JP2000112056A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material suppressing the increase of fog during storage under the conditions of a high temperature and high humidity by incorporating at least one of specified compounds. SOLUTION: This silver halide photographic sensitive material contains at least one of compounds represented by formula in which each of X1 and X2 is SR1, SeR2 or OR3, each of Y1 and Y2 is NR4R5, SR6, SeR7 or OR8, each of Z1 and Z2 is a divalent bonding group, each of R1-R3 and R6-R8 is H atom or an aliphatic or aromatic or hetero-cyclic group, each of R4 and R5 is H atom or an aliphatic, aromatic, heterocyclic, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkylsulfonyl or arylsulfonyl group, Q is an anion and (m) is an integer of 0-4. A fog due to storage is greatly suppressed and especially in the conditions of high temperature and high humidity, the storage stability is remarkably improved by using one of these compounds as the ligands of palladium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive silver halide photographic material. In particular, the present invention relates to a silver halide photographic light-sensitive material in which the photographic performance after storage is small and the fog is small.

[0002]

2. Description of the Related Art In silver halide photographic light-sensitive materials,
It is demanded that the sensitivity be high and that the photographic properties be kept small after storage after the production of the photosensitive material.
In particular, a technique for suppressing fog is required. The addition of a palladium compound for the purpose of suppressing fog is described in U.S. Pat. Nos. 2,566,263 and 2,566,245,
It is disclosed in JP-A-6-202283, JP-A-3-505263, and the like, and has the effect of actually suppressing an increase in fog during storage. However, JP-A-6-202283
However, as described, the viscosity of the coating solution containing the palladium compound may increase significantly due to the interaction between palladium ions and gelatin, and the amount of the palladium compound added may be reduced to such an extent that the viscosity of the coating solution does not increase significantly. It has been used with restraint. In order to sufficiently exert the effect of the palladium compound, there has been a strong demand for a palladium compound in which the increase in the viscosity of the coating solution is suppressed and a method of using the palladium compound in which the increase in the viscosity is suppressed. In this regard, JP-A-8-2
No. 34341 (US-5614360) discloses that a palladium compound coordinated with an organic compound having two nitrogen atoms in one molecule as a coordinating group does not increase in viscosity even under a high gelatin concentration, but is exemplified. Of ethylenediamine
The Pd complex is a compound that has been described for a long time in US-2552229. Although this palladium compound is described in the specification (JP-A-8-234341) as having an effect of suppressing fogging during storage under a moderate humidity of 50%, it has already been disclosed in US-2552229. As described above, when stored under tropical conditions of high temperature and high humidity, there is a problem that there is almost no effect of suppressing fogging. Such a tendency will be described later in Examples, but was also confirmed by our study. As described above, the conventionally known palladium compounds have insufficient effect, particularly the effect of suppressing fogging during storage under high-temperature and high-humidity conditions is insufficient, and a means for solving these problems has been demanded. .

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a means for improving the storability of a silver halide photographic material, and in particular, a means for suppressing an increase in fogging during storage under high temperature and high humidity conditions. It is.

[0004]

The above object is achieved by the following (1).
(4). (1) A silver halide photographic material comprising at least one compound represented by the following general formula (I).

[0005]

Embedded image

In the formula, X ₁ and X ₂ are SR1, SeR2, O
Represents R3, and Y ₁ and Y ₂ are NR4R5, SR6, SeR
7, OR8, and Z ₁ and Z ₂ each represent a divalent linking group.
R1, R2, R3, R6, R7, and R8 represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group; R4 and R5 represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group; Group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, and arylsulfonyl group. Q represents an anionic ion, and m represents an integer of 0 to 4. (2) In the general formula (I), X ₁ and X ₂ are S
R ₁ , Z ₁ and Z _{2 each} represent a substituted or unsubstituted alkylene group, alkenylene group, arylene group having 2 to 6 carbon atoms, or a group comprising these and a carbonyl group or a sulfonyl group, and Y ₁ represents NR4R5, OR8 (1) The silver halide photographic material as described in (1) above.

The silver halide photographic material of the present invention is preferably a color photographic material, more preferably a photographic color photographic material.

Next, the compound represented by formula (I) will be described in detail.

In the general formula (I), X ₁ and X ₂ represent SR
1, represents SeR2 and OR3. R1, R2, and R3
Represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. R
In 1, 1, R2 and R3, the aliphatic group preferably has 1 to 30 carbon atoms, particularly a straight-chain, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group having 1 to 10 carbon atoms. It is. Here, the cyclic may form a saturated heterocycle containing one or more heteroatoms therein. Examples of the alkyl group, alkenyl group, alkynyl group, and aralkyl group include a methyl group, an ethyl group, a propyl group, a cyclopropyl group, an allyl group, a propargyl group, and a benzyl group. R1, R
In 2, 2 and R3, the aromatic group preferably has 6 to 30 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 12 carbon atoms, such as a phenyl group or a naphthyl group. is there. In R1, R2 and R3, the heterocyclic group is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. These may be monocyclic or may form a condensed ring with another aromatic ring. The heterocyclic ring is preferably a 5- to 6-membered aromatic heterocyclic ring, for example, a pyridyl group, an imidazolyl group, a quinolyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolyl group, a thiazolyl group, a thienyl group, Examples include a furyl group and a benzothiazolyl group.

Each group represented by R1, R2 and R3 in the general formula (I) may be substituted, and examples of the substituent include the following. Halogen atom (fluorine atom,
Chlorine atom, bromine atom, iodine atom), cyano group, nitro group, ammonium group (for example, trimethylammonio group, etc.), phosphonio group, sulfo group, sulfino group, carboxy group, phosphono group, hydroxy group, mercapto group, hydrazino Group, alkyl group (for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group,
n-octyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, allyl group, 2-butenyl group, 3-pentenyl group, etc.), alkynyl group (eg, propargyl group, 3-pentynyl group, etc.), Aralkyl groups (eg, benzyl group, phenethyl group, etc.), aryl groups (eg, phenyl group, naphthyl group, 4-methylphenyl group, etc.), heterocyclic groups (eg, pyridyl group,
Furyl group, imidazolyl group, piperidyl group, morpholino group, etc.), alkoxy group (eg, methoxy group, ethoxy group, butyloxy group, etc.), aryloxy group (eg, phenoxy group, 2-naphthyloxy group, etc.), alkylthio group ( For example, methylthio group, ethylthio group, etc., arylthio group (eg, phenylthio group, etc.), amino group (eg, unsubstituted amino group, methylamino group, dimethylamino group, ethylamino group, alinino group, etc.), acyl group (Eg, acetyl group, benzoyl group, formyl group, pivaloyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), carbamoyl group (eg, , Unsubstituted carba Yl group, N, N- dimethylcarbamoyl group, N- ethylcarbamoyl group, N- phenylcarbamoyl group, etc.), an acyloxy group (e.g.,
Acetoxy group, benzoyloxy group, etc., acylamino group (eg, acetylamino group, benzoylamino group, etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, etc.), aryloxycarbonylamino group (eg, phenoxycarbonylamino group Ureido groups (eg, unsubstituted ureido groups, N
-Methylureido group, N-phenylureido group, etc.),
Alkylsulfonylamino group (for example, methylsulfonylamino group), arylsulfonylamino group (for example,
A phenylsulfonylamino group, an alkylsulfonyloxy group (eg, a methylsulfonyloxy group), an arylsulfonyloxy group (eg, a phenylsulfonyloxy group, etc.), an alkylsulfonyl group (eg, a mesyl group, etc.), an arylsulfonyl group (eg, , Tosyl group, etc.), alkoxysulfonyl group (eg, methoxysulfonyl group), aryloxysulfonyl group (eg, phenoxysulfonyl group), sulfamoyl group (eg, unsubstituted sulfamoyl group, N-methylsulfamoyl group, An N, N-dimethylsulfamoyl group,
An N-phenylsulfamoyl group, an alkylsulfinyl group (eg, a methylsulfinyl group), an arylsulfinyl group (eg, a phenylsulfinyl group), an alkoxysulfinyl group (eg, a methoxysulfinyl group), an aryloxysulfinyl group (For example, a phenoxysulfinyl group), a phosphoric amide group (for example, an N, N-diethylphosphoric acid amide group) and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

In the general formula (I), Z ₁ and Z ₂ each represent a divalent linking group. Examples of the divalent linking group include an alkylene group (methylene, ethylene, propylene, cyclopentylene, cyclohexylene, etc.), an alkenylene group (eg, vinylene), an alkynylene group (eg, propynylene), an arylene group (phenylene group, naphthalene group, etc.). ), Divalent heterocyclic group (pyridine as a heterocyclic ring,
Imidazole, quinoline, pyrimidine, thiazole, thiophene, furan, morpholine, piperazine, piperidine, etc.) and a carbonyl group or a sulfonyl group. Further, Z ₁ and Z ₂ may be substituted by those mentioned as the substituents of R1 to R3.

