasing compound: EP3
78,236A1, page (11), (II),
Compounds represented by (III) and (IV) (especially T-101
(Page 30), T-104 (page 31), T-113 (36).
Page), T-131 (page 45), T-144 (page 51),
T-158 (p. 58)), EP 436, 938A2, 7
Compounds represented by formula (I) described on page (especially D-49
(Page 51)), compounds represented by formula (1) of EP568,037A (particularly (23) (page 11)), EP44.
0,195A2 on pages 5-6, (I), (II),
A compound represented by formula (III) (especially I- on page 29)
(1)); Bleach accelerator releasing compound: EP310,125
Compounds represented by formulas (I) and (I ') on page 5 of A2 (particularly (60) and (61) on page 61) and JP-A-6-5.
9411 Compounds of formula (I) according to claim 1 (especially (7) (page 7); Ligand releasing compound: US 4,55
Compounds represented by LIG-X according to claim 1 of 5,478 (particularly compounds on lines 21 to 41 of column 12); Leuco dye-releasing compound: US 4,749,641
Columns 3-8, compounds 1-6; fluorescent dye-releasing compounds:
COUP-DY of claim 1 of US 4,774,181
Compound represented by E (especially compound 1 in columns 7-10)
~ 11); Development accelerator or fogging agent releasing compound: US
Formulas (1), (2) of column 3, 4,656,123,
The compound represented by (3) (particularly (I-2 of column 25
2)) and EP 450, 637 A2, pp. 75, 36-38.
ExZK-2 in line; Compound that releases a group that becomes a dye only upon leaving: a compound represented by the formula (I) in claim 1 of US Pat. No. 4,857,447 (particularly Y-1 to Y- 19).

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: JP-A-62-215272
P-3, 5, 16, 19, 25, 30, 42, 49,
54, 55, 66, 81, 85, 86, 93 (140-
144); latex for impregnation of oil-soluble organic compound: U
Latex described in S4,199,363; Oxidized developer scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US Pat. , (6), (12) (column 4-
5), US Pat. No. 4,923,787, column 2, lines 5-10 (especially compound 1 (column 3); stain inhibitor: E).
P298321A, page 4, lines 30-33, formulas (I)-(II
I), especially I-47, 72, III-1, 27 (24-48)
Anti-fading agent: A-6,7 of EP298321A,
20, 21, 23, 24, 25, 26, 30, 37, 4
0, 42, 48, 63, 90, 92, 94, 164 (6
Pp. 9-118), column 5, US 5,122,444.
-38 II-1 to III-23, especially III-10, EP4
71347A, pages 8-12, I-1 to III-4, especially II.
-A of columns 32-40 of US Pat. No. 5,139,931
-1 to 48, especially A-39, 42; a material for reducing the amount of color-enhancing agent or color-mixing inhibitor used: EP411324
A, pages 1 to 24, I-1 to II-15, especially I-46; formalin scavenger: EP 477932A, 24 to
SCV-1 to 28 on page 29, especially SCV-8; Hardeners:
H-1, 4, 6, on page 17 of JP-A 1-214845.
8, 14; columns 13-23 of US 4,618,573
Compounds (H-1 to 5) represented by formulas (VII) to (XII)
4), compounds (H-1 to 76) represented by the formula (6) at the lower right of page 8 of JP-A-2-214852, particularly H-14 and U.
Compound described in claim 1 of S3,325,287; Development inhibitor precursor: P of JP-A-62-168139
-24, 37, 39 (pages 6-7); US 5,019,4.
92 the compound of claim 1 especially column 7bis
8 and 29; antiseptic and antifungal agents: US Pat.
9, 10, 18, III-25; stabilizer, antifoggant:
US Pat. No. 4,923,793, columns 6-16, I-1.
(14), especially I-1, 60, (2), (13), US
4,952,483 columns 25-32 compounds 1-6
5, especially 36: chemical sensitizer: triphenylphosphine
Selenide, Compound 50 of JP-A-5-40324; Dye:
JP-A-3-156450, pages 15-18, a-1 to b-
20, especially a-1, 12, 18, 27, 35, 36, b
-5, pp. 27-29, V-1-23, especially V-1, EP
445627A, pp. 33-55, FI-I-F-II-
43, especially F-I-11, F-II-8, EP45715.
3A, pages 17-28, III-1 to 36, especially III-1,
3, Dye-1 to 1 of 8 to 26 of WO88 / 04794
24 microcrystalline dispersion, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, EP 519306A.
Compounds D-1 to 8 represented by formulas (1) to (3)
7 (pages 3-28), formula (I) of US 4,268,622.
Compounds 1 to 22 (columns 3 to 10) represented by US
Compounds (1) to (31) represented by formula (I) of 4,923,788 (columns 2 to 9); UV absorber: Compound represented by formula (1) of JP-A-46-3335 (18)
b) to (18r), 101 to 427 (pages 6 to 9), EP
Compound (3) represented by formula (I) of 520938A
(66) (pages 10 to 44) and compounds represented by formula (III) HBT-1 to 10 (page 14), EP521823A.
Compounds (1) to (31) represented by formula (1) in (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Examined Patent Publication 2-352615,
It is suitable for the film unit with a lens described in Japanese Utility Model Publication No. 3-39784. Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643-2
Page 8, page 647, right column to page 648, left column of the same No. 18716, and page 879 of the same No. 307105. 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, further preferably 18 μm or less, particularly preferably 16 μm or less. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is a color developer at 30 ° C for 3 minutes 1
When 90% of the maximum swollen film thickness reached after the treatment for 5 seconds is the saturated film thickness, it is defined as the time until the film thickness reaches 1/2. The film thickness means the film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is A. Green et al.'S Photographic Science and Engineering. (Photogr.Sci.Eng,), 19
The measurement can be performed by using a swellometer (swelling meter) of the type described in Vol. T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling ratio is 150 to 400
% Is preferred. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness. The photosensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. The swelling ratio of this back layer is 150.
~ 500% is preferred.

