JP2003029368A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high contrast silver halide photographic sensitive material excellent in storage stability. SOLUTION: In the silver halide photographic sensitive material having at least one silver halide emulsion layer on a support, a nonionic surfactant having a fluorine substituted alkyl group, e.g. represented by formula 1 is contained, and it is characterized in that the photographic sensitive material has a characteristic curve whose gamma in the optical density range of 0.3-3.0 is >=5.0 as a characteristic curve shown on rectangular coordinate axes having the same unit length of logarithmic light exposure (x-axis) and optical density (y-axis).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a high-contrast negative image forming method using the same. The present invention relates to a photographic light-sensitive material and an image forming method using the same.

[0002]

2. Description of the Related Art In a photoengraving process in the field of graphic arts, a continuous-tone photographic image is converted into a so-called halftone dot image that expresses the density of the image by the size of the halftone dot area, and a character or line drawing is taken on this image. The method of making a printing original plate in combination with is done. The silver halide light-sensitive material used in such applications has a super-hard photographic property in which the image area and the non-image area are clearly distinguished in order to improve the reproducibility of characters, line images, and halftone images. Have been asked to have.

As a system to meet the demand for ultra-high contrast photographic characteristics, a silver halide light-sensitive material made of silver chlorobromide is treated with a hydroquinone developing solution having an extremely low effective concentration of sulfite ion to obtain a high contrast. A so-called lith development method for forming an image has been known. However, in this method, the concentration of sulfite ion in the developing solution is low, so that it is extremely unstable against air oxidation of the developing solution, and a large amount of replenishment was required to keep the solution activity stable.

An image forming system which eliminates the instability of the image formation of the lith development method and is processed with a developer having a good storage stability to obtain super-high contrast photographic characteristics is disclosed in, for example, US Pat. No. 4,166. , 742 and 4,16
No. 8,977, No. 4,221,857, No. 4,2
No. 24,401, No. 4,243,739, No. 4,
269,922, 4,272,606, 4,311,781, 4,332,878, 4,618,574, 4,634,661,
No. 4,681,836, No. 5,650,746 and the like. These are surface latent image type silver halide photographic light-sensitive materials to which a hydrazine derivative is added.
Treated with a developing solution containing 2.3 hydroquinone / methol or hydroquinone / phenidone as a developing agent,
Is a system for forming a negative image of ultra-high contrast exceeding 10. According to this method, ultra-high contrast and high-sensitivity photographic characteristics can be obtained, and since a high concentration of sulfite can be added to the developer, the stability of the developer against air oxidation is higher than that of the conventional lith developer. And dramatically improve.

In order to fully develop a super-high contrast image with a hydrazine derivative, it was necessary to treat with a developer having a pH value of 11 or higher, usually 11.5 or higher. Although it was possible to increase the stability of the developer with a high concentration of sulfite preservative, it is necessary to use a developer with a high pH value as described above in order to obtain a super-high contrast photographic image. However, even if there is a preservative, the developer is likely to be air-oxidized and unstable, and therefore, attempts have been made to realize a super-high contrast image at a lower pH in order to further improve the stability.

For example, US Pat. No. 4,269,929 (Japanese Patent Laid-Open No. 61-267759) and US Pat.
7,452 (JP-A-60-179734), US Pat. Nos. 5,104,769, 4,798,780, JP-A-1-179939, 1-199940, and US Pat. No. 604, No. 4,994, 365,
JP-A-8-272023 discloses a method of using a highly active hydrazine derivative and a nucleation accelerator in order to obtain a super-high contrast image using a developer having a pH of less than 11.0. Since the silver halide photographic light-sensitive material used in such an image forming system contains a highly active compound, there are problems in storage stability such as fluctuation of feeling during storage and increase of fog, and improvement is required. It was being done.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material which has high contrast and is excellent in storage stability.

[0008]

The above objects have been achieved by the following inventions. (1) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, containing a surfactant represented by the following general formula (A), and having a logarithmic exposure amount (x axis): A halogenation characterized by having a characteristic curve on a rectangular coordinate axis having the same unit length of the optical density (y axis) and having a gamma at an optical density of 0.3 to 3.0 of 5.0 or more. Silver photographic light-sensitive material.

[Chemical 3] In the formula, R represents a substituted or unsubstituted alkyl group,
_af represents a perfluoroalkylene group. W represents a hydrogen atom or a fluorine atom, and La represents _a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent group formed by combining these. One of A and B is a hydrogen atom and the other is-.
Represents L _b -SO ₃ M, M represents a cation. L _b is
It represents a single bond or a substituted or unsubstituted alkylene group. (2) The silver halide photographic light-sensitive material according to item (1), wherein the compound of the general formula (A) is a compound represented by the following general formula (B).

[Chemical 4] In the formula, R ¹ represents a substituted or unsubstituted alkyl group having 6 or more carbon atoms in total, but R ¹ is not an alkyl group substituted with a fluorine atom. R _f represents a perfluoroalkyl group having 6 or less carbon atoms, ^one of X ¹ and X ² represents a hydrogen atom, the other represents SO ₃ M, and M represents a cation. n represents an integer of 1 or more. (3) In the general formula (B), R _f has 2 to 4 carbon atoms.
The silver halide photographic light-sensitive material according to item (1) or (2), which is a perfluoroalkyl group of (4) The silver halide photographic light-sensitive material according to any one of (1) to (3), which contains a hydrazine compound. (5) The film surface pH on the emulsion layer side is 6.0 or less (1) to
(4) The silver halide photographic light-sensitive material according to any one of items.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In a light-sensitive material having a characteristic curve specified in the present invention, that is, a light-sensitive material having a high contrast, by containing a surfactant represented by the general formula (A) of the present invention, storage stability is improved. Sex is improved.

The gamma referred to in the present invention is defined as follows. A straight line is drawn at two points of optical densities 0.3 and 3.0 on the characteristic curve shown on the orthogonal coordinate axis with the same unit length represented by the optical density (y axis) and the common logarithmic exposure (x axis). When it is that gradient. That is, when the angle formed by the straight line and the x-axis is θ, it is represented by tan θ. The gamma of the light-sensitive material in the present invention is 5.0 or more and 50 or less.

The specific processing method having the characteristic curve defined in the present invention is as follows. Developer: ND-1 made by Fuji Photo Film Co., Ltd. Fixing solution: NF-1 automatic processor made by Fuji Photo Film Co., Ltd. FG-680AG made by Fuji Photo Film Co., Ltd. Development condition: 35 ° C. 30 seconds

Any method can be used to obtain a light-sensitive material having the characteristic curve specified in the present invention, but a specific example will be shown. As one example, the silver halide emulsion contains a heavy metal capable of achieving high contrast, for example, a metal belonging to Group VIII. In particular, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound and the like. Further, at least one hydrazine derivative or amine compound is contained as a nucleating agent on the side containing the emulsion layer.

The present invention is characterized by using a fluorine compound represented by the following general formula (A).

[0014]

[Chemical 5]

In the general formula (A), R represents a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group represented by R may be linear, branched, or have a cyclic structure. As the substituent, any substituent may be used, but an alkenyl group, an aryl group, an alkoxy group, a halogen atom (preferably C
1), a carboxylic acid ester group, a carbonamido group, a carbamoyl group, an oxycarbonyl group, a phosphoric acid ester group and the like are preferable. R preferably has no fluorine as a substituent, and an unsubstituted alkyl group is more preferable. R preferably has 2 or more carbon atoms, more preferably 4 or more carbon atoms, and even more preferably 6 or more carbon atoms. R _af represents a perfluoroalkylene group. Here, the perfluoroalkylene group refers to a group in which all hydrogen atoms of the alkylene group are fluorine-substituted. The perfluoroalkylene group may be linear or branched, and may have a cyclic structure. R _af preferably has 10 or less carbon atoms, and more preferably 8 or less carbon atoms. W represents a hydrogen atom or a fluorine atom, but is preferably a fluorine atom. L _a is a substituted or unsubstituted alkylene group or a substituted or unsubstituted alkyleneoxy group,
Alternatively, it represents a divalent group formed by combining these. The substituents are preferably those listed for R. L _a has 4 carbon atoms
The following is preferable, and unsubstituted alkylene is preferable. A and B are a hydrogen atom, and the other represents _-L b -SO ₃ M, M represents a cation. Here, as the cation represented by M, for example, an alkali metal ion (lithium ion, sodium ion, potassium ion and the like), alkaline earth metal ion (barium ion, calcium ion and the like), ammonium ion and the like are preferably exemplified. . Of these, lithium ion, sodium ion, potassium ion or ammonium ion is more preferable, and lithium ion, sodium ion or potassium ion is more preferable, and the total carbon number and substituents of the compound of general formula (A), It can be appropriately selected depending on the degree of branching of the alkyl group. R, is the total number of carbon atoms of _{L a} and _{R af} 1
In the case of 6 or more, lithium ions are excellent from the viewpoints of both solubility (particularly in water) and antistatic ability or coating uniformity. L _b represents a single bond or a substituted or unsubstituted alkylene group. The substituents are preferably those listed for R. When L _b is an alkylene group, the C number is 2
It is preferably the following, preferably unsubstituted.
More preferably, it is a methylene group. Most preferably, L _b is a single bond. It is more preferable that the general formula (A) is a combination of the above preferable embodiments. The general formula (A) is preferably represented by the following general formula (B).

[0016]

[Chemical 6]

In the general formula (B), R ¹ represents a substituted or unsubstituted alkyl group having a total carbon number of 6 or more. However, R ¹
Does not become an alkyl group substituted with a fluorine atom. The substituted or unsubstituted alkyl group represented by R ¹ is
It may be linear, branched, or have a cyclic structure. Examples of the substituent include an alkenyl group, an aryl group, an alkoxy group, a halogen atom other than fluorine, a carboxylic acid ester group, a carbonamido group, a carbamoyl group, an oxycarbonyl group, and a phosphoric acid ester group.

The substituted or unsubstituted alkyl group represented by R ¹ preferably has a total carbon number of 6 to 24. Preferred examples of the unsubstituted alkyl group having 6 to 24 carbon atoms include:
n-hexyl group, n-heptyl group, n-octyl group, t
ert-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-
Hexyldecyl group, octadecyl group, eicosyl group, 2
-Octyldodecyl group, docosyl group, tetracosyl group,
Examples thereof include 2-decyltetradecyl group, tricosyl group, cyclohexyl group, cycloheptyl group and the like. Preferred examples of the substituted alkyl group having a total carbon number of 6 to 24, including the carbon atoms of the substituents, include 2-hexenyl group, oleyl group, linoleyl group, linolenyl group, benzyl group, β-phenethyl group, 2- Methoxyethyl group, 4-phenylbutyl group, 4-acetoxyethyl group, 6-phenoxyhexyl group, 12-phenyldodecyl group, 18-phenyloctadecyl group, 12- (p-chlorophenyl) dodecyl group, 2- (diphenyl phosphate) An ethyl group etc. can be mentioned.