In the general formula (I), Y ₁ and Y ₂ are NR4
R5, SR6, SeR7, OR8. R6, R7,
And R8 represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and R4 and R5 represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. , A carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group. R4-R
8 is an aliphatic group, an aromatic group, or a heterocyclic group represented by R ₁ of X ₁ or X ₂ .
It is synonymous with R3. The acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, and arylsulfonyl group of R4 and R5 preferably have 1 to 20 carbon atoms,
Examples include acetyl, benzoyl, formyl, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, mesyl, and tosyl.

In the general formula (I), X₁And X_Two , Y₁
And Y_Two, And Z₁And Z_TwoAre the same but different
It may be. Also, X₁And Z₁Or Y₁And Z₁
May combine to form a saturated or unsaturated heterocyclic ring.
, X_TwoAnd Z_TwoOr Y_TwoAnd Z _TwoAre linked or saturated or
It may form an unsaturated heterocyclic ring. Furthermore, X₁And X_Two
Or / and Y₁And Y_TwoIs linked to one molecule
A compound that coordinates with the cation may be formed.

In the general formula (I), Q represents an anionic ion. Halogen ion, nitrate ion, carbonate ion, hydrogen carbonate ion, sulfate ion, sulfite ion, cyano ion, cyanate ion, isocyanate ion, thiocyanate ion, borate ion, phosphonate ion, perchlorate ion, organic carboxylic acid Ions (e.g., formate ion, acetate ion, oxalate ion, etc.), organic sulfonic acid ions (e.g., methane sulfonic acid ion, benzene sulfonic acid ion, p-toluene sulfonic acid ion, 2,
6-naphthalene-disulfonate ion).
Preferred are halogen ions (chloro ions, bromo ions), nitrate ions, sulfate ions, sulfite ions, cyanate ions, and perchlorate ions.

In the general formula (I), m represents an integer of 0 to 4.

In the general formula (I), preferably X₁
And X_Two , Y₁And Y_Two, And Z₁And Z _TwoAre the same for each
And X₁Is SR1, SeR2, OR3,
Z₁Is a substituted or unsubstituted alkylene group or alkenylene
Group, arylene group, or carbonyl group or
A group consisting of a sulfonyl group,₁Is NR4R5, S
R6, SeR7, OR8, R1 to R3 and R6
To R8 are a hydrogen atom, an unsubstituted or hydrophilic group (for example,
Sulfo group, sulfino group, carboxy group, phosphono group,
Hydroxy group, carbamoyl group (for example, unsubstituted
Bamoyl group, N, N-dimethylcarbamoyl group, N-E
A tylcarbamoyl group, an N-phenylcarbamoyl group,
), An acylamino group (for example, an acetylamino group,
Nzoylamino group), alkoxycarbonylamino
Groups (for example, methoxycarbonylamino group), urea
Group (eg, unsubstituted ureido group, N-methyluree
Group, an N-phenylureido group, etc.)
Honylamino group (for example, methylsulfonylamino
Group), sulfamoyl group (eg, unsubstituted sulfamoyl group)
Yl group, N-methylsulfamoyl group, N, N-dimethyl
Rusulfamoyl group, N-phenylsulfamoyl group
And the like) substituted alkyl group and aryl group,
R4 and R5 represent a hydrogen atom, an unsubstituted or hydrophilic group (parent)
The aqueous groups are the same as the hydrophilic groups of R1 to R3 and R6 to R8.
Definition) substituted alkyl group, aryl group, acyl group,
Alkoxycarbonyl group, carbamoyl group, alkyl sulf
A honyl group (preferably having 1 to 20 carbon atoms,
For example, acetyl group, formyl group, methoxycarbonyl
Group, ethoxycarbonyl group, mesyl group, etc.).

In the general formula (I), more preferably,
X ₁ is SR ₁ , OR 3, and Z ₁ is a substituted or unsubstituted alkylene group, alkenylene group, arylene group having 2 to 6 carbon atoms, or a group comprising these and a carbonyl group or a sulfonyl group, and Y ₁ is NR 4 R 5, SR 6 , OR8
R1 to R3 and R6 to R8 each represent a hydrogen atom, an unsubstituted or hydrophilic group (for example, a sulfo group, a carboxy group, a hydroxy group, an unsubstituted carbamoyl group, N, N-
Dimethylcarbamoyl group, N-ethylcarbamoyl group,
Acetylamino group, unsubstituted ureido group, N-methylureido group, methylsulfonylamino group, unsubstituted sulfamoyl group, N-methylsulfamoyl group) substituted alkyl group having 1 to 8 carbon atoms, aryl Group,
R4 and R5 are a hydrogen atom, an unsubstituted or substituted by a hydrophilic group (the hydrophilic group is the same as the hydrophilic group of R1 to R3 and R6 to R8), an alkyl group having 1 to 8 carbon atoms, an aryl group, and an acyl group. Group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group (preferably acetyl group,
Formyl group, methoxycarbonyl group, ethoxycarbonyl group, mesyl group).

Next, specific examples of the compound represented by formula (I) are shown, but the compounds of the present invention are not limited to these.

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

In the general formula (I), the ligand (for example, X
1-Z1-Y1) can be easily obtained as a commercially available drug or as a compound synthesized from a commercially available drug by a known method. The palladium compound represented by the general formula (I) can be synthesized from a corresponding ligand and an organic or inorganic palladium compound by a known method. As a synthesis method, J. Inorg. Nucl. Che
m., 41, 429 (1979), Inorg. Chim. Act
a, Volume 7, p. 88 (1973), Acta Crystallogr., S
ect. B, 29, 762 (1973), Inorganic Chemistry, 7, 1447 (1968).
Year), Journal of Inorganic Chemistry, 8, 304, 1963, 23, 5
61 (1978).

As the palladium compound used in the synthesis of the general formula (I), for example, Gmelin Handbook (Gmel
in Handbook) and are commercially available, synthetic, and in situ synthetic. Specific examples of useful palladium compounds include palladium (II) chloride, palladium (II) bromide, palladium (II) hydroxide, palladium (II) sulfate, palladium thiocyanate (I
I), tetrachloropalladium (II) acid salt (sodium salt, potassium salt, ammonium salt), hexachloropalladium (IV) acid salt, tetrabromopalladium (II)
Acid salt, hexabromopalladium (IV) acid salt, bis (salicylate) palladium (II) acid salt, bis (dithiooxalate-S, S ′) palladium (II) acid salt, tran
s-Dichlorobis (thioether) palladium (I
I), tetraamminepalladium (II) salt, dichlorodiaminepalladium (II), dibromodiaminepalladium (II), oxalatediaminepalladium (I
I), bis (ethylenediamine) palladium (II)
Salt, dichloroethylenediamine (palladium) (I
I), bis (2,2'-bipyridyl) palladium (II)
Salt, bis (1,10-phenanthroline) palladium (I
I) Salts, bis (glycinate) palladium (II).