The light-sensitive material of the present invention has the above-mentioned RD. No. 1
7643, pp. 28-29, No. 18716, 651 left column to right column, and No. 307105, 880-881.
The development can be carried out by a usual method described on the page. Next, the processing solution for the color negative film used in the present invention will be described. The color developer used in the present invention is described in JP-A-4-121739, page 9, upper right column 1,
The compounds described in lines to page 11, lower left column, line 4 can be used. As a color developing agent for particularly rapid processing, 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline, 2-methyl-4-
[N-ethyl-N- (3-hydroxypropyl) amino] aniline, 2-methyl-4- [N-ethyl-N-
(4-Hydroxybutyl) amino] aniline is preferred. It is preferable to use these color developing agents in the range of 0.01 to 0.08 mol, especially 0.015 to 0.06 mol, and further 0.0 per 1 liter of the color developing solution.
It is preferably used in the range of 2 to 0.05 mol. Further, the replenisher for the color developing solution preferably contains 1.1 to 3 times the concentration of the color developing agent, and particularly preferably 1.3 to 2.5 times.

Hydroxylamine can be widely used as a preservative for the color developing solution, but when higher preservability is required, substitution of an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, or the like is required. A hydroxylamine derivative having a group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl). Hydroxylamine is preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferable. These may be used in combination with hydroxylamine, but it is preferable to use one type or two or more types in place of hydroxylamine. Preservative is 0.02 per liter
It is preferable to use in the range of 0.2 to 0.2 mol, particularly 0.03 to 0.15 cell, and more preferably 0.04 to 0.1 mol. The replenisher preferably contains a preservative at a concentration of 1.1 to 3 times that of the mother liquor (processing tank liquid), as in the case of the color developing agent. In the color developing solution, a sulfite is used as an anti-tarring agent for the oxide of the color developing agent. The sulfite is preferably used in an amount of 0.01 to 0.05 mol, and particularly preferably 0.02 to 0.04 mol, per liter. In the replenisher, these 1.1
It is preferable to use it at a concentration of 3 times. The pH of the color developing solution is preferably in the range of 9.8 to 11.0, particularly preferably 10.0 to 10.5. It is preferable to set a high value within the range. To maintain such a pH stable, known buffering agents such as carbonate, phosphate, sulfosalicylate, borate and the like are used.

The replenishing amount of the color developing solution is preferably 80 to 1300 ml per 1 m ² of the light-sensitive material, but is preferably smaller from the viewpoint of reducing environmental pollution load, specifically 80 to 600 ml, and further. 80-400
Milliliters are preferred. The bromide ion concentration in the color developing solution is usually 0.01 to 0.06 mol per liter, but fog is suppressed while maintaining sensitivity, improving discrimination, and good graininess. 0.015 to 0.03 per liter for the purpose of converting
It is preferable to set it at a mole. When the bromide ion concentration is set in such a range, the replenisher may contain the bromide ion calculated by the following formula. However, C
When is negative, it is preferable that the replenisher do not contain bromide ions. C = A-W / V C: Bromide ion concentration in the color developing replenisher (mol / liter) A: Target bromide ion concentration in the color developing solution (mol / liter) W: 1m ² of light-sensitive material is colored Amount of bromide ion eluted from the light-sensitive material to the color-developing solution when developed (mol) V: Replenishment amount of color-development replenisher for a light-sensitive material of 1 m ² (liter). When the bromide ion concentration is set, 1-phenyl-3-pyrazolidone or 1-phenyl-2-methyl-2 can be used as a method for increasing the sensitivity.
It is also preferable to use development accelerators such as pyrazolidones represented by -hydroxymethyl-3-pyrazolidone and thioether compounds represented by 3,6-dithia-1,8-octanediol.

The compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having a bleaching ability in the present invention. . The bleaching agent preferably has an oxidation-reduction potential of 150 mV or higher, and specific examples thereof include JP-A-5-
Nos. 72694 and 5-1733312 are preferable, and 1,3-diaminopropanetetraacetic acid is particularly preferable,
A ferric complex salt of the compound of Specific Example 1 on page 7 of No. 173312 is preferable. In order to improve the biodegradability of the bleaching agent, JP-A-4-251845, 4-268552, E
P588,289, 591,934, JP-A-6-20.
It is preferable to use the compound ferric complex salt described in 8213 as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per 1 liter of a bleaching solution, and especially for the purpose of reducing the amount discharged to the environment.
It is preferable to design 1 mol to 0.15 mol. When the solution having a bleaching ability is a bleaching solution, it is preferable to contain 0.2 mol to 1 mol of bromide per liter, particularly preferably 0.3 to 0.8 mol. The replenisher for the bleaching solution basically contains the concentrations of the respective components calculated by the following formula. Thereby, the concentration in the mother liquor can be maintained constant. C _R = C _T × (V ₁ + V ₂ ) / V ₁ + C _P C _R : Concentration of component in replenisher C _T : Concentration of component in mother liquor (treatment tank liquid) C _P : Consumed during treatment Concentration of components V ₁ : Replenishing amount of replenishing solution having bleaching ability for a light-sensitive material of 1 m ² (mL) V ₂ : Bring-in amount of a light-sensitive material of 1 m ² from a pre-bath (mL) It is preferable to contain an agent, and it is particularly preferable to contain a dicarboxylic acid having a small odor, such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid. Also, JP-A-53-9563
0, RD No. 17129, US 3,893,858 and known bleaching accelerators are also preferably used. The bleaching solution is preferably supplemented with 50 to 1000 ml of the bleaching replenishing solution per 1 m ² of the light-sensitive material, and particularly 80
It is preferable to replenish ~ 500 ml, more preferably 100-300 ml. Further, the bleaching solution is preferably aerated.