The substituted or unsubstituted alkyl group represented by R ¹ more preferably has 6 to 18 total carbon atoms.
Preferred examples of the unsubstituted alkyl group having 6 to 18 carbon atoms include n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3- Trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-
Hexyldecyl group, octadecyl group, 4-tert-butylcyclohexyl group and the like can be mentioned. In addition, preferred examples of the substituted alkyl group having a total carbon number of 6 to 18 including the carbon number of the substituent include a phenethyl group, a 6-phenoxyhexyl group, a 12-phenyldodecyl group, an oleyl group, a linoleyl group and a linolenyl group. Is mentioned. Among them, R ¹
As, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n
-Nonyl group, 1,1,3-trimethylhexyl group, n-
A decyl group, an n-dodecyl group, a cetyl group, a hexadecyl group, a 2-hexyldecyl group, an octadecyl group, an oleyl group, a linoleyl group, and a linolenyl group are more preferable, and a straight chain, cyclic or branched group having 8 to 16 carbon atoms Is particularly preferably an unsubstituted alkyl group.

In the general formula (B), R _f represents a perfluoroalkyl group having 6 or less carbon atoms. Here, the perfluoroalkyl group means a group in which all hydrogen atoms of the alkyl group are substituted with fluorine. The alkyl group in the perfluoroalkyl group may be linear or branched, and may have a cyclic structure. Examples of the perfluoroalkyl group represented by R _f include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a heptafluoroisopropyl group,
Nonafluoro-n-butyl group, undecafluoro-n-
Examples thereof include a pentyl group, a tridecafluoro-n-hexyl group, and an undecafluorocyclohexyl group. Among them, perfluoroalkyl groups having 2 to 4 carbon atoms (for example,
Pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoroisopropyl group, nonafluoro-
(n-butyl group etc.) is preferable, and a heptafluoro-n-propyl group and a nonafluoro-n-butyl group are particularly preferable.

In the general formula (B), n represents an integer of 1 or more. It is preferably an integer of 1 to 4, and particularly preferably 1 or 2. Further, as a combination of n and R _f , when n = 1, R _f is a heptafluoro-n-propyl group or a nonafluoro-n-butyl group, and when n = 2, R _f is a nonafluoro-n-butyl group. More preferably, it is a group.

In the general formula (B), X ¹ and X ²
Is a hydrogen atom and the other is SO ₃ M,
Represents a cation. Here, as the cation represented by M, for example, an alkali metal ion (lithium ion, sodium ion, potassium ion and the like), alkaline earth metal ion (barium ion, calcium ion and the like), ammonium ion and the like are preferably exemplified. . Of these, lithium ion, sodium ion, potassium ion or ammonium ion is particularly preferable.

Preferred specific examples of the fluorine compound represented by the general formula (B) are shown below, but the present invention is not limited to the following specific examples. In addition,
Hereinafter, for convenience, X ¹ is SO ₃ M, and an exemplary compound in which X ² is a hydrogen atom is shown. However, in the exemplary compounds below, X ¹ may be a hydrogen atom and X ² may be SO ₃ M. Also, those compounds can be mentioned as specific examples of the fluorine compound of the present invention. Unless otherwise specified, in the structural description of the exemplified compounds below, an alkyl group and a perfluoroalkyl group mean a linear structure. Further, among the abbreviations in the structural description, the groups with the symbols 2EH and 2BO represent the groups shown below, respectively. 2EH: 2-ethylhexyl 2BO: 2-butyloctyl

[0024]

[Chemical 7]

[0025]

[Chemical 8]

[0026]

[Chemical 9]

[0027]

[Chemical 10]

[0028]

[Chemical 11]

[0029]

[Chemical 12]

The fluorine compound represented by the general formula (B) can be easily synthesized by combining general esterification reaction and sulfonation reaction.

The fluorine compound used in the present invention is used as a surfactant in a coating composition for forming a layer (particularly, a protective layer, an undercoat layer or a back layer) constituting a silver halide photographic light-sensitive material. It is preferably used. Among them, it is particularly preferable to use it for forming the hydrophilic colloid layer as the uppermost layer of the photographic light-sensitive material, since it is possible to obtain effective antistatic ability and coating uniformity. Hereinafter, the coating composition containing the fluorine compound of the present invention as a surfactant will be described.

The aqueous coating composition containing a fluorine compound used in the present invention contains the surfactant of the present invention and a medium in which the surfactant is dissolved and / or dispersed. In addition, other components may be appropriately contained depending on the purpose.
In the aqueous coating composition of the present invention, the medium is preferably an aqueous medium. The aqueous medium includes water and a mixed solvent of water and an organic solvent other than water (for example, methanol, ethanol, isopropyl alcohol, n-butanol, methyl cellosolve, dimethylformamide, acetone, etc.). In the present invention, the medium of the coating composition preferably contains water in an amount of 50% by mass or more.

In the present invention, one kind of the fluorine compound of the present invention may be used alone, or two or more kinds may be mixed and used. Further, other surfactant may be used together with the fluorine compound of the present invention. Examples of the surfactant that can be used in combination include various anionic, cationic and nonionic surfactants. Further, the surfactant to be used in combination may be a polymer surfactant or a fluorochemical surfactant other than the surfactant of the present invention. The surfactant used in combination is more preferably an anionic or nonionic surfactant. Examples of the surfactant that can be used in combination include, for example, JP-A-62-215272 (pages 649 to 706), Research Disclosure (RD) Item 17643, pages 26 to 27 (1978).
December, pp. 18716, 650 (November 1979)
Mon., 307105, pages 875-876 (November 1989) and the like.

As another component which can be used in combination, a polymer compound can be mentioned as a typical example. The polymer compound may be a polymer soluble in an aqueous medium (hereinafter referred to as “soluble polymer”) or an aqueous dispersion of polymer (so-called polymer latex).
The soluble polymer is not particularly limited, and examples thereof include gelatin, polyvinyl alcohol, casein, agar, gum arabic, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, and the like. Polymer latex includes various vinyl monomers [eg, acrylates. Derivative, methacrylate derivative, acrylamide derivative, methacrylamide derivative,
Styrene derivative, conjugated diene derivative, N-vinyl compound, O-vinyl compound, vinyl nitrile, other vinyl compound (eg ethylene, vinylidene chloride)] homopolymer or copolymer, dispersion of condensation polymer (eg polyester, polyurethane) , Polycarbonate, polyamide). Specific examples of this type of polymer compound are described in, for example, JP-A-62-21527.
No. 2 (pages 707 to 763), Research Disclosure (RD) Items 17643, 651 (197).
December 1988), p. 18716, 650 (1 1979)
Jan., 307105, pp. 873-874 (1989).
Polymer compounds described in (November, 2013) and the like.

The aqueous coating composition containing the fluorine compound of the present invention may contain various other compounds depending on the layer used in the light-sensitive material, and they may be dissolved in a medium or dispersed. It may have been done. Examples thereof include various couplers, ultraviolet absorbers, color mixture preventing agents, antistatic agents, scavengers, antifoggants, film hardeners, dyes and antifungal agents. Also, as mentioned above,
The aqueous coating composition containing the fluorine compound of the present invention is preferably used for forming the hydrophilic colloid layer as the uppermost layer of the photographic light-sensitive material. In this case, the coating composition contains a hydrophilic colloid (eg gelatin). ) And the fluorine compound of the present invention,
Other surfactants, matting agents, sliding agents, colloidal silica, gelatin plasticizers, etc. may be contained.

The amount of the fluorine compound used in the present invention is not particularly limited, and the amount used may be arbitrary depending on the structure of the compound to be used, the place to be used, the type and amount of other materials contained in the composition, and the like. Can be determined. For example, when used as a coating liquid for the hydrophilic colloid (gelatin) layer of the uppermost layer of a silver halide photographic light-sensitive material, the concentration of the fluorine compound in the coating composition is 0.003 to 0.
It is preferably 5% by mass, and is preferably 0.03 to 50% by mass based on the gelatin solid content.

The photosensitive material of the present invention preferably contains at least one hydrazine derivative represented by the general formula (D) as a nucleating agent. General formula (D)

[0038]

[Chemical 13]

In the formula, R ₂₀ represents an aliphatic group, an aromatic group, or a heterocyclic group, R ₁₀ represents a hydrogen atom or a block group, G ₁₀ represents —CO—, —COCO—, —C (=
_{S) -, - SO 2 -} , - SO -, - PO (R 30) - group _{(R 30} is selected from the same range as the groups defined in _{R 10,} may be different from _{R 10),.} Alternatively, it represents an iminomethylene group. A ₁₀ and A ₂₀ are both hydrogen atoms,
Alternatively, one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (D), the aliphatic group represented by R ₂₀ is preferably a substituted or unsubstituted linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 1 to 30 carbon atoms. is there. In the general formula (D), R
_The aromatic group represented by ₂₀ is a monocyclic or condensed-ring aryl group, and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic group represented by R ₂₀ is a monocyclic or condensed ring, saturated or unsaturated, aromatic or non-aromatic heterocyclic group, for example, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring. , Quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, piperidine ring, triazine ring and the like. An aryl group is preferred as R ₂₀ , and a phenyl group is particularly preferred.

The group represented by R ₂₀ may be substituted,
Representative substituents include, for example, halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl Group, heterocyclic group, quaternized nitrogen atom-containing heterocyclic group (for example, pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or salt thereof, sulfonylcarbamoyl group, acyl group Rucarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy group or propyleneoxy group unit), aryloxy group , A heterocyclic oxy group, Syloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocycle) amino group, N-substituted nitrogen-containing heterocyclic group, acylamino group, sulfone Amido group, ureido group, thioureido group, isothioureido group, imide group, (alkoxy or aryloxy)
Carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4
Ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, N-acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocycle) thio group, ( Alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, N-acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, phosphoramide or phosphate ester structure And the like. These substituents may be further substituted with these substituents.

The substituent which R ₂₀ may have is preferably an alkyl group having 1 to 30 carbon atoms (including an active methylene group), an aralkyl group, a heterocyclic group, a substituted amino group, an acylamino group and a sulfonamide. Group, ureido group,
Sulfamoylamino group, imido group, thioureido group,
Phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group (including salts thereof), (alkyl, aryl, or heterocycle) ) Thio group, sulfo group (including salts thereof), sulfamoyl group, halogen atom, cyano group,
Examples thereof include a nitro group.

In the general formula (D), R ₁₀ represents a hydrogen atom or a block group.
It represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group.

The alkyl group represented by R ₁₀ is preferably an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, a trifluoromethyl group, a difluoromethyl group, 2
-Carboxytetrafluoroethyl group, pyridiniomethyl group, difluoromethoxymethyl group, difluorocarboxymethyl group, 3-hydroxypropyl group, methanesulfonamidomethyl group, benzenesulfonamidomethyl group, hydroxymethyl group, methoxymethyl group, methylthiomethyl group, Examples thereof include a phenylsulfonylmethyl group and an o-hydroxybenzyl group. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, and examples thereof include a vinyl group, a 2,2-dicyanovinyl group, a 2-ethoxycarbonylvinyl group, and a 2-trifluoro-2-methoxycarbonylvinyl group. . The alkynyl group is preferably an alkynyl group having 1 to 10 carbon atoms, and examples thereof include an ethynyl group and a 2-methoxycarbonylethynyl group. As the aryl group, a monocyclic or condensed ring aryl group is preferable, and a group containing a benzene ring is particularly preferable. For example, phenyl group, 3,5-dichlorophenyl group, 2-methanesulfonamidophenyl group, 2
-Carbamoylphenyl group, 4-cyanophenyl group, 2
-Hydroxymethylphenyl group and the like. The heterocyclic group is preferably a 5- or 6-membered, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group containing at least one nitrogen, oxygen, and sulfur atom, and a quaternized nitrogen atom. It may be a heterocyclic group containing, for example, morpholino group, piperidino group (N-substituted), piperazino group, imidazolyl group, indazolyl group (4-nitroindazolyl group etc.), pyrazolyl group, triazolyl group, benzimidazolyl group, Examples thereof include a tetrazolyl group, a pyridyl group, a pyridinio group (N-methyl-3-pyridinio group and the like), a quinolinio group and a quinolyl group. A morpholino group, a piperidino group, a pyridyl group, a pyridinio group and the like are particularly preferable.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and examples thereof include a methoxy group, a 2-hydroxyethoxy group and a benzyloxy group. The aryloxy group is preferably a phenoxy group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a saturated or unsaturated heterocyclic amino group (quaternized (Including a nitrogen-containing heterocyclic group containing a nitrogen atom) is preferable. Examples of amino groups include 2,2,6,6-tetramethylpiperidine-
4-ylamino group, propylamino group, 2-hydroxyethylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-
3-pyridinio amino group etc. are mentioned. As the hydrazino group, a substituted or unsubstituted hydrazino group or a substituted or unsubstituted phenylhydrazino group (4-benzenesulfonamidophenylhydrazino group etc.) is particularly preferable.