In the present invention, as a method for adding the compound represented by the general formula (I) to a silver halide photographic light-sensitive material, a method usually used when an additive is added to a photographic light-sensitive material is applied. For example, a water-soluble compound is an aqueous solution of an appropriate concentration, and a compound insoluble or hardly soluble in water is a suitable organic solvent miscible with water, for example, alcohols,
Among the glycols, ketones, esters, and amides, they can be dissolved in a solvent that does not adversely affect photographic properties and added as a solution. Further, as the compound represented by the general formula (I), a compound synthesized and isolated by the method described in the above literature may be used, or a halogenated compound may be used without isolation in the form of a mixed solution of a palladium compound and a ligand. It may be added to a silver halide photographic material.

In the present invention, a solution of a palladium compound can be added to a photosensitive emulsion layer, an intermediate layer, an antihalation layer, and a surface protective layer. Further, the solution of the palladium compound of the present invention may be newly provided as a separate layer together with a binder. When it is added to these layers, it is added to the coating solution of these layers, but it may be any case from the time when the coating solution is adjusted to immediately before the coating. When it is added to the photosensitive emulsion layer, it may be added immediately after grain formation of the silver halide emulsion, but is preferably added after chemical sensitization.

In the present invention, the added amount of the palladium compound is from 1 × 10 ⁻⁷ mol to 1 × per 1 m ² of the light-sensitive material.
It is in the range of 10 ^-3 mol. Preferably it is in the range of 1 × 10 ^-6 mol to 1 × 10 ^-4 mol.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided 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 layers of the same color sensitivity. A non-photosensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers of a high-speed emulsion layer and a low-speed emulsion layer toward a support. It is preferable to arrange them so that the degree is low. Also, JP-A-57-112751, 62-200350, 62-2
As described in JP-A Nos. 06541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support.

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

As described in JP-B-55-34932, the blue-sensitive layer / GH /
They can be arranged in the order of RH / GL / RL. Also, JP-A-56
As described in -25738 and 62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a higher sensitivity than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A-59-202464, in the same color-sensitive layer, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in this order from the side away from the support.

In addition, high-speed emulsion layers / low-speed emulsion layers / medium-speed emulsion layers, or low-speed emulsion layers / medium-speed emulsion layers / high-speed emulsion layers may be arranged in this order.

In the case of four or more layers, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. No. 4,663,27
1, 4,705,744, 4,707,436, JP-A-62-160448,
It is preferable to arrange 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 the specification of JP-A-63-89850, adjacent to or adjacent to the main photosensitive layers. .

Preferred silver halides for use in the present invention are silver iodobromide, silver iodochloride, or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof.

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

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter referred to as RD).
No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and No. 18716 (November 1979), p. 648, No. 307105 (1989
Nov., pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimie)
et Phisique Photographiques, Paul Montel, 1967),
Duffin, Photographic Emulsion Chemistry, GF Duffin, Photographic Emulsion Chemistry, Foc
al Press, 1966), "Production and Coating of Photographic Emulsions", by Zelikman et al., Published by Focal Press (VL Zelikman, et a
l., Making and Coating Photographic Emulsion, Foca
l Press, 164).

US 3,574,628, US 3,655,394 and GB 1,4
Monodisperse emulsions described in 13,748 are also preferred.

Tabular grains having an aspect ratio of about 3 or more are particularly preferable and can be used in the present invention. Tabular grains are described in Photographic Science and Engineering (Gutoff, Photographic S
cience and Engineering), Vol. 14, pp. 248-257 (1970
Year); US 4,434,226, 4,414,310, 4,433,048,
It can be easily prepared by the methods described in 4,439,520 and GB 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used.

The above emulsion preferably has dislocations. In particular, tabular grains preferably have dislocations in the fringe. As a method for introducing dislocation, a method of forming a high silver iodide layer by adding an aqueous solution of an alkali iodide or the like, a method of adding AgI fine particles, and a method described in JP-A-5-3234
87 and the like can be used.

The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside a grain, or a type having a latent image on both the surface and the inside. Type emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm,
-20 nm is particularly preferred.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below.

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

Fused silver halide grains described in US Pat. No. 4,082,553, US Pat. No. 4,626,498, JP-A-59-214852.
It is preferable to apply the silver halide grains and colloidal silver having the inside of the grains described in (1) to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. , Its preparation method is described in US Pat.
It is described in 214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm, particularly 0.05
~ 0.6 μm is preferred. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains has a grain size within ± 40% of the average grain size). Is 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 contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide, average grain size (average value of projected area equivalent circle diameter)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary light-sensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound. Colloidal silver can be contained in the layer containing fine silver halide grains.

The coated silver amount of the light-sensitive material of the present invention is 8.0 g / m ²
The following is 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 Chemical sensitizer page 23, page 648, right column, page 866 2. 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868 Super sensitizer, page 649, right column Brightener page 24 page 647 page right column page 868 5. 5. Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column, dyes, ultraviolet absorbers Binder page 26 page 651 left column pages 873 to 874 7. 7. Plasticizer, page 27 page 650, right column, page 876 Lubricant Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 9. Static 27 pages 650 pages right column pages 876-877 Inhibitors 10. Matting Agents, pages 878 to 879 Various dye-forming couplers can be used in the light-sensitive material of the present invention, but the following couplers are particularly preferred.

Yellow coupler: Formula (I) of EP 502,424A
, (II); EP 513,496A of formula (1)
, (2) (especially Y-28 on page 18); EP 5
A coupler of the formula (I) in claim 1 of Claim 68,037A; U
S Couplers represented by general formula (I) in column 1, lines 45 to 55 of 5,066,576; general formula in paragraph 0008 of JP-A-4-274425
Couplers represented by (I); couplers described in claim 1 on page 40 of EP 498,381 A1 (especially D-35 on page 18); EP 447,96
Coupler represented by formula (Y) on page 4 of 9A1 (especially Y-1
(P. 17), Y-54 (p. 41)); US Pat.
Couplers represented by formulas (II) to (IV) in line 8 (especially II-17,1
9 (column 17), II-24 (column 19)).

Magenta coupler; JP-A-3-39737 (L-57 (1
L-68 (lower right of page 12), L-77 (lower right of page 13); EP
(A-4) -63 (p.134), (A-4) -73, -75 (13
9); EP 486,965 M-4, -6 (page 26), M-7 (page 27); EP 57
M-45 of 1,959A (page 19); (M-1) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-32631.

Cyan coupler: CX-1 of JP-A-4-04843,
3, 4, 5, 11, 12, 14, 15 (pages 14 to 16); JP-A-4-43
345 at C-7, 10 (p. 35), 34, 35 (p. 37), (I-1), (I
-17) (pages 42 to 43);
A coupler represented by (Ia) or (Ib). Polymer couplers: P-1 and P-5 in JP-A-2-44345 (page 11)
.

Examples of couplers in which the coloring dye has a suitable diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86),
Yellow colored magenta coupler ExM-7 described in the EP
(Page 202), EX-1 (page 249), EX-7 (page 251), US 4,83
Magenta colored cyan coupler CC-9 described in 3,069
(Column 8), CC-13 (column 10), US Pat. No. 4,837,136 (2) (column 8), a colorless masking coupler represented by the formula (A) in claim 1 of WO92 / 11575 (especially exemplified on pages 36 to 45). Compound) is preferred.