For the processing solution having fixing ability, compounds and processing conditions described in JP-A-4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19 can be applied. In particular, in order to improve the fixing speed and the homeostasis, the compounds represented by the general formulas (I) and (II) of JP-A-6-301169 are contained alone or in combination in a processing solution having fixing ability. It is preferable. Further, it is also preferable to use the sulfinic acid described in JP-A-1-224762, in addition to p-toluenesulfinate, from the viewpoint of improving the preservability. It is preferable to use ammonium as a cation in a solution having a bleaching ability and a solution having a fixing ability from the viewpoint of improving desilvering ability, but from the viewpoint of reducing environmental pollution, it is preferable to reduce or eliminate ammonium. . bleaching,
In the bleach-fixing and fixing steps, JP-A-1-30905
It is particularly preferable to carry out the jet stirring described in 9.
The replenishing amount of the replenisher in the bleach-fixing or fixing step is 100 to 1000 ml per 1 m ² of the light-sensitive material,
It is preferably 150 to 700 ml, particularly preferably 200 to 600 ml. In the bleach-fixing and fixing steps, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, it is possible to reduce the silver concentration in the solution and process it, and as a result, the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the residual liquid as a replenisher. The bleach-fixing step and the fixing step can be composed of a plurality of processing tanks, and it is preferable that each tank is cascade-piped to form a multistage countercurrent system. In view of the balance with the size of the developing machine, the two-tank cascade configuration is generally efficient, and the ratio of the processing time in the front-stage tank and the rear-stage tank is in the range of 0.5: 1 to 1: 0.5. The range of 0.8: 1 to 1: 0.8 is particularly preferable. In the bleach-fixing solution or the fixing solution, it is preferable to allow a free chelating agent which is not a metal complex to be present from the viewpoint of improving the preservative property. It is preferred to use chelating agents.

Regarding the washing and stabilizing steps, the above JP-A-4-125558, page 12, lower right column, line 6 to 13
The contents described in the lower right column, line 16 of the page can be preferably applied. In particular, instead of formaldehyde, azolylmethylamines described in EP 504,609 and 519,190 or N-methylolazoles described in JP-A-4-362943 are used in the stabilizing solution, and a magenta coupler is used. From the viewpoint of maintaining the working environment, it is preferable to equilibrate to form a liquid of a surfactant containing no image stabilizer such as formaldehyde. Further, in order to reduce the adhesion of dust to the magnetic recording layer coated on the light-sensitive material, the stabilizing solution described in JP-A-6-289559 can be preferably used. The amount of washing and replenishment of the stabilizing solution is preferably 80 to 1000 ml / m ² of the light-sensitive material, and particularly 100
˜500 ml, more preferably 150 to 300 ml is a preferable range from the viewpoint of ensuring the washing or stabilizing function and reducing waste liquid for environmental protection. In the treatment with such supplemental amount, in order to prevent the growth of bacteria and mold, known agents such as thiabendazole, 1,2-benzisothiazolin-3-one and 5-chloro-2-methylisothiazolin-3-one are used. It is preferable to use water that has been deionized with an antifungal agent, an antibiotic such as gentamicin, an ion exchange resin, or the like. It is more effective to use deionized water in combination with antibacterial agents and antibiotics. Further, the liquid in the tank for washing or stabilizing liquid is described in
-46652, 3-53246, 3-55542,
It is also preferable to perform the reverse osmosis membrane treatment described in JP-A-3-121448 and JP-A-3-126030 to reduce the replenishment amount. In this case, the reverse osmosis membrane is preferably a low pressure reverse osmosis membrane.

In the processing of the present invention, it is particularly preferable to carry out the evaporation correction of the processing liquid disclosed in the Technical Report of the Institute of Invention, Technical Report No. 94-4992. In particular, a method of making a correction using the temperature and humidity information of the environment where the developing machine is installed is preferable based on (Equation-1) on page 2. The water used for evaporation correction is preferably collected from a replenishing tank for washing, and in that case, deionized water is preferably used as the washing replenishing water.

As the treating agent used in the present invention, those described in page 15, right column, line 15 to page 4, left column, line 32 of the above-mentioned Kokai Giho are preferable. As the developing machine used for this purpose, the film processor described in lines 22 to 28 in the right column of page 3 is preferable. Specific examples of preferred processing agents, automatic processors, and evaporation correction methods for carrying out the present invention are as follows.
It is described from page 5, right column, line 11 to page 7, right column, last line of the above-mentioned public technical report.

The form of supply of the treating agent used in the present invention is as follows:
It may be in any form such as a concentrated or concentrated liquid preparation, a granule, a powder, a tablet, a paste or an emulsion. As an example of such a treating agent, JP-A-63-63
-17453 is a liquid agent stored in a container with low oxygen permeability,
Japanese Patent Application Laid-Open Nos. 4-19655 and 4-230748 disclose vacuum-packed powder or granules, and JP-A-4-2211951 discloses granules containing a water-soluble polymer.
7, tablets in JP-A-6-102628, Japanese Patent Publication No. 57-5
No. 00485 discloses a processing agent in a paste form,
Although any of them can be preferably used, it is preferable to use a liquid which is prepared in advance at the concentration of the use state from the viewpoint of convenience in use. The container that stores these treatment agents,
Polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon and the like are used alone or as a composite material. These are selected according to the level of oxygen permeability required. For a liquid such as a color developing solution which is easily oxidized, a material having low oxygen permeability is preferable, and specifically, polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500-1500 μm and are used for containers, and have an oxygen permeability of 20 ml / m ² · 24 hrs · at.
It is preferably m or less.

Next, the processing liquid for the color reversal film used in the present invention will be described. Regarding the processing for the color reversal film, known technology No. 6 (April 1, 1991), page 1, line 5 to page 10, 5 issued by Aztec Co., Ltd.
Lines, page 15, line 8 to page 24, line 2, all of which can be preferably applied. In color reversal film processing, image stabilizers are included in either the conditioning bath or the final bath. Examples of such an image stabilizer include formaldehyde sodium bisulfite and N-methylolazoles in addition to formalin, and sodium formaldehyde bisulfite or N-methylolazoles are preferable from the viewpoint of working environment,
As the N-methylolazoles, N-methyloltriazole is particularly preferable. Further, the color developing solution, the bleaching solution, the fixing solution described in the processing of the color negative film,
The contents regarding washing water and the like can be preferably applied to the processing of the color reversal film. As a preferable color reversal film processing agent containing the above contents, Eastman Kodak E-6 processing agent and Fuji Photo Film Co., Ltd. CR are used.
-56 treating agent can be used.