The group represented by R ₁₀ may be substituted, and preferable examples of the substituent include those exemplified as the substituent of R ₂₀ .

In the general formula (D), R ₁₀ is G ₁₀ -R
₁₀ part is split from the rest of the molecule, -G ₁₀ -R
It may be one that causes a cyclization reaction to form a cyclic structure containing ₁₀ atoms, for example,
For example, those described in JP-A-63-29751 can be mentioned.

The hydrazine derivative represented by the general formula (D) may incorporate an adsorptive group that adsorbs to silver halide. Examples of the adsorptive group include alkylthio groups, arylthio groups, thiourea groups, thioamide groups, mercaptoheterocyclic groups, and triazole groups, which are disclosed in U.S. Pat. Nos. 4,385,108, 4,459,347, and Japanese Patent Laid-Open No. 59-347. -195233, 59-200231, 59-201045, 59-201046, 5
9-201047, 59-201048, 59
-201049, JP-A-61-170733, and JP-A-6-170733.
1-270744, 62-948, 63-23
No. 4244, No. 63-234245, No. 63-234.
The groups described in No. 246 are mentioned. The adsorbing group for these silver halides may be a precursor. As such a precursor, JP-A-2-285
The groups described in No. 344 are mentioned.

R ₁₀ or R _{20 in} the general formula (D) may have a ballast group or a polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. In the present invention, the ballast group is a linear or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group), alkylamino group (or alkyleneamino group), alkylthio having 6 or more carbon atoms. Represents a group or a group having these as a partial structure, and more preferably has a carbon number of 7 or more and 24 or less, a linear or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group), It represents an alkylamino group (or alkyleneamino group), an alkylthio group, or a group having these as a partial structure. Examples of the polymer include those described in JP-A No. 1-100530.

R ₁₀ or R ₂₀ in the general formula (D) may contain a plurality of hydrazino groups as a substituent, and at this time, the compound represented by the general formula (D) is a multimer with respect to the hydrazino group. And specifically, for example, JP-A-64-
86134, JP-A-4-16938, JP-A5-1.
97091, WO95-32452, WO95-3
No. 2453, JP-A-9-179229, and JP-A-9-2.
35264, JP-A-9-235265, JP-A-9-
The compounds described in JP-A No. 235266, JP-A No. 9-235267 and the like can be mentioned.

R ₁₀ or R _{20 in} the general formula (D) represents a cationic group (specifically, a group containing a quaternary ammonio group, a group containing a quaternized phosphorus atom, or Four
Nitrogen-containing heterocyclic group containing a quaternized nitrogen atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, (alkyl, aryl, or heterocycle)
A thio group or a dissociative group (a group or partial structure having a proton having a low acidity capable of dissociating in an alkaline developing solution, or a salt thereof, specifically, for example, a carboxy group /-COOH, a sulfo group / _-SO 3 H, a phosphonic acid group / _-PO 3 H, phosphoric acid group / -OPO ₃ H, hydroxy group / -OH group, mercapto group / -SH, -SO
₂ NH ₂ group, N-substituted sulfonamide group / -SO ₂ N
H- group, -CONHSO ₂ -group, -CONHSO ₂ NH
- based on, -NHCONHSO ₂ - _group, -SO ₂ NHSO 2
-Group, -CONHCO- group, active methylene group, -NH- group inherent in nitrogen-containing heterocyclic group, or salts thereof)
May be included. Examples of these groups include, for example, JP-A-7-234471 and JP-A-5-33.
3466, JP-A-6-19032, JP-A-6-19
031, JP-A-5-45761, and US Pat. No. 4,99.
4,365, US Pat. No. 4,988,604, JP-A-7-259240, JP-A-7-5610, and JP-A-7-5610.
-244348, German Patent 4006032, JP-A-1
The compounds described in 1-7093 and the like can be mentioned.

In the general formula (D), A ₁₀ and A ₂₀ are a hydrogen atom, an alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group, or the sum of Hammett's substituent constants is -0.5). A phenylsulfonyl group substituted as described above), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more, Alternatively, a linear, branched, or cyclic, substituted or unsubstituted aliphatic acyl group (wherein the substituent is, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxy group, a carboxy group, a sulfo group, or the like). Can be mentioned)). A hydrogen atom is most preferable as A ₁₀ and A ₂₀ .

Next, in the present invention, a particularly preferred hydrazine derivative will be described. R ₂₀ is particularly preferably a substituted phenyl group, and as the substituent, a sulfonamide group, an acylamino group, a ureido group, a carbamoyl group, a thioureido group, an isothioureido group, a sulfamoylamino group,
N-acyl sulfamoylamino group and the like are particularly preferable,
Further, a sulfonamide group and a ureido group are preferable, and a sulfonamide group is most preferable. The hydrazine derivative represented by the general formula (D) is a group containing a ballast group, a group adsorbing to silver halide, a quaternary ammonio group, as a substituent, in R ₂₀ or R ₁₀ , directly or indirectly. A nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, a group containing a repeating unit of an ethyleneoxy group, a (alkyl, aryl, or heterocycle) thio group, a dissociable group capable of dissociating in an alkaline developing solution. Or at least one hydrazino group (group represented by —NHNH—G ₁₀ —R ₁₀ ) capable of forming a multimer is particularly preferably substituted. Further, as a substituent of R ₂₀ , directly or indirectly,
It is preferable to have any one of the above-mentioned groups, and most preferable is that R ₂₀ represents a phenyl group substituted with a benzenesulfonamide group, and R ₂₀ directly or directly as a substituent on the benzene ring of the benzenesulfonamide group. Indirectly, it is a case where any one of the groups described above is contained.

Preferred among the groups represented by R ₁₀ are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group when G ₁₀ is a —CO— group, A hydrogen atom, an alkyl group or a substituted aryl group is more preferable (an electron-withdrawing group or an o-hydroxymethyl group is particularly preferable as the substituent), and a hydrogen atom or an alkyl group is most preferable.
When G ₁₀ is a —COCO— group, an alkoxy group, an aryloxy group, and an amino group are preferable, and a substituted amino group, particularly an alkylamino group, an arylamino group, or a saturated or unsaturated heterocyclic amino group is preferable. . When G ₁₀ is a —SO ₂ — group, R ₁₀ is preferably an alkyl group, an aryl group or a substituted amino group.

In formula (D), G ₁₀ is preferably a --CO-- group or a --COCO-- group, and particularly preferably a --CO-- group.

Specific examples of the compound represented by formula (D) are shown below. However, the present invention is not limited to the following compounds.

[0057]

[Chemical 14]

[0058]

[Chemical 15]

[0059]

[Chemical 16]

[0060]

[Chemical 17]

[0061]

[Chemical 18]

[0062]

[Chemical 19]

[0063]

[Chemical 20]

[0064]

[Chemical 21]

[0065]

[Chemical formula 22]

[0066]

[Chemical formula 23]

[0067]

[Chemical formula 24]

As the hydrazine derivative used in the present invention, the following hydrazine derivative is preferably used in addition to the above. The hydrazine derivative used in the present invention can also be obtained by various methods described in the following patents,
Can be synthesized.

[Chemical formula 1] described in JP-B-6-77138
And specifically described on pages 3 and 4 of the same publication. Compounds represented by formula (I) described in JP-B-6-93082, specifically, pages 8 to 1 of the publication;
1 to 38 compounds described on page 8. JP-A-6-23049
Compounds represented by the general formula (4), the general formula (5) and the general formula (6) described in No. 7, specifically, page 25 of the same publication;
Compounds 4-1 to 4-10 described on page 26, Compounds 5-1 to 5-42 described on pages 28 to 36, and 39
Compound 6-1 to compound 6-7 described on page 40. Compounds represented by the general formula (1) and the general formula (2) described in JP-A-6-289520, specifically, from page 5 of the same publication.
Compounds 1-1) to 1-17) and 2-described on page 7
1). The compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically the compounds described on pages 6 to 19 of the same. The compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically the compounds described on pages 3 to 5 of the publication. Compounds represented by formula (I) described in JP-A-7-5610, specifically compounds I-1 to I-38 described on pages 5 to 10 of the same; Compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the publication. Compounds represented by the general formula (H) and the general formula (Ha) described in JP-A-7-104426, specifically Compound H described on pages 8 to 15 of the publication.
-1-H-44. A compound described in JP-A-9-22082, which has an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group, and particularly, a compound represented by the general formula (A) , A compound represented by the general formula (B), the general formula (C), the general formula (D), the general formula (E), and the general formula (F), specifically, the compound N-1 described in the publication. ~ N-30. JP-A-9-2
A compound represented by the general formula (1) described in No. 2082,
Specifically, compounds D-1 to D-55 described in the publication. In addition, WO95-32452 and WO95-32453
No. 9, JP-A-9-179229, JP-A-9-23526
4, JP-A-9-235265, JP-A-9-2352.
66, JP-A-9-235267, JP-A-9-319.
019, JP-A-9-319020, JP-A-10-1
30275, JP-A-11-7093, JP-A-6-3
32096, JP-A-7-209789, JP-A-8-
6193, JP-A-8-248549, JP-A-8-2
48550, JP-A-8-262609, JP-A-8-
314044, JP-A-8-328184, JP-A-9
-80667, JP-A-9-127632, JP-A-9-
-146208, JP-A-9-160156, JP-A-10-161260, JP-A-10-221800,
JP-A-10-213871 and JP-A-10-25408
No. 2, JP-A-10-254088, JP-A-7-120.
864, JP-A-7-244348, and JP-A-7-33.
3773, JP-A-8-36232, and JP-A-8-36.
No. 233, JP-A-8-36234, and JP-A-8-362.
35, JP-A-8-272022, and JP-A-9-220.
83, JP-A-9-22084, and JP-A-9-5438.
1, hydrazine derivatives described in JP-A-10-175946.

A hydrazine compound used in the present invention, which is a dimer in which a monomer containing both an acylhydrazide moiety and a nicotinamide moiety is bound by a linking group, will be described. It is used as a nucleating agent (hardening agent) and is specifically represented by the following general formula (1) or (2).

[0071]

Embedded image General formula (1)

Embedded image General formula (2)

Wherein each monomer linked by a divalent linking group L is the same or different, J is a nicotinamide residue, E is a substituted aryl or heterocycle, and A ₁ and A _{One of 2} is a hydrogen atom, the other is a hydrogen atom, an acyl group, or an alkylsulfonyl group or an arylsulfonyl group, which may be substituted, D is a blocking group, and a divalent group L is a linking group, and X ⁻ is an anionic counterion.