Examples of compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound:
Formulas (I), (II), (III) and (I) described on page 11 of EP 378,236A1.
V) (especially T-101 (page 30), T-104 (31
), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-
158 (page 58)), a compound represented by the formula (I) described on page 7 of EP 436,938A2 (particularly D-49 (page 51)), a compound of the formula of EP 568,037A
Compounds represented by (1) (especially (23) (page 11)), EP440,19
Compounds of the formulas (I), (II) and (III) described on pages 5 to 6 of 5A2 (especially I- (1) on page 29); Bleaching accelerator releasing compounds: EP 310,125 A2, page 5 Compounds represented by formulas (I) and (I ') (especially (60) and (61) on page 1) and compounds represented by formula (I) in claim 1 of JP-A-6-59411 (especially (7) (P. 7);
Ligand releasing compound: a compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478 (especially, a compound on lines 21 to 41 of column 12); leuco dye releasing compound: compounds 1 to 6 of columns 3 to 8 of US 4,749,641 ; Fluorescent dye releasing compound: US
4,774,181, a compound represented by COUP-DYE of claim 1 (especially, compounds 1 to 11 in columns 7 to 10); a development accelerator or fogging agent releasing compound: the formula in column 3 of US 4,656,123
Compounds represented by (1), (2) and (3) (particularly in column 25)
(I-22)) and EP 450, 637A2, ExZK-
2; Compound that releases a group that becomes a dye only when it is released: US
Compounds of the formula (I) in claim 1 of 4,857,447 (especially Y-1 to Y-19 in columns 25 to 36).

As the additives other than the coupler, the following are preferable.

Latex for impregnation of oil-soluble organic compounds: US
Latex according to 4,199,363; oxidized developer scavenger: US Pat. No. 4,978,606, column 2, lines 54-62, formula (I)
(Particularly I-, (1), (2), (6), (12)
(Columns 4-5), formulas in rows 5-10 of column 2 of US 4,923,787 (especially compound 1 (column 3); stain inhibitor: EP
Formulas (I) to (III) on page 4, lines 30 to 33 of 298321A, especially I-47, 7
2, III-1, 27 (pages 24 to 48); anti-fading agent: EP 298321A
A-6, 7, 20, 21, 23, 24, 25, 26, 30, 37, 40, 4
2, 48, 63, 90, 92, 94, 164 (pp. 69-118), US 5,122,
444 columns 25-38 II-1 to III-23, especially III-10, EP
471347A, pages 8-12, I-1 to III-4, especially II-2, US
5,139,931 columns 32-40 A-1 to 48, especially A-39,4
2; Material for reducing the amount of the coloring enhancer or the color mixture inhibitor used: EP 411324A, pages 1 to 24, I-1 to II-15, especially I-
46; formalin scavenger: SCV-1 to 28 on pages 24 to 29 of EP 477932A, especially SCV-8; hardener: JP-A 1-214845
Compounds represented by formulas (VII) to (XII) in columns 13 to 23 of H-1, 4, 6, 8, 14, U.S. Pat.
54), a compound (H-1 to 76) represented by the formula (6) on the lower right of page 8 of JP-A-2-214852, particularly H-14, a compound described in claim 1 of US 3,325,287; a development inhibitor precursor: JP
P-24, 37, 39 at 62-168139 (pages 6-7); compounds described in claim 1 of US 5,019,492, especially at 28, 29 in column 7;
Preservatives and fungicides: I-1 of columns 3 to 15 of US 4,923,790
III-43, especially II-1, 9, 10, 18, III-25; stabilizers,
Antifoggant: US 4,923,793 columns 6 to 16 I-1 to (1
4), especially I-1, 60, (2), (13), compounds 1-65 of columns 25-32 of US 4,952,483, especially 36: Chemical sensitizer: triphenylphosphine selenide, JP-A-5-40324. Compound 50; dye: JP-A-3-156450, pages 15-18, a-1 and b-
20, especially a-1, 12, 18, 27, 35, 36, b-5, V-1 to 23 on pages 27 to 29, especially V-1, F- on page 33 to 55 of EP 445627A.
I-1 to F-II-43, especially FI-11, F-II-8, EP 457153A
III-1 to 36 on pages 17 to 28, especially III-1, 3, WO 88/0479
4-8-26 Microcrystalline dispersion of Dye-1 to 124, EP 319999A
Compounds 1 to 22 on pages 6 to 11, especially compound 1, EP 519
Compounds D-1 to 87 represented by formulas (1) to (3) of 306A
(Pages 3 to 28), compounds 1 to 22 represented by the formula (I) of US Pat. No. 4,268,622 (columns 3 to 10), and compounds (1) to (31) represented by the formula (I) of US Pat. 9); UV absorber:
Compounds (18b) to (1b) represented by formula (1) of JP-A-46-3335
8r), 101 to 427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) represented by the formula (I) and compounds HBT-1 represented by the formula (III) in EP 520938A. 10 (page 14), compounds (1) to (31) represented by the formula (1) in EP 521823A (columns 2 to 3)
9). The following compounds are used as dispersion media for oil-soluble organic compounds:

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

The following compounds are used as surfactants:

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

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, Tokuhei 2-32615, actual fairness
It is suitable for a film unit with a lens described in 3-39784.

Suitable supports usable in the present invention include, for example, RD. No. 17643, page 28, RD. No. 18716, page 647, right column to page 648, left column, and RD. No. 307105, page 879. It is described in.

The specific photographic sensitivity in the present invention is described in
It is determined by the method described in 3-23635. This measuring method is based on JIS K 7614-1981.
The differences are that the development processing is completed within 30 minutes or more and 6 hours after exposure for sensitometry, and that the development processing is based on the Fujicolor standard processing recipe CN-16. Others are substantially the same as the measurement method described in JIS.

The light-sensitive material of the present invention has a sensitivity closest to the support.
From the light-sensitive silver halide layer to the surface of this photographic material
The thickness is preferably 24 μm or less, and 22 μm or less.
Below is more preferred. The film swelling speed T_1/2Is less than 30 seconds
Preferably, the time is 20 seconds or less. T_1/2Is the color expression
Maximum swelling film reached when processed at 30 ° C for 3 minutes 15 seconds with imaging solution
Assuming that 90% of the thickness is the saturated thickness, the thickness reaches half of that
It is defined as the time to do. The film thickness is 25 ° C and relative humidity 55.
% Means the film thickness measured under humidity control (2 days). _1/2Is
A. Green and other photographic services
Jens and Engineering (Photogr.Sci.En
g.), Vol. 19, pp. 2,124-129
It can be measured by using a tar (swelling meter). T
_1/2Add hardener to gelatin as binder
Or by changing the aging conditions after application
Can be adjusted. The swelling ratio is 150-400%
preferable. The swelling ratio is the maximum swelling under the conditions described above.
From the wet film thickness, the formula: (maximum swollen film thickness-film thickness) / film thickness
Can be calculated.

In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, and a surfactant. The swelling ratio of this back layer is 150 ~ 500
% Is preferred.

The light-sensitive material of the present invention is obtained by using the above-mentioned RD.
No. 18716, No. 18716, 651 left column to right column, and No. 18716
No. 307105, pages 880 to 881 can be used for development.

Next, the processing solution for a color negative film used in the present invention will be described.

The compounds described in JP-A-4-21739, page 9, upper right column, line 1 to page 11, lower left column, line 4 can be used in the color developer used in the present invention. 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.

These color developing agents are used in an amount of preferably 0.01 to 0.08 mol, more preferably 0.015 to 0.06 mol, and even more preferably 0.02 to 0.05 mol, per liter of the color developing solution. The replenisher of the color developing solution preferably contains a color developing agent having a concentration of 1.1 to 3 times, more preferably 1.3 to 2.5 times the concentration.

As a preservative for the color developing solution, hydroxylamine can be used widely. However, when higher preservation is required, substitution with an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, or the like can be used. A hydroxylamine derivative having a group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) Hydroxylamines are preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred. These may be used in combination with hydroxylamine, but it is preferable to use one or more of them instead of hydroxylamine.

The preservative is preferably used in the range of 0.02 to 0.2 mol per liter, particularly preferably 0.03 to 0.15 mol, more preferably 0.04 to 0.1 mol. As in the case of the color developing agent, the replenisher preferably contains a preservative at a concentration of 1.1 to 3 times the concentration of the mother liquor (processing tank solution).

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 the range of 0.01 to 0.05 mol per liter, particularly preferably in the range of 0.02 to 0.04 mol.
In the replenisher, it is preferable to use the replenisher at a concentration 1.1 to 3 times the above.