Next, the transparent magnetic recording layer used in the present invention will be described. The transparent magnetic recording layer used in the present invention is one in which an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder is coated on a support.
Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co-coated magnetite,
It is possible to use Co-containing magnetite, ferromagnetic dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, or the like. Co-deposited ferromagnetic iron oxides such as Co-deposited γFe ₂ O ₃ are preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. S _BET 20 in specific surface area
m ² / g or more is preferable, and 30 m ² / g or more is particularly preferable. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0
× 10 ^{4 to} 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be surface-treated with silica and / or alumina or an organic material. Further, the magnetic particles may be surface-treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. In addition, JP-A-4-259911 and 5-816
The magnetic particles described in No. 52 whose surface is coated with an inorganic or organic substance can also be used.

Next, the binder used for the magnetic particles is
Thermoplastic resins, thermosetting resins, radiation-curable resins, reactive resins, acids, alkalis or biodegradable polymers, natural products polymers (cellulose derivatives, sugar derivatives, etc.) described in JP-A-4-219569 and their Mixtures can be used. The Tg of the above resin is -40 ° C to 300 ° C, and the weight average molecular weight is 20,000 to 1,000,000. For example, vinyl copolymer, cellulose diacetate, cellulose triacetate, cellulose acetate propionate,
Examples thereof include cellulose derivatives such as cellulose acetate butyrate and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable. The binder can be hardened by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based cross-linking agent include isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, tolylene diisocyanate). Reaction products of 3 mol of isocyanate and 1 mol of trimethylolpropane), and polyisocyanates produced by condensation of these isocyanates are mentioned, for example, as described in JP-A-6-59357.

As a method of dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill or the like is preferable, and a combination thereof is also preferable, as in the method described in JP-A-6-35092. JP-A-5-088283
The dispersants described in 1 above and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to
It is 3 μm. The weight ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of magnetic particles is 0.005 to 3 g / m ² , preferably 0.01.
~ ² g / m ² , more preferably 0.02-0.5 g / m ²
Is. The magnetic recording layer used in the present invention can be provided on the back surface of the photographic support by coating or printing and provided in the entire surface or in a stripe shape. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar,
Extrusion and the like can be used, and it is disclosed in Japanese Patent Laid-Open No. 5-341
The coating solutions described in 436 and the like are preferable.

The magnetic recording layer has improved lubricity, curl adjustment,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and preferably the same binder as that of the magnetic recording layer is used. Regarding a photosensitive material having a magnetic recording layer, US Pat.
250,404, 5,229,259, 5,21
5,874, EP 466,130.

Next, the polyester support used in the present invention will be described. For details including the light-sensitive material, processing, cartridges and examples described later, open technical report, official technique number 94-6023 (Invention Society; 1994). It is described in 3. 15.). The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and the aromatic dicarboxylic acid is 2,6-, 1,5-, 1,4.
-, And 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A and bisphenol. Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferable. The average molecular weight range is about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, and further 90 ° C.
The above is preferable.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg −20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or the heat treatment may be performed while cooling. This heat treatment time is 0.1 hours or more and 1500 hours or less, and more preferably 0.5 hours or more and 200 hours or less. The heat treatment of the support may be carried out in the form of a roll, or may be carried in the form of a web while being conveyed. The surface condition may be improved by imparting unevenness to the surface (for example, applying conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ ). Further, it is desirable to take measures such as giving a knurl to the end and slightly raising only the end so as to prevent the cut end of the winding core from being exposed. These heat treatments may be carried out at any stage after the film formation on the support, after the surface treatment, after the coating of the back layer (antistatic agent, lubricant, etc.), and after the coating of the undercoat. Preferred is after the antistatic agent is applied. An ultraviolet absorber may be kneaded into this polyester. Also, to prevent light piping, Di from Mitsubishi Kasei
The purpose can be achieved by kneading a commercially available dye or pigment for polyester such as aresin and Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to carry out a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment and ozone oxidation treatment can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment and glow treatment are preferable. Next, the undercoating method may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid,
Starting with copolymers starting from monomers selected from acrylic acid, itaconic acid, maleic anhydride and the like, polyethyleneimine, epoxy resins, grafted gelatin, nitrocellulose and gelatin are listed. Compounds that swell the support include resorcin and p-chlorophenol. As a gelatin hardening agent for the undercoat layer, chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-) are used.
(Hydroxy-S-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferable antistatic agent is Zn.
O ₂ , TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO,
Particle size 0.001 to 1.0 μm crystal in which at least one selected from MoO ₃ and V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. Metal oxides or their complex oxides (Sb, P, B, In, S, Si, C
Etc.), and further sol-like metal oxides or fine particles of composite oxides thereof. The content in the light-sensitive material is preferably 5 to 500 mg / m ² , and particularly preferably 10
~ 350 mg / m ² . The ratio of the conductive crystalline oxide or its composite oxide to the binder is 1/300 to 100.
/ 1 is preferable, and more preferably 1 to 100 to 100 /
It is 5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable sliding property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents a value when conveyed to a stainless ball having a diameter of 5 mm at 60 cm / min (25 ° C., 60% RH). In this evaluation, the value is almost the same level even if it is replaced with the other material on the surface of the photosensitive layer. Examples of the slip agent that can be used in the present invention include polyorganosiloxane, higher fatty acid amide, higher fatty acid metal salt,
Examples of the polyorganosiloxane include esters of higher fatty acids and higher alcohols, and polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, and the like can be used. The addition layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane and ester having a long chain alkyl group are preferable.

The sensitive material of the present invention preferably contains a matting agent. The matting agent may be either on the emulsion side or the back side, but it is particularly preferable to add it to the outermost layer on the emulsion side.
The matting agent may be soluble in the treatment liquid or insoluble in the treatment liquid, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, the particle size distribution is preferably narrow, and 90% or more of the total number of particles is preferably contained within 0.9 to 1.1 times the average particle size. . It is also preferable to add fine particles of 0.8 μm or less at the same time in order to enhance the matt property. For example, polymethylmethacrylate (0.2 μm), poly (methylmethacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm )), Polystyrene particles (0.25
μm) and colloidal silica (0.03 μm).

Next, the film cartridge used in the present invention will be described. The main material of the cartridge used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the cartridge of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A 1-312537 and 1-312.
538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured by using a plastic in which carbon black, a pigment and the like are kneaded in order to impart a light shielding property. . The size of the cartridge may be the same as the current 135 size, and it is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less in order to miniaturize the camera. The volume of the cartridge case is 30 cm ³ or less, preferably 25 cm ³ or less. The weight of the plastic used for the cartridge and the cartridge case is preferably 5 to 15 g.