The compounds represented by the following general formula (3), (4) or (5) are more preferable, and the compound of the general formula (3) is most preferable.

General formula (3)

[Chemical 27]

General formula (4)

[Chemical 28]

General formula (5)

[Chemical 29]

In these compounds, each R ₁ CO
Is a block group, in particular each R ₁ is the same or different and is selected from a hydrogen atom and an unsubstituted or substituted alkyl, aryl, alkoxycarbonyl or aryloxycarbonyl and alkylaminocarbonyl or arylaminocarbonyl group. Or each R ₁ is an unsubstituted or substituted heterocyclic group having a 5 or 6 membered ring containing at least one nitrogen, oxygen or sulfur atom, or Containing, the ring may be attached to the carbonyl group directly or through an alkyl, alkoxy, carbonyl, aminocarbonyl or alkylaminocarbonyl group, and the ring may be fused to a benzene ring. , Are each R ₂ , R ₃ , and R ₇ the same? Or different and selected from hydrogen and unsubstituted or substituted alkyl or aryl groups, and p is 0 or 1 and each R ₄ , R ₅ and R
₆ is the same or different and is hydrogen, halogen, hydroxy, cyano, and unsubstituted or substituted alkyl, aryl, heterocycle, alkoxy, acyloxy, aryloxy, carbonamide, sulfonamide, ureido,
Thioureido, semicarbazide, thiosemicarbazide,
Urethane, quaternary ammonium, alkylthio or arylthio, alkylsulfonyl or arylsulfonyl, alkylsulfinyl or arylsulfinyl, carboxyl, alkoxycarbonyl or aryloxycarbonyl, carbamoyl, sulfamoyl, phosphonamide, diacylamino, imide, or acylurea group, selenium or They may be individually or jointly selected from a group containing a tellurium atom and a group having a tertiary sulfonium structure, and each q and m are the same or different, and q is 0 to 0.
4 is an integer of 4, m is an integer of 0 to 3, each X is the same or different, and C, S═O, and C—N
Selected from H, each (link ₁ ) is the same or different and is selected from unsubstituted or substituted alkylene, polyalkylene, aryl, arylaminocarbonyl, or heterocyclic groups, each n being 0 or 1 And
And each (link ₂ ) is a polyalkylene containing one or more heteroatoms selected from unsubstituted or substituted polyalkylenes, polyalkylene oxides, nitrogen, oxygen, and sulfur separated from each other by alkylene groups. Or a linking group selected from an unsubstituted or substituted polyalkylene in which the alkylene group is separated by an unsubstituted or substituted aryl or heterocycle,
And X ⁻ is an anionic counterion.

The term alkyl herein refers to an unsubstituted or substituted straight or branched chain alkyl group (including alkenyl) having 1 to 20 atoms, and cycloalkyl having 3 to 8 carbon atoms. including. The term aryl includes within its scope aralkyl (and certain fused aryls). The term heterocycle specifically includes within its scope fused heterocycles. The term polyalkylene is defined as a group (CH _{2) n (n} is 2 to 50 of an integer). The term "blocking group" also refers to groups which are suitable for protecting the (hydrazine) group but which are easily removable if necessary.

R ₁ is a hydrogen atom or is an unsubstituted or substituted alkyl (eg methyl, trifluoromethyl, 1,3-methylsulfonamido-propyl, methylsulfonylmethyl or phenylsulfonylmethyl,
Carboxytetrafluoroethyl), unsubstituted or substituted aryl (eg phenyl, 3,5-dichlorophenyl, o-methane-sulfonamidophenyl, 4-methanesulfonylphenyl, 2- (2'-hydroxyethyl))
-Phenyl, 2-hydroxy-4-methylphenyl, o
-Hydroxybenzyl), a carbonyl-containing group (eg alkylaminocarbonyl, alkoxycarbonyl, aryloxycarbonyl, or hydroxyalkylaminocarbonyl), or imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyridyl, pyridinium, piperidinyl, morpholino. A quinolinium or quinolinyl group, or R ₁ is a group which splits a photographically useful fragment, such as phenylmercaptotetrazole or 5- or 6-
It may contain a nitroindazole group. Some examples of these are disclosed in US Pat. No. 5,328,801. R ₂ and R ₃ are preferably hydrogen atoms or alkyl groups in which p is preferably 1 and R ₄ , R ₅ and R ₆ are preferably hydrogen, or q is preferably 0 or 1 and m
Is an alkyl or alkoxy group, preferably 0. R ₇ is preferably hydrogen or an alkyl group optionally substituted, eg with a dialkylamino group.

If X is S = O, then n is 1,
It is preferred that (link ₁ ) comprises an arylamino group or an aryl-aminocarbonyl group, preferably one or more alkyl, carbonyl groups or a phenylaminocarbonyl group whose ring may be substituted with a halogen atom. When X is C or C-NH, it is preferred that n is 0 and no (link ₁ ) group is present.

The (link ₂ ) group comprises an alkylene group, preferably a polyalkylene group, which generally comprises 4 or 6 methylene groups, which may be separated by one or more O or S atoms. Is preferred. For example,
(link ₂ ) is (CH ₂ ) ₄ , (CH ₂ ) ₆ , (C
_{H 2) 2 S (CH 2} ) 2 or _{(CH 2) 2 O (CH} 2)
_It may be ₂ O (CH ₂ ) ₂ . Alternatively, (lin
k ₂ ) is a polyalkylene oxide chain extending with an even number of methylene groups, for example (CH ₂ CH ₂ O) ₁₄ CH ₂ CH
₂ or, for example, CH ₂ C ₆ H ₄ CH
_It may contain _two groups.

The anionic counterion may be selected from those well known in the art and is generally Cl ⁻ , Br.
_{^{-, I -, CF 3 COO}} -, CH 3 SO 3 -, TsO -
You may choose from.

Unless otherwise specified, the substituents that can be used in the molecules herein include, whether substituted or unsubstituted,
Any group is included as long as it does not interfere with the properties required for photographic use. Substituents also include forms that are further substituted with any of the groups (which may be more than one) mentioned herein.

Preferably, the substituents may be halogen or may be attached to the rest of the molecule by a carbon, silicon, oxygen, nitrogen, phosphorus or sulfur atom. Substituents may be, for example, halogen (eg chlorine, bromine or fluorine), nitro, hydroxyl, cyano, carboxyl, or alkyl including straight chain or branched chain alkyl (eg methyl, trifluoromethyl, ethyl, t-butyl, 3- (2,4-di-t-
Pentylphenoxy) -propyl, and tetradecyl), alkenyl (eg ethylene, 2-butene), alkoxy (eg methoxy, ethoxy, propoxy, butoxy, 2-methoxy-ethoxy, sec-butoxy,
Hexyloxy, 2-ethylhexyloxy, tetra-
Decyloxy, 2- (2,4-di-t-pentylphenoxy) -ethoxy, and 2-dodecyloxyethoxy), aryl (eg phenyl, 4-t-butylphenyl, 2,4,6-trimethylphenyl, naphthyl). ,
Aryloxy (eg phenoxy, 2-methylphenoxy, α- or β-naphthyloxy, and 4-tolyloxy), carbonamide (eg acetamide, benzamide, butyramide, tetradecanamide, α-)
(2,4-Di-t-pentylphenoxy) -acetamide, α- (2,4-di-t-pentylphenoxy) -butylamide, α- (3-pentadecylphenoxy) -hexanamide, α- (4- Hydroxy-3-t-butylphenoxy) -tetradecanamide, 2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolidin-1-yl, N-methyltetradecanamide, N
-Succinimide, N-phthalimide, 2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl, and N-acetyl-N-
Dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino, phenyl-
Carbonylamino, 2,5- (di-t-pentylphenyl) -carbonylamino, p-dodecylphenylcarbonylamino, p-toluylcarbonylamino, N-methylureido, N, N-dimethylureido, N-methyl-
N-dodecyl ureido, N-hexadecyl ureido,
N, N-dioctadecyl ureido, N, N-dioctyl-N'-ethyl ureido, N-phenyl ureido, N,
N-diphenylureido, N-phenyl-Np-toluylureido, N- (m-hexadecylphenyl) -ureido, N, N- (2,5-di-t-pentylphenyl) -N'-ethylureido , T-butyl carbonamide), sulfonamide (eg methyl sulfonamide,
Benzenesulfonamide, p-toluylsulfonamide, p-dodecylbenzenesulfonamide, N-methyltetradecylsulfonamide, N, N-dipropylsulfamoylamino, and hexadecylsulfonamide), sulfamoyl (eg, N-methylsulfaamide) Moyl, N-ethylsulfamoyl, N, N-dipropyl-
Sulfamoyl, N-hexadecyl sulfamoyl,
N, N-dimethyl-sulfamoyl, N- [3- (dodecyloxy) -propyl] -sulfamoyl, N- [4
-(2,4-di-t-pentylphenoxybutyl] -sulfamoyl, N-methyl-N-tetradecylsulfamoyl, and N-dodecylsulfamoyl), carbamoyl (eg N-methylcarbamoyl, N, N-). Dibutyl-carbamoyl, N-octadecylcarbamoyl,
N- [4- (2,4-di-t-pentylphenoxy)-
Butyl] -carbamoyl, N-methyl-N-tetradecylcarbamoyl, N, N-dioctylcarbamoyl),
Acyl (eg acetyl, (2,4-di-t-amylphenoxy) -acetyl, phenoxycarbonyl, p-dodecyloxyphenoxycarbonyl, methoxy-carbonyl, butoxycarbonyl, tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 3 -Pentadecyloxycarbonyl, and dodecyloxycarbonyl), sulfonyl (eg methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl, 2-ethylhexyloxysulfonyl, phenoxysulfonyl, 2,4-di-t-pentylphenoxysulfonyl, methylsulfonyl). , Octyl sulfonyl, 2-ethylhexyl sulfonyl, dodecyl sulfonyl, hexadecyl sulfonyl, phenyl sulfonyl, 4-nonyl phenyl Sulfonyl, p-toluylsulfonyl), sulfonyloxy (eg dodecylsulfonyloxy, and hexadecylsulfonyloxy), sulfinyl (eg methylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecyl-sulfinyl, phenylsulfinyl, 4-nonyl). Phenylsulfinyl, and p-toluylsulfinyl), thio (eg, ethylthio, octylthio, benzylthio, tetradecylthio,
2- (2,4-di-t-pentylphenoxy) -ethylthio, phenylthio, 2-butoxy-5-t-octyl-phenylthio, p-tolylthio), acyloxy (eg acetyloxy, benzoyloxy, octadecanoyloxy, p-dodecylamidobenzoyloxy, N
-Phenylcarbamoyloxy, N-ethyl-carbamoyloxy, and cyclohexylcarbonyloxy), amines (eg phenylanilino, 2-chloroanilino, diethylamine, dodecylamine), imides (eg 1- (N-phenylimido) -ethyl, N -Succinimide, or 3-benzylhydantoinyl),
Phosphates (for example dimethyl phosphate and ethylbutyl phosphate), phosphites (for example diethyl phosphite and dihexyl phosphite), heterocyclic groups, heterocyclic oxy groups or heterocyclic thio groups (each of which may be substituted, It may contain a 3- to 7-membered heterocycle consisting of at least one heteroatom selected from the group consisting of oxygen, nitrogen, and sulfur and a carbon atom (for example, 2-furyl, 2-cenyl, 2- Benzimidazolyloxy, or 2-benzo-thiazolyl),
It may be an optionally further substituted group such as quaternary ammonium (eg triethylammonium), as well as silyloxy (eg trimethylsilyloxy). If desired, these substituents may themselves be further substituted one or more times with the above-mentioned substituents. The particular substituents used can be chosen by one skilled in the art to achieve the photographic properties desired for a particular application,
For example, it may contain a hydrophobic group, a solubilizing group, a blocking group, a releasing group or a releasable group, and a group adsorbing to silver halide. Generally, the above groups and their substituents are
It may contain up to 8 carbon atoms, generally 1 to 36 carbon atoms, usually less than 24 carbon atoms, depending on the particular substituent selected, higher numbers are possible. is there.