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, and the replenisher is set to a high value within the range of 0.1 to 1.0 from these values. Preferably. In order to stably maintain such a pH, a known buffer such as carbonate, phosphate, sulfosalicylate, and borate is used. The replenishment amount of the color developing solution is preferably from 80 to 1300 ml per m ² of the light-sensitive material, but is preferably smaller from the viewpoint of reducing the environmental pollution load, specifically from 80 to 600 ml, more preferably from 80 to 400 ml. Milliliters are preferred.

The bromide ion concentration in the color developing solution is usually from 0.01 to 0.06 mol per liter. However, fog is suppressed while maintaining sensitivity, discrimination is improved, and graininess is improved. For this purpose, it is preferably set to 0.015 to 0.03 mol per liter. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferred that the replenisher does 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: 1 m ² exposure When the material is color-developed, the amount of bromide ion eluted from the light-sensitive material into the color-developing solution (mol) V: The replenishment amount of the color-developing replenisher for 1 m ² of the light-sensitive material (liter) In addition, when a high bromide ion concentration is set, 1-phenyl-3-pyrazolidone or 1-phenyl-2-methyl-2 may be used as a method for increasing sensitivity.
It is also preferable to use a development accelerator 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 bleaching ability in the present invention. .

The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more. Specific examples thereof are described in JP-A-5-72694 and JP-A-5-72694.
Preferred are those described in 5-173312, and in particular, 1,3-diaminopropanetetraacetic acid, and specific example 1 on page 7 of JP-A-5-73312.
Are preferred.

In order to improve the biodegradability of the bleaching agent, JP-A-4-251845, JP-A-4-268552, EP588,289, and 591,
934, a compound ferric complex salt described in JP-A-6-208213 is preferably used as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of a liquid having a bleaching ability.
It is preferable to design from 1 mol to 0.15 mol. If the bleaching solution is bleaching solution,
It is preferable to contain 0.2 mol to 1 mol of bromide, particularly preferably 0.3 to 0.8 mol.

The replenisher of the solution having bleaching ability basically contains the concentration of each component calculated by the following formula. Thereby, the concentration in the mother liquor can be kept 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 (processing tank liquid) C _P : during processing Concentration of consumed components V ₁ : Replenishment amount of replenisher having bleaching ability for photosensitive material of 1 m ² (milliliter) V ₂ : Amount brought in from prebath by photosensitive material of 1 m ² (milliliter) Preferably contains a pH buffer, particularly preferably a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid. Also, JP-A-53-95630, RDN
It is also preferable to use known bleaching accelerators described in O. 17129, US 3,893,858.

The bleaching solution contains 50 to 1000 per m ² of the light-sensitive material.
It is preferable to replenish milliliter of bleach replenisher,
Particularly, it is preferable to replenish 80 to 500 ml, more preferably 100 to 300 ml. Further, it is preferable to perform aeration on the bleaching solution.

The processing solution having a fixing ability is disclosed in
The compounds and processing conditions described on page 7, lower left column, line 10 to page 8, lower right column, line 19 of 4-125558 can be applied.

Particularly, in order to improve the fixing speed and the preservability, the processing solution having the fixing ability by using the compounds represented by the general formulas (I) and (II) of JP-A-6-301169, alone or in combination. Is preferably contained. In addition to the use of p-toluenesulfinic acid salts, the use of sulfinic acids described in JP-A-1-224762 is also preferable from the viewpoint of improving the preservation.

It is preferable to use ammonium as a cation in the solution having the bleaching ability or the solution having the fixing ability from the viewpoint of improving the desilvering property. However, from the viewpoint of reducing environmental pollution, ammonium is reduced or reduced to zero. Is more preferred.

In the bleaching, bleach-fixing and fixing steps, it is particularly preferable to carry out jet stirring described in JP-A-1-309590.

The replenishment rate of the replenisher in the bleach-fixing or fixing step is from 100 to 1000 ml, preferably from 150 to 700 ml, and particularly preferably from 200 to 600 ml, per m ² of the light-sensitive material.

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, the processing can be carried out with a reduced silver concentration in the solution, so that the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the remaining liquid as a replenisher.

The bleach-fixing step and the fixing step can be constituted by a plurality of processing tanks, and it is preferable that each tank is cascaded to form a multistage countercurrent system. From the balance with the size of the developing machine, a two-tank cascade configuration is generally effective, and the ratio of the processing time in the former tank and the latter tank is preferably in the range of 0.5: 1 to 1: 0.5. In particular, the range of 0.8: 1 to 1: 0.8 is preferable.

The bleach-fixing solution and the fixing solution preferably contain a free chelating agent which is not in the form of a metal complex from the viewpoint of improving the preservability. These chelating agents are described in connection with the bleaching solution. Preferably, a biodegradable chelating agent is used.

Regarding the washing and stabilizing steps, the contents described in the above-mentioned JP-A-4-125558, page 12, lower right column, line 6 to page 13, right lower column, line 16 can be preferably applied. In particular,
EP 504,609 instead of formaldehyde
Azolylmethylamines described in 519,190 and JP-A-4-36
From the viewpoint of preserving the working environment, it is preferable to use the N-methylolazoles described in 2943, or to dimerize the magenta coupler to obtain a surfactant-free liquid containing no image stabilizer such as formaldehyde. .

In order to reduce the adhesion of dust to the magnetic recording layer applied to the light-sensitive material, a stabilizer described in JP-A-6-289559 can be preferably used.

The amount of washing and replenishment of the stabilizing solution can be adjusted according to the photosensitive material 1
m is preferably from ² per 80 to 1,000 ml, in particular 100
~ 500 ml, and more preferably 150-300 ml, is a preferable range in terms of both securing a washing or stabilizing function and reducing waste liquid for environmental protection. In the treatment carried out with such a replenishing amount, a known method such as thiabendazole, 1,2-benzisothiazolin-3-one and 5-chloro-2-methylisothiazolin-3-one is used to prevent the growth of bacteria and fungi. It is preferable to use water deionized with an antifungal agent, an antibiotic such as gentamicin, or an ion exchange resin. It is more effective to use a combination of deionized water and a bactericide or antibiotic.

Further, the liquid in the washing or stabilizing liquid tank is
JP-A-3-46652, JP-A-3-53246, JP-A-355542, JP-A-3-12144
8, it is also preferable to reduce the replenishment amount by performing the reverse osmosis membrane treatment according to 3-126030, the reverse osmosis membrane in this case,
Preferably, it is a low pressure reverse osmosis membrane.

In the process of the present invention, it is particularly preferable to carry out the correction of evaporation of the processing solution disclosed in the Invention Association's Published Technical Report, Publication No. 94-4992. In particular, a method of performing correction using temperature and humidity information of a developing machine installation environment based on (Equation 1) on page 2 is preferable. The water used for evaporation correction is preferably collected from a replenishment tank for washing,
In that case, it is preferable to use deionized water as the washing replenishing water.

As the treating agent used in the present invention, those described in the above-mentioned published technical report, from page 3, right column, line 15 to page 4, left column, line 32 are preferred. In addition, as a developing machine used for this,
The film processor described on page 22, right column, lines 22 to 28 is preferred.

Specific examples of preferred processing agents, automatic developing machines, and evaporation correction systems for carrying out the present invention are described in the above-mentioned published technical report, from page 5, right column, line 11 to page 7, right column, last line. Have been.

The supply form of the treating agent used in the present invention is as follows.
It may be in any form, such as a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, pastes, and emulsions. As an example of such a treating agent, JP-A-63-1
7453 discloses a liquid agent contained in a container having low oxygen permeability,
19655, 4-230748, vacuum-packed powders or granules, 4-221951, granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 describe tablets and JP-A-57-5
Discloses a paste-like treating agent, which can be preferably used, but from the viewpoint of simplicity at the time of use,
It is preferable to use a liquid that has been prepared in advance in a concentration for use.