Further, the cartridge used in the present invention may be a cartridge that rotates the spool to feed the film. Further, the structure may be such that the leading end of the film is housed in the cartridge body and the leading end of the film is fed to the outside from the port portion of the cartridge by rotating the spool shaft in the feeding direction of the film. These are US 4,834,306 and 5,2.
26,613. The photographic film used in the present invention may be a so-called raw film before development,
It may be a photographic film that has been developed. Further, the raw film and the developed photographic film may be stored in the same new cartridge, or may be different cartridges.

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples as long as the scope of the present invention is not exceeded.

[0071]

【Example】

Example 1 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
After drying 0 part by weight and 2 parts by weight of Tinuvin P. 326 (manufactured by Ciba-Geigy Co., Ltd.) as an ultraviolet absorber, the resulting mixture was melted at 300 ° C. and extruded from a T-shaped die,
The film was longitudinally stretched 3.3 times at 0 ° C., then laterally stretched 3.3 times at 130 ° C., and heat-set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. The PEN film contains a blue dye, a magenta dye and a yellow dye (I-1, I-4, I-6, I-24, I-26, I-described in Kokai Giho No. 94-6023).
27, II-5) was added in an appropriate amount. Furthermore, diameter 20 cm
It was wound on a stainless steel core of No. 1 and subjected to a heat history of 110 ° C. for 48 hours to obtain a support having less winding tendency.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and sodium α-on each side. Sulfodi-2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g / m ² ,
(CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.012 g / m ² , polyamide-epichlorohydrin polycondensate 0.02 g / m ² Apply an undercoat liquid (10 cc / m ² , using a bar coater) ), The undercoat layer was provided on the high temperature side during stretching. Drying was carried out at 115 ° C for 6 minutes (rollers and conveyors in the drying zone are
15 ° C). 3) Coating of back layer After the undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer were coated as back layers on one surface of the support.

3-1) Coating of antistatic layer Tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm as a dispersion of fine particle powder (secondary agglomerated particle size of about 0.08 μm). ) and 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.02
It was coated with g / m ² , poly (degree of polymerization of 10) oxyethylene-p-nonylphenol 0.005 g / m ² and resorcin. 3-2) Coating of magnetic recording layer 3-Cobalt-γ-iron oxide coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g, Long axis 0.
14 μm, uniaxial 0.03 μm, saturation magnetization 89 emu /
g, Fe ²⁺ / Fe ⁺³ = 6/94, the surface is treated with aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06 g
/ M ² of diacetyl cellulose 1.2 g / m ² (iron oxide was dispersed by an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) as a curing agent ₃ 0.3 g / m ²
Was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a film thickness of 1.2.
A μm magnetic recording layer was obtained. Silica particles (0.3 μm) as a matting agent and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight)
Aluminum oxide (0.15 μm) as an abrasive coated with
Were added so that the respective amounts would be 10 mg / m ² . Dry 1
It was carried out at 15 ° C. for 6 minutes (all the rollers in the drying zone and the conveying device were 115 ° C.). The color density increase of D ^B of the magnetic recording layer by the X-light (blue filter) is about 0.1,
The saturation magnetization moment of the magnetic recording layer is 4.2 emu /
g, coercive force 7.3 × 10 ⁴ A / m, and squareness ratio of 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀
H ₂₀ COOC ₄₀ H ₈₁ (the compound III-10, 6 mg / m ² ) / C
_{A 50} H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (9 mg / m ² ) mixture was applied.
This mixture was prepared by melting it in xylene / propylene monomethyl ether (1/1) at 105 ° C. and pouring and dispersing it in propylene monomethyl ether (10 times the volume) at room temperature. Average particle size 0.01μ
m) and then added. Silica particles (0.3 μm) as a matting agent and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15) as an abrasive.
Aluminum oxide (0.15 μm) coated by weight% was added to a concentration of 15 mg / m ² . Drying is 115
C., 6 minutes (115.degree. C. for all rollers and conveyors in the drying zone).

4) Coating of Photosensitive Layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was multilayer coated to prepare a color negative film.
These are designated as Samples 101 to 108.

(Photosensitive layer composition) For silver halide and colloidal silver, the coating amount is the amount expressed in g / m ^{2 of} silver,
For couplers, additives and gelatin, g / m ²
The amount expressed in units is shown, and for the sensitizing dye, it is shown as the number of moles per mole of silver halide in the same layer. The symbols indicating additives have the following meanings. However, when there are multiple utilities, one of them is listed as a representative. UV: UV absorber, Solv: High boiling organic solvent, Ex
F: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additive

First layer (antihalation layer) Black colloidal silver 0.15 Gelatin 2.33 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ^-2 ExF-1 1.0 × 10 ^-2 ExF -2 4.0 x 10 ^-2 ExF-3 5.0 x 10 ^-3 ExM-3 0.11 Cpd-5 1.0 x 10 ^-3 Solv-1 0.16 Solv-2 0.10

Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A Coating amount 0.35 Silver iodobromide emulsion B Coating silver amount 0.18 Gelatin 0.77 ExS-1 6.5 × 10 ^-4 ExS-2 3.6 × 10 ^-4 ExS-5 6.2 x 10 ^-4 ExS-7 4.1 x 10 ^-6 ExC-1 9.0 x 10 ^-2 ExC-2 5.0 x 10 ^-3 ExC-3 4.0 x 10 ^-2 ExC-5 8.0 x 10 ^-2 ExC-6 2.0 x 10 ^-2 ExC-9 2.5 x 10 ^-2 Cpd-1 2.2 x 10 ^-2

Third Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide Emulsion C Coating amount 0.55 Gelatin 1.46 ExS-1 4.3 × 10 ^-4 ExS-2 2.4 × 10 ^-4 ExS-5 4.1 × 10 ^-4 ExS-7 4.3 × 10 ^-6 ExC-1 0.19 ExC-2 1.0 × 10 ^-2 ExC-3 1.0 × 10 ^-2 ExC-4 1.6 × 10 ^-2 ExC-5 0.19 ExC-6 2.0 × 10 ^-2 ExC- 7 2.5 x 10 ^-2 ExC-9 3.0 x 10 ^-2 Cpd-4 1.5 x 10 ^-2