Specific examples of the nucleating agent of the present invention are shown below.
The present invention is not limited to these.

[0086]

[Chemical 30]

[0087]

[Chemical 31]

[0088]

[Chemical 32]

[0089]

[Chemical 33]

[0090]

[Chemical 34]

[0091]

[Chemical 35]

[0092]

[Chemical 36]

[0093]

[Chemical 37]

[0094]

[Chemical 38]

[0095]

[Chemical Formula 39]

[0096]

[Chemical 40]

[0097]

[Chemical 41]

[0098]

[Chemical 42]

[0099]

[Chemical 43]

In the present invention, the hydrazine nucleating agent is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methylethylketone), dimethylformamide, dimethylsulfoxide, It can be used by dissolving it in methyl cellosolve or the like. Further, by well-known emulsion dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate,
It is possible to dissolve it using an auxiliary solvent such as ethyl acetate or cyclohexanone and mechanically prepare an emulsified dispersion for use. Alternatively, by a method known as a solid dispersion method, a hydrazine derivative powder is ball-milled in water,
It can be dispersed in a colloid mill or ultrasonic waves before use.

In the present invention, the hydrazine nucleating agent may be added to the silver halide emulsion layer on the silver halide emulsion layer side of the support, or to any other hydrophilic colloid layer. It is preferably added to the silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto. Further, two or more kinds of hydrazine-based nucleating agents can be used in combination. In the present invention, the amount of the nucleating agent added is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol, and more preferably 2 × 10 1 mol per mol of silver halide. Most preferably, it is ^{-5 to} 5 x 10 ^-3 mol.

In the present invention, a nucleation accelerator can be incorporated in the light-sensitive material. Examples of the nucleation accelerator used in the present invention include amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives.
The examples are listed below. The compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically 49
Compounds A-1) to A-73) described on pages 58 to 58. The compounds represented by (Chemical formula 21), (Chemical formula 22) and (Chemical formula 23) described in JP-A-7-84331, specifically, the compounds described on pages 6 to 8 of the publication. Compounds represented by the general formula [Na] and the general formula [Nb] described in JP-A-7-104426, specifically, compounds Na-1 to Na-22 described on pages 16 to 20 of the publication. And Nb-1 to Nb-
12 compounds. General formula (1), general formula (2), general formula (3), general formula (4), general formula (5), general formula (6) and general formula (7) described in JP-A-8-272023. Specifically, the compounds 1-1 to 1-19, the compounds 2-1 to 2-22, the compounds 3-1 to 3-36, and the compound 4-1 described in the same specification. ~ 4-5 compounds, 5-1-5-41 compounds, 6-1-6-58 compounds, and 7-1-7-38 compounds. JP-A-9-2
No. 97377, p55, column 108, line 8 to p69,
The nucleation accelerator according to column 136, line 44.

The nucleation accelerator used in the present invention includes
The quaternary salt compounds represented by the general formulas (a) to (f) are preferable, and the compound represented by the general formula (b) is particularly preferable.

[0104]

[Chemical 44]

In the general formula (a), R ₁₀₀ , R ₁₁₀ , R
_The aliphatic group represented by ₁₂₀ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group,
sec-butyl group, tert-butyl group, octyl group,
2-ethylhexyl group, dodecyl group, hexadecyl group,
Linear or branched alkyl group such as octadecyl group; aralkyl group such as substituted or unsubstituted benzyl group; cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group; allyl group, vinyl group, 5-hexenyl group An alkenyl group such as a group; a cyclopentenyl group,
Examples thereof include cycloalkenyl groups such as cyclohexenyl group; and alkynyl groups such as phenylethynyl group. The aromatic group is a phenyl group, a naphthyl group, an aryl group such as a phenanthryl group, and the heterocyclic group is a pyridyl group, a quinolyl group, a furyl group, an imidazolyl group, a thiazolyl group, a thiadiazolyl group, a benzotriazolyl group, Examples thereof include a benzothiazolyl group, a morpholyl group, a pyrimidyl group, and a pyrrolidyl group.

Examples of the substituents substituted on these groups include, in addition to the groups represented by R ₁₀₀ , R ₁₁₀ and R ₁₂₀ , halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, Nitro group, (alkyl or aryl) amino group, alkoxy group, aryloxy group, (alkyl or aryl) thio group, carbonamido group, carbamoyl group, ureido group, thioureido group, sulfonylureido group, sulfonamide group, sulfamoyl group, Hydroxyl group, sulfonyl group, carboxyl group (including carboxylate), sulfo group (including sulfonate), cyano group, oxycarbonyl group, acyl group, heterocyclic group (heterocyclic group containing a quaternized nitrogen atom) (Including) and the like. These substituents may be further substituted with these substituents. The groups represented by R ₁₀₀ , R ₁₁₀ and R ₁₂₀ in the general formula (a) may be bonded to each other to form a cyclic structure.

Examples of the group represented by M in the general formula (a) include groups having the same meanings as R ₁₀₀ , R ₁₁₀ and R ₁₂₀ when m ₁₀ is 1. When m ₁₀ represents an integer of 2 or more, M
Represents an m ₁₀ -valent linking group that is bonded to Q ₁ ⁺ at a carbon atom contained in M, and specifically, an alkylene group, an arylene group, a heterocyclic group, further these groups and a —CO— group, —
O- group, -N _{(R N)} - group, -S- group, -SO- group, -
M formed by combining SO ₂ − and —P═O— groups
Represents a _10- valent linking group ( _RN is a hydrogen atom or R ₁₀₀ ,
It represents a group having the same meaning as R ₁₁₀ and R _120, and when a plurality of R _N are present in the molecule, they may be the same or different, and may be bonded to each other). M may have an arbitrary substituent, and as the substituent, R is
Examples thereof include the same substituents that the groups represented by ₁₀₀ , R ₁₁₀ and R ₁₂₀ may have.

In the general formula (a), R ₁₀₀ , R ₁₁₀ , R
₁₂₀ is preferably a group having 20 or less carbon atoms, particularly preferably an aryl group having 15 or less carbon atoms when Q ₁ represents a phosphorus atom, and an alkyl group having 15 or less carbon atoms when Q ₁ represents a nitrogen atom. , Aralkyl groups and aryl groups are particularly preferable. m ₁₀ is preferably 1 or 2, and when m ₁₀ is 1, M is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group, aralkyl group, or aryl group having 15 or less total carbon atoms. When m ₁₀ represents 2, the divalent organic group represented by M is preferably an alkylene group, an arylene group, and further these groups and a —CO— group, an —O— group, a —O— group,
N _{(R N)} - is a divalent group formed by combining groups - group, -S- group, -SO _2. When m ₁₀ represents 2, M
Is a carbon atom contained in M and the total number of carbon atoms bonded to Q ₁ ⁺ is 2
It is preferably a divalent group of 0 or less. When M, or R ₁₀₀ , R ₁₁₀ , and R ₁₂₀ include a plurality of repeating units of ethyleneoxy group or propyleneoxy group, the preferable range of the total carbon number described above is not limited thereto. Further When m ₁₀ represents an integer of 2 or more, R _100, R ₁₁₀ in the molecule, R ₁₂₀ is each plurality of, the plurality of R _100, R _110, R ₁₂₀ is optionally substituted by one or more identical respectively May be.

The quaternary salt compound represented by the general formula (a) is
There are a total of 20 or more repeating units of ethyleneoxy groups or propyleneoxy groups in the molecule, which may be substituted at one position or may be distributed over a plurality of positions. When m ₁₀ represents an integer of 2 or more,
It is more preferable that the linking group represented by M has a total of 20 or more repeating units of ethyleneoxy groups or propyleneoxy groups.

In the general formula (b), general formula (c) or general formula (d), A ₁ , A ₂ , A ₃ , A ₄ and A _{5 each} contain a quaternized nitrogen atom and are substituted or non-substituted. It represents an organic residue for completing a substituted unsaturated heterocycle, which may contain a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a hydrogen atom, and may further have a condensed benzene ring.
Examples of unsaturated heterocycles formed by A ₁ , A ₂ , A ₃ , A ₄ and A ₅ include pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, thiazole ring, thiadiazole ring, benzotriazole ring, benzothiazole. Examples thereof include a ring, a pyrimidine ring, a pyrazole ring and the like. Particularly preferred are a pyridine ring, a quinoline ring, and an isoquinoline ring. The unsaturated heterocycle formed by A ₁ , A ₂ , A ₃ , A ₄ , and A ₅ together with the quaternized nitrogen atom may have a substituent. Examples of the substituent in this case include the same substituents that the groups represented by R ₁₀₀ , R ₁₁₀ and R ₁₂₀ of the general formula (a) may have. The substituent is preferably a halogen atom (particularly a chloro atom), an aryl group having 20 or less carbon atoms (particularly preferably a phenyl group), an alkyl group, an alkynyl group, a carbamoyl group,
(Alkyl or aryl) amino group, (alkyl or aryl) oxycarbonyl group, alkoxy group,
Aryloxy group, (alkyl or aryl) thio group, hydroxy group, mercapto group, carbonamido group,
Sulfonamide group, sulfo group (including sulfonate),
Examples thereof include a carboxyl group (including carboxylate), a cyano group, and the like. Particularly preferred are phenyl group, alkylamino group, carbonamido group, chloro atom, alkylthio group and the like, and most preferred is phenyl group.

The divalent linking group represented by L ₁₀ and L ₂₀ is alkylene, arylene, alkenylene, alkynylene, divalent heterocyclic group, —SO ₂ —, —SO—, —O.
-, -S-, -N ( _RN ')-, -C (= O)-, -P
It is preferable that O-is used alone or in combination.
However R _{N 'represents} an alkyl group, an aralkyl group, an aryl group, a hydrogen atom. The divalent linking group represented by L ₁₀ and L ₂₀ may have an arbitrary substituent. Examples of the substituent include the same substituents that the groups represented by R ₁₀₀ , R ₁₁₀ and R ₁₂₀ of the general formula (a) may have. Particularly preferred examples of L ₁₀ and L ₂₀ are alkylene, arylene, -C (= O)-, -O-, -S-,-.
SO ₂ − and —N ( _RN ′) — may be used alone or in combination.