[0113] In the container for storing these treating agents, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon or the like is used alone or as a composite material. These are selected according to the required level of oxygen permeability. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials are used in containers having a thickness of 500 to 1500 μm, and preferably have an oxygen permeability of 20 ml / m ² · 24 hrs · atm or less.

Next, the processing solution for a color reversal film used in the present invention will be described. For the processing for the color reversal film, see page 6, line 5 to page 10, line 5 and page 15, line 8 to page 24, 2 of the publicly known technique No. 6 (April 1, 1991) issued by Aztec Co., Ltd. Each row is described in detail, and any of the contents can be preferably applied.

In processing a color reversal film, an image stabilizer is contained in a conditioning bath or a final bath. Such image stabilizers include, in addition to formalin, formaldehyde sodium bisulfite and N-methylolazole, and from the viewpoint of working environment, sodium formaldehyde sodium bisulfite or N-methylolazole is preferable, and N-methylol is preferred. As the azoles, N-methyloltriazole is particularly preferred. Further, the contents relating to the color developing solution, bleaching solution, fixing solution, washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film.

As a preferred color reversal film treating agent containing the above contents, Eastman Kodak E-6
Examples of the treating agent include CR-56 treating agent manufactured by Fuji Photo Film Co., Ltd.

Next, the magnetic recording layer used in the present invention will be described.

The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder.

The magnetic particles used in the present invention are γFe_TwoO
_ThreeSuch as ferromagnetic iron oxide, Co-coated γFe _TwoO_Three, Co deposited magne
Tight, Co-containing magnetite, ferromagnetic chromium dioxide, strong
Magnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr
Ferrite, Pb ferrite, Ca ferrite, etc. can be used.
You. Co deposited γFe_TwoO_ThreePreferred is Co-coated ferromagnetic iron oxide such as
No. Needle shape, rice grain shape, spherical shape, cubic shape, plate shape
And so on. S for specific surface area_BETAt 20m^Two/ g or more
Preferred, 30m^Two/ g or more is particularly preferred.

The saturation magnetization (σs) of the ferromagnetic material is preferably
3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, particularly preferably 4.
It is 0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in
The surface may be treated with a silane coupling agent or a titanium coupling agent as described in the above item. Also JP
Magnetic particles having a surface coated with an inorganic or organic substance described in JP-A Nos. 4-259911 and 5-81652 can also be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural material described in JP-A-4-219569. Combinations (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin has a Tg of -40 ° C to 300 ° C and a weight average molecular weight of 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates with polyalcohols (for example, 3mol of isocyanate and 1m of trimethylolpropane
ol reaction product), and polyisocyanates formed by condensation of these isocyanates.
For example, it is described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 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.
m, more preferably 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100.
And more preferably from 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m2, preferably 0.01 to ² g.
/ m ² , more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50,
0.03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable. The magnetic recording layer may be provided on the entire back surface of the photographic support by coating or printing, 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, etc. can be used. The coating solution described in 341436 is preferred.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. 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. These abrasives may have their surfaces 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 the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the polyester support preferably used in the present invention will be described. For details including photosensitive materials, treatments, cartridges and examples described later, refer to Published Technical Report, Official Technique No. 94-6023 (Invention Association; 1994.15.). The polyester used in the present invention is formed by using diol and aromatic dicarboxylic acid as essential components. As aromatic dicarboxylic acids, 2,6-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, and terephthalic acid are used. Acids, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred are polyesters containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene-2,
6-naphthalate. Average molecular weight range of about 5,000
Or 200,000. The Tg of the polyester of the present invention is 50
° C or higher, and more preferably 90 ° C or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg, in order to make it difficult to form a curl.
The heat treatment may be performed at a constant temperature within this temperature range,
The heat treatment may be performed while cooling. This heat treatment time is
The time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web. Unevenness is applied to the surface (for example, SnO ₂ or Sb ₂ O ₅
And the like, for example, may be applied to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and raising the ends only slightly to prevent cut-out of the core. These heat treatments are performed after forming the support film.
It may be carried out at any stage after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.) and after the application of the undercoat. Preferably after application of the antistatic agent.

The polyester may contain an ultraviolet absorber. In order to prevent light piping, the purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to perform 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, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, the undercoating method will be described. It may be a single layer or two or more layers. As a binder for the undercoat layer,
Starting from copolymers starting from monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., polyethylene imine, epoxy resin, grafting Gelatin, nitrocellulose and gelatin are included.
Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, as a gelatin hardener, chromium salt (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6) are used.
-Hydroxy-S-triazine), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate 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. As those antistatic agents, carboxylic acid and carboxylate, polymers including sulfonate,
Examples include cationic polymers and ionic surfactant compounds.

The most preferred antistatic agent is Zn.
O, TiO_Two, SnO_Two, Al_TwoO_Three, In_TwoO_Three, SiO_Two, MgO, BaO,
MoO_Three, V_TwoO_FiveAt least one volume resistivity selected from
Is 10 ⁷Ωcm or less, more preferably 10^FiveΩcm or less
Particle size 0.001 ~ 1.0μm crystalline metal oxide
Or these composite oxides (Sb, P, B, In, S, Si, C
Fine particles), sol-like metal oxide or
Fine particles of these composite oxides.

The content in the light-sensitive material is 5 to 500 mg / m ²
And particularly preferably 10 to 350 mg / m ² . The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably 1/300 to 100/1, more preferably 1/1.
00 to 100/5.

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 slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25
° C, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.

The slipping agents usable in the present invention include polyorganosiloxanes, higher fatty acid amides, metal salts of higher fatty acids, esters of higher fatty acids and higher alcohols, and the like. Siloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / 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, and the particle size distribution is preferably narrow, and the average particle size is 0.9 to 10 μm.
It is preferable that 90% or more of the total number of particles is contained during 1.1 times. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. Polystyrene particles (0.25 μm), colloidal silica (0.03
μm).

Next, the film cartridge used in the present invention will be described. The main material of the patrone 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 patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are disclosed in
37, 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be the same as the current 135 size, and it is effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less in order to reduce the size of the camera.
The volume of a cartridge case, 30cm ³ or less, preferably 25
It is preferably set to not more than cm ³ . The weight of plastic used for patrone and patrone case can range from 5g to 15g
g is preferred.

Further, a patrone used in the present invention to feed a film by rotating a spool may be used. Alternatively, a structure may be employed in which the leading end of the film is housed in the patrone main body, and the leading end of the film is sent out from the port portion of the patrone by rotating the spool shaft in the film sending direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development or a photographic film that has been subjected to development processing. Also, raw film and developed photographic film may be stored in the same new patrone,
A different patrone may be used.

The color photographic light-sensitive material of the present invention is also suitable as a negative film for an advanced photo system (hereinafter referred to as an AP system), and NEXIA A manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film). NEXI
Films processed into the AP system format such as AF and NEXIA H (in order, ISO 200/100/400) and stored in a special cartridge can be mentioned. These APs
The system cartridge film is used by loading it onto an AP system camera such as the EPION series (e.g., EPION 300Z) manufactured by Fujifilm. Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as a super color slim made by Fujifilm.

The film photographed by the above is printed in the mini-lab system through the following steps. (1) Reception (exposed cartridge film received from customer) (2) Detaching process (transfer film from cartridge to intermediate cartridge for developing process) (3) Film development (4) Retouching process (developed negative (Return the film to the original cartridge.) (5) Print (continuous automatic printing of C / H / P 3 type prints and index prints on color paper (preferably SUPER FA8 made by FUJIFILM)) (6) Verification and shipment (The cartridge and index print are collated by ID number and shipped together with the print.) These systems include Fujifilm Minilab Champion Super FA-298 / FA-278 / FA-258 / FA-238 and Fujifilm Digital Lab System Frontier. preferable. Minilab Champion film processors include FP922AL / FP562B / FP562B, AL / FP362B / FP362B, and AL, and the recommended processing chemical is Fujicolor Justit CN
-16L and CN-16Q. As a printer processor, PP3008AR / PP3008A / PP1828AR / PP1828A / PP1258AR / PP1
258A / PP728AR / PP728A, and the recommended treatment chemicals are Fujicolor Justit CP-47L and CP-40FAII. In Frontier System, Scanner & Image Processor SP-1000 and Laser Printer & Paper Processor LP-1000P or Laser Printer LP-1000W
Is used. The detacher used in the detaching step and the reattacher used in the rear attaching step are preferably DT200 / DT100 and AT200 / AT100 of Fujifilm, respectively.