4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Coating amount 1.05 Gelatin 1.38 ExS-1 3.6 × 10 ^-4 ExS-2 2.0 × 10 ^-4 ExS-5 3.4 × 10 ^-4 ExS-7 1.4 x 10 ^-5 ExC-1 2.0 x 10 ^-2 ExC-3 2.0 x 10 ^-2 ExC-4 9.0 x 10 ^-2 ExC-5 5.0 x 10 ^-2 ExC-8 1.0 x10 ^-2 ExC- 9 1.0 x 10 ^-2 Cpd-4 1.0 x 10 ^-3 Solv-1 0.70 Solv-2 0.15

Fifth layer (intermediate layer) Gelatin 0.62 Cpd-1 0.13 Polyethyl acrylate latex 8.0 × 10 ^-2 Solv-1 8.0 × 10 ^-2

Sixth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion B Coating amount of silver 0.10 Silver iodobromide emulsion A Coating amount of silver 0.28 Gelatin 0.31 ExS-4 12.8 × 10 ^-4 ExS-5 2.1 × 10 ^-4 ExS-8 1.2x10 ^-4 ExM-1 0.12 ExM-7 2.1x10 ^-2 Solv-1 0.09 Solv-3 7.0x10 ^-3

Seventh layer (medium-sensitive green sensitive emulsion layer) Silver iodobromide emulsion C Coating amount 0.37 Gelatin 0.54 ExS-4 8.5 × 10 ^-4 ExS-5 1.4 × 10 ^-4 ExS-8 8.3 × 10 ^-5 ExM-1 0.27 ExM-7 7.2 x 10 ^-2 ExY-1 5.4 x 10 ^-2 Solv-1 0.23 Solv-3 1.8 x 10 ^-2

Eighth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion D Coating amount 0.53 Gelatin 0.61 ExS-4 7.1 × 10 ^-4 ExS-5 1.4 × 10 ^-4 ExS-8 4.6 × 10 ^-5 ExM-2 5.5 x 10 ^-3 ExM-3 1.0 x 10 ^-2 ExM-5 1.0 x 10 ^-2 ExM-6 3.0 x 10 ^-2 ExY-1 1.0 x 10 ^-2 ExC-1 4.0 x10 ^-3 ExC- 4 2.5 × 10 ⁻³ Cpd-6 1.0 × 10 ⁻² Compound represented by (A-No) of the present invention (see Table 2) Solv-1 0.12

Ninth layer (intermediate layer) Gelatin 0.56 UV-4 4.0 × 10 ^-2 UV-5 3.0 × 10 ^-2 Cpd-1 4.0 × 10 ^-2 Polyethyl acrylate latex 5.0 × 10 ^-2 Solv-1 3.0 × 10 ^-2

The tenth layer (donor layer having a multi-layer effect on the red-sensitive layer) Silver iodobromide emulsion E coating amount 0.40 Silver iodobromide emulsion F coating amount 0.20 Silver iodobromide emulsion G coating amount 0.39 Gelatin 0.87 ExS -3 9.8 x 10 ^-4 ExM-2 0.16 ExM-4 3.0 x 10 ^-2 ExM-5 5.0 x 10 ^-2 ExY-2 2.5 x 10 ^-3 ExY-5 2.0 x 10 ^-2 Solv-1 0.30 Solv-5 3.0 x 10 ^-2

Eleventh layer (yellow filter layer) Yellow colloidal silver 4.2 × 10 ^-2 DYE-1 1.02 × 10 ^-1 gelatin 0.84 Cpd-1 5.0 × 10 ^-2 Cpd-2 5.0 × 10 ^-2 Cpd-5 2.0 × 10 ^-3 Solv-1 0.13 H-1 0.25

Twelfth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion A Coating amount 0.50 Silver iodobromide emulsion H Coating amount 0.40 Gelatin 1.75 ExS-6 9.0 × 10 ^-4 ExY-1 8.5 × 10 ^-2 ExY-2 5.5 x 10 ^-3 ExY-3 6.0 x 10 ^-2 ExY-5 1.00 ExC-1 5.0 x 10 ^-2 ExC-2 8.0 x 10 ^-2 Solv-1 0.54

Thirteenth layer (intermediate layer) Gelatin 0.30 ExY-1 0.14 Solv-1 0.14

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion I Coating amount of 0.40 Gelatin 0.95 ExS-6 6.3 × 10 ^-4 ExY-2 1.0 × 10 ^-2 ExY-3 2.0 × 10 ^-2 ExY-5 0.18 ExC-1 1.0 × 10 ^-2 Solv-1 9.0 × 10 ^-2

Fifteenth Layer (First Protective Layer) Fine grain silver iodobromide emulsion J Coating amount 0.12 Gelatin 0.63 UV-4 0.11 UV-5 0.18 Cpd-3 0.10 Solv-1 2.0 × 10 ^-2 Polyethyl acrylate latex 9.0 × 10 ^-2

16th layer (second protective layer) Fine grain silver iodobromide emulsion J Coating amount 0.36 Gelatin 0.85 B-1 (diameter 2.0 μm) 8.0 × 10 ⁻² B-2 (diameter 2.0 μm) 8.0 × 10 ^{− 2} B-3 1.3 x 10 ^-1 W-5 2.0 x 10 ^-2 H-1 0.18

In addition to the above, the samples thus prepared include
1,2-Benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm the same), and 2-phenoxyethanol (about 10,000 ppm the same) were added. In addition, each layer has appropriate storage properties, processability, pressure resistance, mildew / bacterial resistance,
In order to improve the antistatic property and coating property, W-1 to W-
6, B-1 to B-6, F-1 to F-10, F-13 to F
-16 and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt. The above silver halide emulsions are shown in Table 1.

[0094]

[Table 1]

In Table 1, (1) Emulsions A to I were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (3) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (4) Emulsions A to N are BH Carroll, Photographic Scien
Ce and Engineering, 24, 265 (1980) and the like contain iridium inside the particles.