R ₁₁₁ , R ₂₂₂ and R ₃₃₃ are preferably an alkyl group having 1 to 20 carbon atoms or an aralkyl group, and they may be the same or different. R ₁₁₁ , R ₂₂₂ , and R ₃₃₃ may have a substituent, and the substituent may be a group represented by R ₁₀₀ , R ₁₁₀ , and R ₁₂₀ of the general formula (a). The same thing as a substituent is mentioned. Particularly preferably, R
₁₁₁ , R ₂₂₂ , and R ₃₃₃ are each an alkyl group having 1 to 10 carbon atoms or an aralkyl group. Examples of preferable substituents include carbamoyl group, oxycarbonyl group, acyl group, aryl group, sulfo group (including sulfonate), carboxyl group (including carboxylate), hydroxy group, (alkyl or aryl) amino group, An alkoxy group can be mentioned. However, when R ₁₁₁ , R ₂₂₂ , and R ₃₃₃ contain a plurality of repeating units of ethyleneoxy group or propyleneoxy group, the above R ₁₁₁ , R ₂₂₂ , and R _{333 can be used.}
The preferred range of the number of carbons mentioned above is not limited to this.

The quaternary salt compound represented by the general formula (b) or the general formula (c) has a total of 20 or more repeating units of ethyleneoxy group or propyleneoxy group in the molecule. It may be substituted, or may be substituted at a plurality of positions, and A ₁ , A ₂ , A ₃ ,
It may be substituted with any of A ₄ , R ₁₁₁ , R ₂₂₂ , L ₁₀ and L ₂₀ , but it is preferable that the connecting group represented by L ₁₀ or L _{20 has} a repeating ethyleneoxy group or a propyleneoxy group. It is preferable to have a total of 20 or more units.

The quaternary salt compound represented by the general formula (d) is
It has a total of 20 or more repeating units of ethyleneoxy groups or propyleneoxy groups in the molecule, which may be substituted at one position or at multiple positions, and is either A ₅ or R ₃₃₃ . The group represented by R ₃₃₃ preferably has a total of 20 or more repeating units of ethyleneoxy groups or propyleneoxy groups.

The quaternary salt compound represented by the general formula (a), the general formula (b), the general formula (c) or the general formula (d) contains an ethyleneoxy group and a propyleneoxy group repeatedly at the same time. You can leave. Further, when a plurality of repeating units of ethyleneoxy group or propyleneoxy group is contained, the repeating number may take exactly one value or may be given as an average value. In the latter case, quaternary salt The compound is a mixture having a certain molecular weight distribution. In the present invention, it is more preferable to have a total of 20 or more ethyleneoxy repeating units, and it is more preferable to have a total of 20 to 67 total repeating units.

[0116]

[Chemical formula 45]

In the general formula (e), Q ₂ , R ₂₀₀ ,
R ₂₁₀ and R ₂₂₀ are each Q ₁ in the general formula (a),
It represents a group having the same meaning as R ₁₀₀ , R ₁₁₀ and R _120, and the preferred ranges are also the same. In the general formula (f), A ₆ is
It represents a group having the same meaning as A ₁ or A ₂ in the general formula (b), and its preferable range is also the same. However, the nitrogen-containing unsaturated heterocycle formed by A _{6 of} the general formula (f) together with the quaternized nitrogen atom may have a substituent,
It does not have a substituent containing a primary hydroxyl group.

In formulas (e) and (f), L ₃₀ represents an alkylene group. As the alkylene group,
A linear, branched, or cyclic, substituted or unsubstituted alkylene group having 1 to 20 carbon atoms is preferable. Further, not only saturated one represented by ethylene group but also -CH
₂ C ₆ H ₄ CH ₂ - and _{-CH 2} CH = CHCH 2 - in may be those that contain groups of unsaturation represented. When L ₃₀ has a substituent, examples of the substituent include the substituents which the groups represented by R ₁₀₀ , R ₁₁₀ and R ₁₂₀ of the general formula (a) may have. As L ₃₀ , a linear or branched saturated group having 1 to 10 carbon atoms is preferable. More preferably, it is a substituted or unsubstituted methylene group, ethylene group or trimethylene group, particularly preferably a substituted or unsubstituted methylene group or ethylene group, and most preferably a substituted or unsubstituted methylene group.

In formulas (e) and (f), L ₄₀ represents a divalent linking group having at least one hydrophilic group. Here _-SO the hydrophilic group 2 -, - SO
-, -O-, -P (= O) =, -C (= O)-, -CO
_{NH -, - SO 2 NH -} , - NHSO 2 NH -, - NH
CONH-, amino group, guadinino group, ammonio group,
It represents each group of a heterocyclic group containing a quaternized nitrogen atom, or a group consisting of a combination of these groups. L ₄₀ is constituted by appropriately combining these hydrophilic groups with an alkylene group, an alkenylene group, an arylene group and a heterocyclic group. Groups such as an alkylene group, an arylene group, an alkenylene group, and a heterocyclic group that form L ₄₀ may have a substituent. Examples of the substituent include R ₁₀₀ and R in the general formula (a).
_The same examples as the examples of the substituent which the groups represented by ₁₁₀ and R ₁₂₀ may have are mentioned. In L ₄₀ , the hydrophilic group is L
_It may be present in the form of splitting ₄₀ or as a part of the substituent on L ₄₀ , but it is more preferably present in the form of splitting L ₄₀ . For example -C
_{(= O) -, - SO} 2 -, - SO -, - O -, - P (=
_{O) =, - CONH -,} - SO 2 NH -, - NHSO 2
NH-, -NHCONH-, a cationic group (specifically, a quaternary salt structure of nitrogen or phosphorus, or a nitrogen-containing heterocycle containing a quaternized nitrogen atom), an amino group, a guadinino group, or 2 consisting of a combination of these groups
This is the case where the valent group is present in a form that divides L ₄₀ .

One of the preferable examples of the hydrophilic group which L ₄₀ has is a group having a plurality of repeating units of ethyleneoxy group or propyleneoxy group, which is a combination of an ether bond and an alkylene group. The degree of polymerization or the average degree of polymerization is preferably 2 to 67. The hydrophilic group that L ₄₀ has also includes —SO ₂ —, —SO—, —O—, and —.
P (= O) =, -C (= O)-, -CONH-, -SO
₂ NH-, -NHSO ₂ NH-, -NHCONH-, amino group, guanidino group, ammonio group, as a result of combining groups such as heterocyclic group containing a quaternized nitrogen atom, or or having L ₄₀ It is also preferable to include a dissociative group as a substituent. Here, the dissociative group means a group or a partial structure having a proton having a low acidity which can be dissociated in an alkaline developing solution, or a salt thereof, and specifically, for example, a carboxy group /-COOH, a sulfo group. / _-SO 3 H, a phosphonic acid group / _-PO 3 H, phosphoric acid group / -OPO ₃ H, hydroxy group / -OH group, mercapto group / -SH, _{-SO 2} NH 2 group, N- substituted sulfonamide group / _-SO 2 NH- group, -CONHSO ₂ -
Group, —SO ₂ NHSO ₂ — group, —CONHCO— group, active methylene group, and —NH— inherent in a nitrogen-containing heterocyclic group.
A group or a salt thereof.

L ₄₀ is preferably an alkylene group or an arylene group, and —C (═O) —, —SO ₂ —, —O—,
_{-CONH -, - SO 2 NH -} , - NHSO 2 NH-,
A combination of —NHCONH— and an amino group is used. More preferably -C alkylene group having 2 to 5 carbon atoms _{(= O) -, - SO} 2 -, - O -, - C
_{ONH -, - SO 2 NH -} , - NHSO 2 NH -, - N
An appropriate combination of HCONH- is used.

[0122] Y is -C (= O) - or -SO ₂ - represents a. Preferably -C (= O)-is used.

X in the general formulas (a) to (f)
^As an example of the counter anion represented by ^n- , a chlorine ion,
Halogen ions such as bromine ion and iodine ion, acetate ion, oxalate ion, fumarate ion, carboxylate ion such as benzoate ion, p-toluenesulfonate, methanesulfonate,
Examples thereof include sulfonate ion such as butane sulfonate and benzene sulfonate, sulfate ion, perchlorate ion, carbonate ion, nitrate ion and the like. The counter anion represented by X ^n- is preferably a halogen ion, a carboxylate ion, a sulfonate ion or a sulfate ion,
n is preferably 1 or 2. As ^Xn- , a chloro ion or a bromo ion is particularly preferable, and a chloro ion is most preferable. However, when another anion group is present in the molecule to form an intramolecular salt with Q ₁ ⁺ , Q ₂ ⁺ or N ⁺ , X ^n- is not necessary.

The quaternary salt compound of the present invention is more preferably a quaternary salt compound represented by the general formula (b), the general formula (c) or the general formula (f). The quaternary salt compound represented by the formula (f) is particularly preferable. Further, in the general formula (b), it is preferable that the linking group represented by L ₁₀ has 20 or more ethyleneoxy repeating units, and particularly preferably 20 to 67 repeating units. Further, in the general formula (f), it is particularly preferable that the unsaturated heterocyclic compound formed by A ₆ represents 4-phenylpyridine, isoquinoline or quinoline.

Specific examples of the quaternary salt compounds represented by the general formulas (a) to (f) are shown below. (In the formula, Ph represents a phenyl group.) However, the present invention is not limited to the following compound examples.

[0126]

[Chemical formula 46]

[0127]

[Chemical 47]

[0128]

[Chemical 48]

[0129]

[Chemical 49]

[0130]

[Chemical 50]

[0131]

[Chemical 51]

[0132]

[Chemical 52]

[0133]

[Chemical 53]

The quaternary salt compounds represented by the general formulas (a) to (f) of the present invention can be easily synthesized by a known method. The synthetic examples are shown below.

Synthesis Example 1 (Synthesis of Exemplified Compound 3) Polyethylene glycol (average molecular weight 2000, 800)
g), thionyl chloride (584 ml) and DMF (4 ml)
Were mixed at room temperature, then heated to 90 ° C. and stirred for 5 hours.
After distilling off excess thionyl chloride, 4-phenylpyridine (372 g) was added and the mixture was reacted at 150 ° C. for 7 hours.
The reaction mixture was treated with ethyl acetate / 2-propanol (10 /
The solution of 1) was prepared, cooled, and the precipitated solid was collected by filtration. This was dried to obtain the target Exemplified Compound 3. (58
4g, yield 62%)

Synthesis Example 2 (Synthesis of Exemplified Compound 6) Polyethylene glycol (average molecular weight: 2000, 10)
g), thionyl chloride (7.3 ml) and DMF (0.1 m)
l) was mixed at room temperature, then heated to 90 ° C. and stirred for 5 hours. After distilling off excess thionyl chloride, isoquinoline (4.0 g) was added and the mixture was reacted at 150 ° C. for 7 hours. The reaction mixture was made into a solution of ethyl acetate / 2-propanol (10/1), cooled, and the precipitated solid was collected by filtration. This was dried to obtain the target Exemplified Compound 6. (7.1 g, yield 60%)

Synthesis Example 3 (Synthesis of Exemplified Compound 4) Exemplified Compound 3 was prepared in the same manner as in Synthesis Example 1 except that polyethylene glycol (average molecular weight 2000) was used instead of polyethylene glycol (average molecular weight 2000). Got 4.

Synthesis Example 4 (Synthesis of Exemplified Compound 65) 1,10-Diamino-4,7-dioxadecane (17.
6 g, 0.1 mol), potassium carbonate (27.6 g, 0.
2 mol), ethyl acetate (100 ml), water (50 ml)
Was vigorously stirred at room temperature, and chloroacetyl chloride (34 g, 0.3 mol) was added dropwise thereto. The reaction mixture was separated, the ethyl acetate layer was dried over sodium sulfate, and concentrated to give 1,10-bis (chloroacetylamino) -4,7-.
Dioxadecane was obtained (23 g, 70% yield). 3.3 g of this compound and triphenylphosphine (7.9
g) were mixed and heated at 150 ° C. for 5 hours. The reaction mixture was cooled and washed three times with ethyl acetate to obtain 5.4 g (yield 63%) of Exemplified Compound 65 as a brown viscous liquid.