The AP system can also be enjoyed by a photo joy system centered on the Fuji Film Aladdin 1000 digital image workstation. For example, Aladdin 1000 can be directly loaded with a developed AP system cartridge film, or negative, positive, and print image information can be transferred to a 35mm film scanner FE.
The digital image data obtained by inputting using the -550 or PE-550 flat head scanner can be easily processed and edited. The data are stored in a digital color printer NC-550AL using a light fixing type thermal color printing system and a pictograph 3000 using a laser exposure thermal development transfer system.
Or as prints by existing laboratory equipment through a film recorder. The Aladdin 1000 can also transfer digital information directly to a floppy disk, Zip disk, or via a CD writer.
You can also output to CD-R.

On the other hand, at home, the developed AP system cartridge film is transferred to a Fujifilm photo player AP.
You can enjoy photos on TV just by loading it in -1,
By loading it onto a Fujifilm AS-1 photo scanner, image information can be continuously and rapidly captured on a personal computer. To input a film, print or three-dimensional object to a personal computer, use Fujifilm PhotoVision FV-10 / FV
-5 is available. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using Fujifilm's application software Photo Factory. In order to output high-quality prints from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fujifilm of a light fixing type thermal color print system is suitable.

In order to store the developed AP system cartridge film, the Fuji Color Pocket Album AP-5 POP L, AP-1 POP L, AP-1 POP KG or the cartridge file 16 is preferable.

[0143]

EXAMPLES Example 1 On an undercoated cellulose triacetate film support,
Samples 101 to 113, which are multilayer color photosensitive materials, were prepared by coating each layer having the composition shown below in multiple layers. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer. (Sample 101) First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.155 Silver Iodobromide Emulsion P Silver 0.01 Gelatin 0.87 ExC-1 0.002 ExC-3 0.002 Cpd-2 0.001 HBS-1 0.004 HBS-2 0.002 Second layer (second antihalation layer) Black colloidal silver Silver 0.066 Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid disperse dye ExF-2 0.015 Solid disperse dye ExF-3 0.020 Third layer (intermediate layer) Silver iodobromide emulsion O 0.020 ExC-2 0.022 Polyethyl acrylate latex 0.085 gelatin 0.294 4th layer (low-speed red-sensitive emulsion layer) silver iodobromide emulsion A silver ^{0.323 ExS-1 5.5 × 10 -4} ExS-2 1.0 × 1 ^{-5 ExS-3 2.4 × 10 -4} ExC-1 0.109 ExC-3 0.044 ExC-4 0.072 ExC-5 0.011 ExC-6 0.003 Cpd-2 0.025 Cpd- 4 0.025 HBS-1 0.17 Gelatin 0.80 Fifth layer (Medium sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion B Silver 0.28 Silver iodobromide emulsion C Silver 0.54 ExS-1 0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 2.0 × 10 ^-4 ExC-1 0.14 ExC-2 0.026 ExC-3 0.020 ExC-4 0.12 ExC -5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18 6th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.47 ExS-1 3.7 × 10 ^-4 ExS-2 1 × 10 ^-5 ExS-3 1.8 × 10 ^-4 ExC-1 0.18 ExC-3 0.07 ExC-6 0.029 ExC-7 0.010 ExY-5 0.008 Cpd-2 0.046 Cpd- 4 0.077 HBS-1 0.25 HBS-2 0.12 Gelatin 2.12 7th layer (intermediate layer) Evaluation compound (compound shown in Table 2) Addition amount shown in Table 2 Cpd-1 0.089 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.83 Gelatin 0.84 Eighth layer (layer giving a multilayer effect to red-sensitive layer) Silver iodobromide emulsion E Silver 0.560 ExS-6 1.7 × 10 ^-4 ExS-10 4.6 × 10 ^-4 Cpd-4 0.030 ExM-2 0.096 ExM-3 0.028 ExY-1 0.031 HBS-1 0.085 HBS-30 003 Gelatin 0.58 Ninth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion F Silver 0.39 Silver iodobromide emulsion G Silver 0.28 Silver iodobromide emulsion H Silver 0.35 ExS-42 0.4 × 10 ^-5 ExS-5 1.0 × 10 ^-4 ExS-6 3.9 × 10 ^-4 ExS-7 7.7 × 10 ^-5 ExS-8 3.3 × 10 ^-4 ExM-20 0.36 ExM-3 0.045 HBS-1 0.28 HBS-3 0.01 HSB-4 0.27 Gelatin 1.39 10th layer (Medium-speed green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 0.03 45 ExS-4 5.3 × 10 ^-5 ExS-7 1.5 × 10 ^-4 ExS-8 6.3 × 10 ^-4 ExC-6 0.009 ExM-2 0.031 ExM-3 0.029 ExY -1 0.006 ExM-4 0.028 HBS-1 0.064 HBS-3 2.1 × 10 ^-3 Gelatin 0.44 Eleventh layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I silver 0.19 silver iodobromide emulsion J silver 0.80 ExS-4 4.1 × 10 ^-5 ExS-7 1.1 × 10 ^{− 4} ExS-8 4.9 × 10 ^-4 ExC-6 0.004 ExM-1 0.016 ExM-3 0.036 ExM-4 0.020 ExM-5 0.004 ExY-5 0.003 ExM-2 0.013 Cpd-3 0.004 Cpd-4 0.007 HBS-1 0.18 Polyethyl acrylate latex 0.099 Gelatin 1.11 12th layer (yellow filter layer) Yellow colloidal silver Silver 0.047 Cpd-1 0.16 solid disperse dye ExF-5 0.020 solid disperse dye ExF-6 0.020 oil-soluble dye ExF-7 0.010 HBS-1 0.082 gelatin 1.057 Layer 13 (low sensitivity blue Agent layer) Silver iodobromide emulsion K silver 0.18 Silver iodobromide emulsion L silver 0.20 Silver iodobromide emulsion M silver ^{0.07 ExS-9 4.4 × 10 -4} ExS-10 4.0 × 3. Ex- ⁴ ExC-1 0.041 ExC-8 0.012 ExY-1 0.035 ExY-2 0.71 ExY-3 0.10 ExY-4 0.005 Cpd-2 0.10 Cpd-3 0 × 10 ⁻³ HBS-1 0.24 Gelatin 1.41 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion N silver 0.75 ExS-9 3.6 × 10 ⁻⁴ ExC-10 0.013 ExY-2 0.31 ExY-3 0.05 ExY-6 0.062 Cpd-2 0.075 Cpd-3 1.0 × 10 ^-3 HBS-1 0.10 Gelatin 0.91 15th layer ( First protective layer) Silver iodobromide emulsion O silver 0.30 UV-1 0.21 UV-2 0.1 UV-3 0.20 UV-4 0.025 F-18 0.009 HBS-1 0.12 HBS-4 5.0 × 10 -2 Gelatin 2.3 Layer 16 (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 gelatin 0.75 Storage, processing, pressure resistance, fungicide
In order to improve antibacterial properties, antistatic properties and coatability, W-
1 to W-5, B-4 to B-6, F-1 to F
-18 and iron, lead, gold, platinum, palladium, iridium, ruthenium, and rhodium salts. The coating solution for the eighth layer was 8.5 × 10 ^-3 g per mol of silver halide, and the coating solution for the eleventh layer was 7.9 × 10 ^-3 g.
^A sample was prepared by adding ^-3 grams of calcium with an aqueous solution of calcium nitrate.