[0096]

[Chemical 10]

[0097]

[Chemical 11]

[0098]

[Chemical 12]

[0099]

[Chemical 13]

[0100]

Embedded image

[0101]

[Chemical 15]

[0102]

Embedded image

[0103]

[Chemical 17]

[0104]

Embedded image

[0105]

[Chemical 19]

[0106]

Embedded image

[0107]

[Chemical 21]

[0108]

[Chemical formula 22]

[0109]

[Chemical formula 23]

[0110]

[Chemical formula 24]

[0111]

[Chemical 25]

[0112]

[Chemical formula 26]

The light-sensitive material produced as described above is set to 24 mm.
The width is cut into 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm at a position 0.7 mm from one side width direction of the photosensitive material. We made one with these two sets at 32 mm intervals,
296, 887 was housed in the plastic film cartridge illustrated in FIGS. For this sample, an input / output head having a head gap of 5 μm and a number of turns of 2,000 was used from the coated surface side of the magnetic recording layer, and an FM signal was sent at a feed rate of 1,000 / s during the perforation of the photosensitive material. Was recorded.

This sample 101 was cut to a width of 24 mm and photographed with a camera, and the following treatment was carried out for 1 m ² per day for 15 days. (Running processing) Each processing was carried out as follows using an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd. The overflow solution of the bleaching bath was reflowed to the waste solution tank without flowing into the post-bath. This FP-360B is published by the Invention Association Public Technical Report 94
Evaporation correction means described in No. 4992 is mounted. The treatment process and the treatment liquid composition are shown below.

(Treatment Step) Step Treatment time Treatment temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C. 20 ml 17 liters Bleach 50 seconds 38.0 ° C. 5 ml 5 liters Fixed (1) 50 seconds 38.0 ° C-5 liters Settlement (2) 50 seconds 38.0 ° C 8 ml 5 liters Water wash 30 seconds 38.0 ° C 17 ml 3.5 liters Stability (1) 20 seconds 38.0 ° C-3 liters Stability (2) 20 seconds 38.0 ° C. 15 ml 3 liters Dry 1 minute 30 seconds 60 ° C. * Replenishment amount is calculated per 1.1 mm of 35 mm width of photosensitive material (equivalent to 24 Ex. 1 bottle). The stabilizing solution was a countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into fixing (2). The fixer is also connected from (2) to (1) by countercurrent piping. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the fixing process, and the amount of the fixing solution brought into the water washing process are 2.5 ml and 2.0 ml per 35 mm width of the photosensitive material and 1.1 m, respectively. , 2.0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. The opening area of the above processor is 100 cm for color developer.
² , 120 cm ^{2 of} bleaching solution, about 100 for other processing solutions
cm ² .

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.3 Carbonic acid Potassium 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 2.0 2.0 Hydroxylamine sulfate 2. 4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.4 Add water 1.0 liter 1.0 liter pH (hydroxylation Prepared with potassium and sulfuric acid) 10.05 10.18

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropaneferric Acid Ammonium Ferric Acid Monohydrate 118 180 Ammonium Bromide 80 115 Ammonium Nitrate 14 21 Succinic Acid 40 60 Maleic Acid 33 50 Water was added to 1.0 liter 1.0 liter pH [prepared with aqueous ammonia] 4.4 4.0

(Fixer) Tank liquid (g) Replenisher (g) Ammonium methanesulfinate 10 30 Ammonium methanethiosulfonate 4 12 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 7 20 Ethylenediaminetetraacetic acid 15 45 Water was added to 1.0 liter 1.0 liter pH [prepared with ammonia water] 7.4 7.45

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH type strongly basic anion exchange resin (the same Amberlite IR-400) are passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 m.
g / l or less, followed by sodium diisocyanurate dichloride 20 mg / l and sodium sulfate 1
50 mg / l was added. The pH of this liquid is 6.5.
It was in the range of ~ 7.5.

(Stabilizing Solution) Tank Solution and Replenishing Solution Common (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid diester Sodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-benzisothiazolin-3-one 0.10 1.0 liter PH 8.5 with water added

The produced film cartridges of Samples 101 to 108 were loaded in the lens-fitted film unit described in JP-A-6-130558. At this time, Everea
dy (Fujifilm) AA alkaline batteries were loaded at the same time. Samples 101 to 103 were also prepared without a dry battery. The volume of aluminum foil surface-treated with polypropylene on both sides is 150 cm ³ and 12
It was stored in a package body of 0 cm ³ and hermetically sealed by heat sealing.

One set of these hermetically sealed packages is 4
After storing in a thermostatic chamber at 0 ° C for 7 days and the other set in a thermostatic chamber at 5 ° C for the same period, the samples of both sets were opened, and the light-sensitive material was exposed to grayscale gradation, and then the above color development processing was performed. Then, the density was measured, and the following photographic properties were evaluated from the characteristic curve. It should be noted that no apparent change was observed in the dry cell.

(1) Minimum density value of magenta density (ΔGmi
n) Read the minimum concentration values from the characteristic curves obtained by measuring the magenta concentration, and read the minimum concentration value (G ₄₀ ) of the same sample stored at 40 ° C and the minimum concentration value of the sample stored at 5 ° C ( The difference from G ₅ ) (ΔG min = G ₄₀ −G ₅ ) was determined. The smaller the value, the better the storage stability over time.

(2) Sensitivity of magenta color image (ΔG _0.2 ) From the characteristic curve obtained by measuring magenta density, the minimum density +
Calculate the logarithm of the reciprocal of the exposure dose that gives a density of 0.2,
Sensitivity value (DG of the same sample stored at 40 ° C)
₄₀ ) and the sensitivity value (DG ₅ ) of the sample stored at 5 ° C (△
G _0.2 = DG ₄₀ -DG ₅₎ was determined. The smaller the value, the better the storage stability over time. The results of representative samples are shown in Table 2.