Synthesis Example 5 (Synthesis of Exemplified Compound 62) Instead of triphenylphosphine in Synthesis Example 4, 4 was used.
-Except that phenylpyridine was used, the same operation was performed to obtain Exemplified Compound 62.

Synthesis Example 6 (Synthesis of Exemplified Compound 71) O, O′-bis (2-aminopropyl) polyethylene glycol 800 was used in place of 1,10-diamino-4,7-dioxadecane in Synthesis Example 4, and tri Except that 4-phenylpyridine was used instead of phenylphosphine, the same operation was performed to obtain Exemplified Compound 71.

The nucleation accelerator of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl. It can be used by dissolving it in cellosolve or the like.

By a well-known emulsification and dispersion method, oils such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are used to dissolve and mechanically dissolve them. An emulsified dispersion can be prepared and used. Alternatively, the powder of the nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The nucleation accelerator of the present invention is preferably added to a non-photosensitive layer consisting of a hydrophilic colloid layer containing no silver halide emulsion on the side of the silver halide emulsion layer with respect to the support. It is preferably added to a non-photosensitive layer consisting of a hydrophilic colloid layer between a silver halide emulsion layer and a support. The addition amount of the nucleation accelerator of the present invention is preferably 1 × 10 ⁻⁶ to 2 × 10 ⁻² mol, based on 1 mol of silver halide.
× 10 ^{−5 to} 2 × 10 ⁻² mol is more preferable, and 2 × 1.
Most preferably, it is 0 ⁻⁵ to 1 × 10 ⁻² mol. Further, two or more kinds of nucleation accelerators can be used in combination.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited as silver halide, and silver chloride, silver chlorobromide, silver bromide, silver iodochlorobromide, silver iodobromide. However, silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride are preferable. The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, amorphous and plate-like, but cubic is preferred. The average grain size of silver halide is preferably 0.1 μm to 0.7 μm, more preferably 0.1 to 0.5 μm, and {(standard deviation of grain size) / (average grain size)} × 100 It is preferable that the variation coefficient represented is 15% or less, more preferably 10% or less and the particle size distribution is narrow. The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases. Also, a localized layer having a different halogen composition may be provided inside or on the surface of the grain. The photographic emulsion used in the present invention is P. Gl.
afkides Chimie et Physique Photographique (Pa
ul Montel, 1967), GF Dufin Photograph
icEmulsion Chemistry (The Forcal Press, 1966
), By VL Zelikman et al Making and Coating Phot
ographic Emulsion (Published by The Forcal Press, 1964)
And the like.
That is, any of an acidic method and a neutral method may be used, and as a method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used.

As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. Tetrasubstituted thiourea compounds are more preferred, and they are described in JP-A Nos. 53-82408 and 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-dimethyl-
It is 2-imidazolidinethione. The addition amount of the silver halide solvent varies depending on the kind of the compound used, the intended grain size and the halogen composition, but is preferably 10 ⁻⁵ to 10 ⁻² mol per mol of the silver halide.

The controlled double jet method and the grain forming method using a silver halide solvent make it easy to form a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and are used in the present invention. It is a useful tool for making silver halide emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016,
As described in JP-B-48-36890 and JP-A-52-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent 4,242,445, Kaisho 55-158124
It is preferable to use the method of changing the concentration of the aqueous solution as described in No. 3, to rapidly grow in a range not exceeding the critical saturation.

The silver halide emulsion used in the present invention is
It may contain a metal belonging to Group VIII. In particular, in order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound and the like. In addition, K ₄ [F
e (CN) ₆ ], K ₄ [Ru (CN) ₆ ], K ₃ [Cr
Doping with a metal hexacyanide complex such as (CN) ₆ ] is advantageously carried out.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having halogen, amines, oxalate, aco, etc. as a ligand, for example, hexachlororhodium (III) complex salt, pentachloroacorodium complex salt, tetrachlorodiaco Examples thereof include rhodium complex salt, hexabromorhodium (III) complex salt, hexaamine rhodium (III) complex salt, and trizalatrodium (III) complex salt. These rhodium compounds are used by dissolving them in water or a suitable solvent, and they are generally used for stabilizing the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or alkali halides (eg KCl, NaCl, KB
r, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.

Rhenium, ruthenium and osmium used in the present invention are described in JP-A-63-2042 and JP-A-1.
-2859451, 2-20852, 2-208
It is added in the form of a water-soluble complex salt described in No. 55, etc. Particularly preferred are hexacoordinated complexes represented by the following formulas. [ML ₆ ] ^n- where M is Ru, Re,
Or Os, L is a ligand, and n is 0, 1, 2, 3 or 4. In this case, the counterion has no significance,
Ammonium or alkali metal ions are used. Further, a preferred ligand is a halide ligand,
Cyanide ligands, cyan oxide ligands, nitrosyl ligands, thionitrosyl ligands and the like can be mentioned. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[ReCl ₆ ] ^3- [ReBr ₆ ] ^3- [ReCl ₅ (NO)] ^2- [Re (NS) Br ₅ ] ^2- [Re (NO) (CN) ₅ ] ^2- [Re (O ) ₂ (CN) ₄ ] ^3- [RuCl ₆ ] ^3- [RuCl ₄ (H ₂ O) ₂ ] ^1- [RuCl ₅ (NO)] ^2- [RuBr ₅ (NS)] ^2- [Ru (CO) ₃ Cl ₃ ] ^2- [Ru (CO) Cl ₅ ] ^2- [Ru (CO) Br ₅ ] ^2- [OsCl ₆ ] ^3- [OsCl ₅ (NO)] ^2- [Os (NO) (CN) ₅ ] ^2- [Os (NS) Br ₅ ] ^2- [Os (CN) ₆ ] ^4- [Os (O) ₂ (CN) ₄ ] ^4-

The addition amount of these compounds is 1
The range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol is preferable, and the range of 1 × 10 ⁻⁸ mol to 1 × 10 is particularly preferable.
^-6 mol. Examples of the iridium compound used in the present invention include hexachloroiridium, hexabromoiridium, hexaammineiridium, pentachloronitrosyliridium and the like. Examples of the iron compound used in the present invention include potassium hexacyanoferrate (II),
Ferrous thiocyanate is mentioned.

The silver halide emulsion used in the present invention is preferably chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and a noble metal sensitization method can be used, and they can be used alone or in combination. When used in combination, for example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization, etc. Is preferred.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. As the sulfur sensitizer, known compounds can be used. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines are used. be able to. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer added varies depending on various conditions such as pH, temperature and size of silver halide grains during chemical ripening, but it is 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. And more preferably 10 ⁻⁵ to 10 ⁻³ mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748 and 43-13489,
The compounds described in JP-A-4-109240 and JP-A-4-324855 can be used. In particular, JP-A-4-3
It is preferable to use the compounds represented by the general formulas (VIII) and (IX) in 24855.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride, which is presumed to serve as a sensitizing nucleus, on the surface or inside of the silver halide grain. Regarding the formation rate of silver telluride in a silver halide emulsion, the method disclosed in JP-A-5-187
It can be tested by the method described in No.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496.
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Laid-Open No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No. 3, No. 5-303157, Journal of Chemical Society Chemical Communication
(J.Chem.Soc.Chem.Commun.) 635 (1980), ibid 1102 (197
9), ibid 645 (1979), Journal of Chemical Society Perkin Transactions (J. Chem. Soc.
Perkin.Trans.) 1,2191 (1980), edited by S. Patai, The Chemistry of Organic Selenium and Tellurium Campounds (The Chemistry of
Organic Serenium and Tellunium Compounds), Vol 1 (1
986) and Vol 2 (1987). In particular, the general formula (II) in JP-A-4-324855
The compounds represented by (III) and (IV) are preferable.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions and the like, but generally 10 ⁻⁸ to 10 ⁻² mol per mol of silver halide, Preferably 10 ⁻⁷ to 1
0 ^-3 mol is used. The chemical sensitization conditions in the present invention are not particularly limited, but the pH is 5 to 8, p
The Ag is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium and iridium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, and gold sulfide.
About 10 ⁻⁷ to 10 ⁻² mol can be used per mol of silver halide. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of forming silver halide grains or physically ripening. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound and the like can be used. To the silver halide emulsion of the present invention, a thiosulfonic acid compound may be added according to the method disclosed in European Patent Publication (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, different halogen compositions, different crystal habits, chemically sensitized ones). Different conditions and different sensitivities) may be used together. Among them, in order to obtain high contrast, it is preferable to apply an emulsion having higher sensitivity as it is closer to the support, as described in JP-A-6-324426.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized by a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. Furthermore, JP-A-5
The compound of the general formula [I] described in JP-A-5-45015 and the compound of the general formula [I] described in JP-A-9-160185 are preferable, and the compound of the general formula [I] described in JP-A-9-160185 is particularly preferable. Compounds of I] are preferred. In particular,
(1) to (19) described in JP-A-55-45015
And the compounds of I-1 to I-40 and the compounds of I-56 to I-85 described in JP-A No. 9-160185.

Other sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes,
Complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used. Other useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOSURE Item 17643IV-A (1
December 978 p. 23), Item 18341X item (1)
August 979 p. 437) or cited therein. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various scanners, imagesetters and plate-making cameras can be advantageously selected. For example, in A) an argon laser light source, Japanese Patent Laid-Open No.
(I) -1 to (I) -8 compounds described in JP-A-162247 and I-1 to I described in JP-A-2-48653.
-28 compound, I described in JP-A-4-330434
-1 to compounds of I-13, U.S. Pat. No. 2,161,33
Sample 1 to Sample 14 described in No. 1
Compounds, 1 to 7 compounds described in West German Patent No. 936,071, and B) helium-neon laser light source, I-1 to I-described in JP-A-54-18726.
38 compound, I-1 described in JP-A-6-75322
To I-35 and compounds I-1 to I-34 described in JP-A-7-287338 and C) LED light sources, the dyes 1 to 20 described in JP-B-55-39818, Compounds I-1 to I-37 described in JP-A-62-284343 and compounds I-1 to I-34 described in JP-A-7-287338, D) JP-A-59-59 for a semiconductor laser light source. Compounds I-1 to I-12 described in JP-A-191032, JP-A-60-80841.
Compounds I-1 to I-22 described in Japanese Patent Application Laid-Open No. 4-3
Compounds I-1 to I-29 described in JP-A-35342 and I-1 to I-described in JP-A-59-192242.
No. 18 compound, E) the tungsten and xenon light sources of the plate-making camera, in addition to the compounds described above, compounds I-41 to I-55 and I-86 to I- described in JP-A-9-160185. The compound of 97, the compounds of 4-A to 4-S, the compounds of 5-A to 5-Q, the compounds of 6-A to 6-T, etc. described in JP-A-6-242547 can be advantageously selected. it can.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosur.
e) Volume 176, 17643 (issued in December 1978), second
Item J of page 3, IV, or the aforementioned Japanese Patent Publication No. 49-2550
0, 43-4933, JP-A-59-19032, 5
9-192242 and the like.