Table 1 below shows the AgI content, grain size, surface iodine content and the like of the emulsions represented by the above-mentioned abbreviations. The surface iodine content can be determined by XPS as follows. The sample was transferred to -115 in a 1x10 torr transfer vacuum.
C., and irradiated with MgKα as a probe X-ray at an X-ray source voltage of 8 kV and an X-ray current of 20 mA.
2, measured for Br3d and I3d5 / 2 electrons, the integrated intensity of the measured peak was corrected by a sensitivity factor, and the iodine content of the surface was determined from the intensity ratio.

[0145]

[Table 1]

In Table 1, (1) Emulsions L to O were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

(2) Emulsions A to O are disclosed in JP-A-3-23745.
According to the example of No. 0, gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer.

(3) The preparation of tabular grains is disclosed in
According to the example of 58 426, low molecular weight gelatin is used.

(4) JP-A-3-2374 for tabular grains
Dislocation lines as described in No. 50 have been observed using a high voltage electron microscope.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were put into a 700 ml pot mill. , Dye ExF-
2 and 5.0 g of zirconium oxide beads (diameter 1 mm)
500 ml was added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles is 0.4
It was 4 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameter of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
m. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP-A-549,489A. The average particle size was 0.06 μm.

The compounds used for forming the above layers are as shown below.

[0153]

Embedded image

[0154]

Embedded image

[0155]

Embedded image

[0156]

Embedded image

[0157]

Embedded image

[0158]

Embedded image

[0159]

Embedded image

[0160]

Embedded image

[0161]

Embedded image

[0162]

Embedded image

[0163]

Embedded image

[0164]

Embedded image

[0165]

Embedded image

[0166]

Embedded image

[0167]

Embedded image

[0168]

Embedded image

[0169]

Embedded image

Table 2 shows the types and amounts of the compounds (evaluation compounds) added to the seventh layer and the sample numbers thereof.

Next, a method of developing each sample will be described.

(Processing method) Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C. Bleaching 3 minutes 00 seconds 38 ° C. Water washing 30 seconds 24 ° C. Fixing 3 minutes 00 seconds 38 ° C. Water washing (1) 30 seconds 24 ° C. Washing with water (2) 30 seconds 24 ° C. Stability 30 seconds 38 ° C. Drying 4 minutes 20 seconds 55 ° C. Next, the composition of the treatment liquid is described. (Color developing solution) (unit: g) diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 sodium sulfite 4.0 potassium carbonate 30.0 potassium bromide 1.4 potassium iodide 1.5 mg hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) 4.5 amino] -2-methylaniline sulfate 1.0 liter by adding water pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 (bleach-fix solution) (g) Ethylenediaminetetraacetic acid Ferric 100.0 Sodium trihydrate Ethylenediaminetetraacetic acid disodium salt 10.0 3-Mercapto-1,2,4-triazole 0.03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Add water 1.0 liter pH (ammonia Adjusted with water and nitric acid) 6.0 (Fixer) Ethylene Amine tetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / L) 295.0 mL Acetic acid (90%) 3.3 Add water to 1.0 L pH (adjusted with ammonia water and acetic acid) 6.7 (Stabilized solution) (Unit g) ) P-Nonylphenoxy polyglycidol (glycidol average polymerization degree 10) 0.2 ethylenediaminetetraacetic acid 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 hydroxyacetic acid 0.02 Hydroxyethylcellulose 0.1 (Daicel Chemical HEC SP-2000) 1,2-benzisothiazolin-3-one 0.05 Add water and add 1.0 liter pH 8.5

As a result of performing the above-mentioned development processing, all the samples had ISO 420.

In order to evaluate the storage stability, these unexposed
Were stored at 50% relative humidity and 50 ° C. for 4 weeks. This
Of the same sample stored at 5 ° C. for 4 weeks
00 ⁰Sensit for 1/100 second through continuous wedge at K
Exposure for metrology and color development
Was. Next, the concentration was measured and the sample stored at 50 ° C.
Difference between the fog value and the fog value of the sample stored at 5 ° C (△ fog1)
I asked. Also stored at 50% relative humidity 80% for 4 weeks
Treated sample and sample stored at 5 ℃ for 4 weeks
Then, the difference between the fogging values (△ fog2) was determined. The results are shown in Table 2.
You.

[0175]

[Table 2]

From Table 2 above, it can be seen that the use of the compound of the present invention can suppress the storage fog over time (Sample 10
1, 107-113). The effect far exceeds the conventionally known effect of improving the storage stability of Comparative Compound A (bis (ethanediamine-N, N) -palladium (2+) dichloride described in US-5614360) (Sample 102 , 107-11
3). Ethylenediamine which is a ligand of the compound,
Under a moderate humidity condition of 50% relative humidity, the storage stability is only slightly deteriorated (sample 103, Δfog1), whereas under a high humidity condition of 80% relative humidity, the fogging during storage is significantly deteriorated. (Sample 103, Δfog2).
Then, it was found that under this high humidity condition, the comparative compound A could not suppress the fogging during storage (sample 102, Δfog2). On the other hand, we have found that the ligand of the Pd complex of the present invention hardly deteriorates storage stability or does not deteriorate storage stability at all (samples 104 to 6). By using these compounds as ligands of Pd, it became possible to significantly reduce storage fogging. In particular, even under high humidity conditions, the compound has a storage stability improving effect that is not found in the conventionally known compound (Comparative Compound A) (Sample 101).
-102, 107-113). Incidentally, the viscosity of the gelatin solution of the seventh layer before coating, the compound of the present invention (I) -1, (I) -3,
It was examined whether the change was caused by the addition of (I) -5 and (I) -6, but no increase in viscosity was observed.

Comparative compound and compound (II) used in Table 2
The structures of -1, 2, and 3 are as shown below.

[0178]

Embedded image

Embodiment 2 In the embodiment 1, instead of W-1 to W-5, We
-1 to We-28 (see the above [Chemical Formula 20] to [Chemical Formula 22])
Example 1 was used alone or in combination as appropriate.
And similar results were obtained.

Example 3 In Example 1, compound 1 was used as a dispersant for an oil-soluble organic solvent instead of HBS-1 to HBS-4. To compound 129. When the above-mentioned [Chemical Formula 9] to [Chemical Formula 19] were used singly or in combination, the same results as in Example 1 were obtained.

Example 4 In the samples 101 to 113 of Example 1, the cellulose triacetate film as the support was replaced with US Pat.
No. 7,682, column 1, line 57 to column 23, line 29, the support used for sample 104 in Example 1 of No. 7,682. , And a practical evaluation was performed in the same manner as in Example 1 using the heat-treated PEN support.

As a result, a result similar to that of Example 1 was obtained.

[0183]

The ligand of the Pd complex of the present invention hardly deteriorates storage stability or does not deteriorate storage stability at all. By using these compounds as ligands of Pd, the effect of significantly reducing storage fogging was obtained. In particular, even under high humidity conditions, it has an effect of improving storage stability, which is not found in conventionally known compounds.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takeshi Kenboku 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H016 BD01 2H023 CC02

Claims (2)

[Claims] 1. A silver halide photographic material comprising at least one compound represented by the following general formula (I). Embedded image In the formula, X ₁ and X ₂ represent SR1, SeR2, OR3,
Y ₁ and Y ₂ represent NR4R5, SR6, SeR7 and OR8, and Z ₁ and Z ₂ represent a divalent linking group. R1, R2,
R3, R6, R7, and R8 are a hydrogen atom, an aliphatic group,
Represents an aromatic group or a heterocyclic group, wherein R4 and R5 are a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, and an arylsulfonyl group; Represents a group. Q represents an anionic ion;
Represents an integer. 2. In the general formula (I), X ₁ and X ₂
Represents SR1, Z ₁ and Z _{2 each} represent a substituted or unsubstituted alkylene group, alkenylene group, arylene group having 2 to 6 carbon atoms, or a group consisting of these and a carbonyl group or a sulfonyl group; Y ₁ represents NR4R5; 2. The silver halide photographic material according to claim 1, wherein the material is OR8.