[0125]

[Table 2]

From Table 2, at least one of the silver halide light-sensitive layers of the light-sensitive material of the present invention has the general formulas (AI) to (A).
Samples 102B1, 103B1, 104 to 108 containing the compound represented by the formula (V) and hermetically packaged in a package having a capacity of less than 140 cm ³ by combining dry batteries,
It is clear that in the storage stability of photographic properties under the condition of accelerated storage over time, the increase in fog is small and the increase in sensitivity is small. In addition, the deterioration of the photographic storability with time due to the presence of the dry battery is due to the fact that A1 and A2 of Sample 101 are
This can be seen by comparing B1 and B2. Furthermore, it is also clear by comparing A1 and B1 of sample 101 that the aging property of the photographic property is deteriorated when a dry battery is present and the volume of the package is small. In the present invention, by using the compound A-No. 9, the volume of the package is further increased to 150 even in the presence of the dry battery.
It can be seen by comparing each of Samples 102 and 103 that even if the size is reduced from cm ³ to 120 cm ³ , it exhibits an excellent effect that the storability is not changed as compared with the case where it is hermetically packaged in a package without a dry battery. Example 2 Using the samples 101-108 prepared in Example 1, these samples were cut to a length of 12 cm, one set in the presence of air and the other set completely replaced by hydrogen gas. Example 1
Similarly to the above, a sealed package of 150 cm ³ and 120 cm ³ was prepared, and both were stored for 7 days under a constant temperature condition of 25 ° C. After storage with time, these samples were subjected to white gradation exposure, the color development processing described in Example 1 was performed, and the density was measured to obtain the characteristic curve. Based on these characteristic curves, the following photographic properties were examined between the same samples in accordance with Example 1. (1) the difference between the minimum density value of the magenta density (△ Gmin) minimum density value of the hydrogen gas replacement sample (G _H) and the minimum density value of the sample in the presence of air and _{(G A) (△ Gmin =} G H -G
_A ) asked.

(2) Sensitivity of magenta color image (ΔG _0.2 ) The relative value of the reciprocal of the exposure amount giving the density of the minimum density + _0.2 was calculated, and the sensitivity value (D _H ) of the sample replaced with hydrogen gas and the air were calculated. Difference from the sensitivity value (D _A ) of the sample in the presence (ΔG _0.2 = D
_H- D _A ) was determined. Table 3 shows representative results.

[0128]

[Table 3]

From the results of Table 3, (A-I) of the present invention ~
The sample containing the compound represented by (A-V) has a small increase in the minimum concentration value and the sensitivity in both the samples filled with air and hydrogen gas, but the sample 101 containing no compound of the present invention is Due to the hydrogen gas filling and the size of the hermetically sealed package, the above photographic performance varies greatly,
It can be seen that the influence of hydrogen gas and its amount change. It can also be seen that this variation in photographic properties shows a completely similar tendency when compared with the results of Example 1 (Table 2) with and without dry batteries. As a result, it is speculated that the influence of the photographic property due to the presence of the dry cell may be due to the generation of hydrogen gas accompanying the discharge of the dry cell.

Example 3 Samples 301 to 308, excluding the magnetic substance of the magnetic recording layer of Samples 101 to 108, were prepared and evaluated in the same manner as in Example 1. The magnetic properties were also evaluated. The results of representative samples are shown in Table 4.

[0131]

[Table 4]

From Table 4, although the sample containing the magnetic substance can be magnetically recorded, it has a dry battery and has the general formula (A-
Sample 1 containing no compounds represented by I) to (A-V)
01B1 has a greater variation in photographic properties due to forced aging than Sample 301B1 containing no magnetic material. However, it can be seen that, even if it has a magnetic substance, it has a dry battery and contains the compound of the present invention, the variation in photographic properties due to storage over time hardly changes.

[0133]

According to the present invention, a lens having both a multi-layer silver halide color photographic light-sensitive material containing (AI) to (A-V) in at least one silver halide light-sensitive layer and a dry battery is provided. The volume of the film unit is 50 to 140 cm
It is possible to provide a hermetically sealed package having a range of ³ and having excellent stability over time with little fluctuation in fog density and photographic characteristics of sensitivity even when the package is stored over time.

Claims (2)

[Claims] 1. A multi-layer silver halide color photographic light-sensitive material having at least one red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, and a dry battery in the same package. A multi-layer silver halide color photographic light-sensitive material package which is hermetically sealed inside, wherein at least one of the silver halide-containing photosensitive layers of the multi-layer silver halide color photographic light-sensitive material has the following general formula (AI) to
A multi-layer silver halide color photographic light-sensitive material package containing the compound represented by (AV) and having a volume of 50 cm ³ or more and 140 cm ³ or less. Embedded image In formula (AI), R _a1 is an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group,
Represents a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, R
_a2 represents a hydrogen atom or a group represented by R _a1 . However,
When R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R _a1 and R _a2 may combine with each other to form a 5- to 7-membered ring. In formula (A-II), X represents a heterocyclic group, and R _b1 represents an alkyl group, an alkenyl group or an aryl group.
X and R _b1 may combine with each other to form a 5- to 7-membered ring. In the general formula (A-III), Y represents a nonmetallic atom group necessary for forming a 5-membered ring with -N = C-.
Y represents a group of non-metal atoms necessary for forming a 6-membered ring together with a -N = C- group, and the terminal of Y bonded to the carbon atom of the -N = C- group is -N (R _C1 ). -, -C (R _C2 ) (R _C3 )-,
-C (R _C4 ) = represents a group selected from -O- and -S- (bonded to the carbon atom of -N = C- on the left side of each group).
R _{C1 to} R _C4 represent a hydrogen atom or a substituent. In formula (A-IV), R _d1 and R _{d2, which} may be the same or different, each represents an alkyl group or an aryl group. However, when R _d1 and R _d2 are simultaneously an unsubstituted alkyl group and R _d1 and R _d2 are the same group, R _d1 and R _d2
Is an alkyl group having 8 or more carbon atoms. General formula (A-V)
In, R _e1 and R _e2 may be the same or different,
Each represents a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl group or an aryl group. However, R _e1 and R _e2 are not —NHR _e3 (R _e3 is an alkyl group or an aryl group) at the same time. R _a1 and R _a2 , X and R
_b1 may combine with each other to form a 5- to 7-membered ring. 2. A multi-layer silver halide color photographic light-sensitive material having a magnetic layer containing a ferromagnetic powder on the back surface opposite the photosensitive emulsion layer and the support. The multi-layered silver halide color photographic light-sensitive material package described.