The sensitizing dyes used in the present invention may be used in combination of two or more kinds. To add the sensitizing dyes to the silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3. -A single solvent such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. Further, as disclosed in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent and the solution is dispersed in water or a hydrophilic colloid. Method of adding to emulsion, JP-B-44-23389,
As disclosed in JP-A-44-27555, JP-A-57-22091, etc., a dye is dissolved in an acid and the solution is added to the emulsion, or an acid or a base is coexisted and added as an aqueous solution to the emulsion. Method, US Pat. No. 3,822,135
No. 4,006,025, etc., a method of adding an aqueous solution or a colloidal dispersion in which a surfactant coexists into an emulsion, as disclosed in Japanese Patent Laid-Open No. Sho 5-6
A method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion, as disclosed in JP-A-3-102733 and JP-A-58-105141, and JP-A-51-251.
As disclosed in Japanese Patent No. 74624, it is also possible to use a method of dissolving a dye by using a compound that causes red shift and adding the solution into an emulsion. Ultrasonic waves can also be used for the solution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion at any stage in the preparation of emulsions which has been found to be useful so far.
For example, US Pat. Nos. 2,735,766 and 3,62.
No. 8,960, No. 4,183,756, No. 4,2
25,666, JP-A-58-184142, 60
As disclosed in the specification such as -196749,
It is disclosed in the specification of JP-A-58-113920, etc. during the grain forming step of silver halide or / and before desalting, during the desilvering step and / or after desalting and before the start of chemical ripening. As described above, they may be added at any time or step immediately before or during the chemical ripening, during the step, after the chemical ripening, and before the coating of the emulsion before the coating. Further, as disclosed in the specifications of US Pat. No. 4,225,666 and JP-A-58-7629,
The same compound alone or in combination with a compound having a different structure may be divided into, for example, a grain formation step and a chemical ripening step or after chemical ripening, or a pre-chemical ripening step or a step after and after chemical ripening. The compound and the combination of compounds may be added in different portions.

In the present invention, the amount of the sensitizing dye added varies depending on the shape and size of the silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, etc.
4 × 10 ⁻⁶ to 8 × 10 per mol of silver halide
It can be used at ^-3 mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, 2 × 10 ^{−7 to} 3.5 × per 1 m ² of surface area of the silver halide grain.
The addition amount of 10 ⁻⁶ mol is preferable and 6.5 × 10 ⁻⁷ to
The addition amount of 2.0 × 10 ⁻⁶ mol is more preferable.

There are no particular restrictions on various additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used.

Polyhydroxybenzene compounds described in JP-A-3-39948, page 10, lower right, line 11 to page 12, lower left, line 5; Specifically, the compounds of Compounds (III) -1 to 25 described in the publication.

A compound represented by the general formula (I) described in JP-A-1-118832, which has substantially no absorption maximum in the visible region. Specifically, the compound I-described in the above publication is used.
Compounds 1 to 1-26.

The antifoggant described in JP-A-2-103536, page 17, lower right line, line 17 to page 18, upper right line, fourth line.

Polymer latices described in JP-A-2-103536, page 18, lower left line 12 to lower left line 20, same page. Polymer latex having an active methylene group represented by the general formula (I) described in JP-A-9-179228, specifically, compounds I-1 to I described in the specification.
I-16. Polymer latex having a core / shell structure described in JP-A-9-179228, specifically, compounds P-1 to P-55 described in the specification. JP-A-7-1
No. 04413, page 14, left column, line 1 to page right, line 30; acidic polymer latices, specifically, compounds II-1) to II-9) described on page 15 of the same.

Matting agents, slip agents, and plasticizers described in JP-A-2-103536, page 19, upper left line, line 15 to page 19, upper right line, line 15.

Hardeners described in JP-A-2-103536, page 18, upper right, line 5 to upper right, line 17 of the same page.

Compounds having an acid group described in JP-A-2-103536, page 18, lower right line, line 6 to page 19, upper left line, line 1.

JP-A-2-18542, page 2, lower left 1
Conductive substances from the third line to the seventh line on the upper right of page 3 of the publication. Specifically, the metal oxides described in page 2, lower right line, page 2 to lower right line, line 10 of the same publication, and conductive polymer compounds of compounds P-1 to P-7 described in the same publication. .

Water-soluble dyes described in JP-A-2-103536, page 17, lower right column, line 1 to upper right, line 18 of the same page.

Solid disperse dyes represented by formula (FA), formula (FA1), formula (FA2) and formula (FA3) described in JP-A-9-179243. Specifically, compounds F1 to F34 described in the above publication, JP-A-7-152112.
(II-2) to (II-24) described in JP-A-7-152.
(III-5) to (III-18) described in JP-A No. 112-112, JP-A-7-78
(IV-2) to (IV-7) described in No. 152112. Solid disperse dyes described in JP-A-2-294638 and JP-A-5-11382.

Redox compounds capable of releasing a development inhibitor when oxidized as described in JP-A-5-274816. Preferably, the general formula (R-1) described in the above publication,
A redox compound represented by the general formula (R-2) or the general formula (R-3). Specifically, the compound R-1 described in the above publication
~ R-68 compounds.

JP-A-2-18542, page 3, lower right corner 1
The binder described in lines 20 to 20.

The swelling ratio of the hydrophilic colloid layer including the emulsion layer and the protective layer of the silver halide photographic light-sensitive material of the present invention is 80.
To 150% is preferable, and 90 to 1 is more preferable.
It is in the range of 40%. For the swelling ratio of the hydrophilic colloid layer, the thickness (d ₀ ) of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic light-sensitive material was measured, and the silver halide photographic light-sensitive material was distilled at 25 ° C. Immersed in water for 1 minute, the swollen thickness (Δd) was measured, and the swollen rate (%) =
It is obtained by the calculation formula of (Δd ÷ d ₀ ) × 100.

The film surface pH of the silver halide photographic light-sensitive material of the present invention on the side coated with the silver halide emulsion layer is 4.0.
The range is from to 7.5, preferably from 4.2 to 6.0.

Examples of the support usable in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, and polyester film such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material. A support made of a styrene-based polymer having a syndiotactic structure described in JP-A-7-234478 and US Pat. No. 5,558,979 is also preferably used.

The processing agents and processing methods such as the developing solution and fixing solution in the present invention will be described below, but needless to say, the present invention is not limited to the following description and specific examples.

Any known method can be used for the development treatment of the present invention, and a known development processing solution can be used.

Developer used in the present invention (hereinafter, both the development starter and the development replenisher are collectively referred to as a developer).
The developing agent used in (1) is not particularly limited, but preferably contains dihydroxybenzenes, ascorbic acid derivatives, and hydroquinone monosulfonate, and may be used alone or in combination. In particular, it is preferable to contain a dihydroxybenzene-based developing agent and an auxiliary developing agent exhibiting superadditivity therewith, a combination of dihydroxybenzenes or ascorbic acid derivatives and 1-phenyl-3-pyrazolidones, or dihydroxybenzenes or Examples thereof include a combination of an ascorbic acid derivative and p-aminophenols. Examples of the developing agent used in the present invention include dihydroxybenzene developing agents such as hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferable. Ascorbic acid derivative developing agents include ascorbic acid, isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferable from the viewpoint of material cost.

The developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention includes 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4. -Methyl-
4-hydroxymethyl-3-pyrazolidone and the like.
N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine as a p-aminophenol-based developing agent used in the present invention,
There are o-methoxy-p- (N, N-dimethylamino) phenol, o-methoxy-p- (N-methylamino) phenol and the like. Among them, N-methyl-p-aminophenol or JP-A-9- Aminophenols described in JP-A-297377 and JP-A-9-297378 are preferable.

The dihydroxybenzene type developing agent is preferably used usually in an amount of 0.05 mol / liter to 0.8 mol / liter. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 mol / liter to 0.6 mol / liter, preferably 0.10 mol / liter. ˜0.5 mol / liter, the latter is preferably used in an amount of 0.06 mol / liter or less, preferably 0.03 mol / liter to 0.003 mol / liter.

The ascorbic acid derivative developing agent is preferably used in an amount of usually 0.01 mol / l to 0.5 mol / l, preferably 0.05 mol / l.
0.3 mol / liter is more preferable. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the amount of the ascorbic acid derivative is 0.01 mol / liter or more.
It is preferable to use 0.5 mol / liter, 1-phenyl-3-pyrazolidones or p-aminophenols in an amount of 0.005 mol / liter to 0.2 mol / liter.

The developer used for processing the light-sensitive material in the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffer, preservative, chelating agent, etc.). Specific examples of these are shown below, but the present invention is not limited thereto. The buffer used in the developing solution when developing the light-sensitive material in the present invention,
Carbonates, boric acid described in JP-A-62-186259, sugars described in JP-A-60-93433 (eg saccharose), oximes (eg acetoxime), phenols (eg 5-sulfosalicylic acid), third phosphorus Acid salts (for example, sodium salt, potassium salt) and the like are used, and carbonate and boric acid are preferably used. The amount of buffering agent, especially carbonate, used is preferably 0.1 mol / liter or more, and particularly 0.2 to 1.5 mol / liter.

Examples of preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite is preferably 0.2 mol / liter or more,
In particular, it is used in an amount of 0.3 mol / liter or more, but if added in an excessively large amount, it will cause silver stain in the developing solution, so the upper limit is preferably 1.2 mol / liter. Particularly preferably, it is 0.35 to 0.7 mol / liter. As a preservative for the dihydroxybenzene-based developing agent, a small amount of the ascorbic acid derivative may be used in combination with sulfite. Of these, sodium erythorbate is preferably used from the viewpoint of material cost. The addition amount is 0.03 to molar ratio based on the dihydroxybenzene type developing agent.
The range of 0.12 is preferable, and particularly preferably 0.05 to
It is in the range of 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Additives other than those mentioned above include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide,
Alkanolamines such as diethanolamine and triethanolamine, development accelerators such as imidazole and its derivatives, heterocyclic mercapto compounds (for example, 3-
(5-Mercaptotetrazol-1-yl) benzenesulfonate sodium salt, 1-phenyl-5-mercaptotetrazole, etc.) and the compounds described in JP-A No. 62-212651 may be added as a physical development unevenness preventing agent. In addition, a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, or a benzimidazole-based compound is used as an antifoggant or a black spot (blackpe).
pper) inhibitor may be included. Specifically, 5
-Nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzo Imidazole, 5-nitrobenzotriazole, 4-((2-mercapto-1,
3,4-thiadiazol-2-yl) thio) butanesulfonate sodium, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5
-Methylbenzotriazole, 2-mercaptobenzotriazole, etc. can be mentioned. The amount of these additives is usually 0.01 to 10 mmol, and more preferably 0.1 to 2 mmol, per liter of the developing solution.

Further, in the developer of the present invention, various organic compounds,
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate, etc. can be used. On the other hand, as the organic chelating agent, mainly organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be used. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acieleic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid. Acid, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

Examples of aminopolycarboxylic acids include:
Iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediamine monohydroxyethyl triacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid,
1,2-Diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol etherdiaminetetraacetic acid, and others, JP-A-52-25632 and 5
5-67747, 57-102624, and the compounds described in JP-B-53-40900 can be mentioned.

Examples of the organic phosphonic acid include hydroxyalkylidene groups described in US Pat. Nos. 3,214,454 and 3,794,591 and West German Patent Publication No. 2,227,369.
Diphosphonic Acid and Research Disclosure No. 181
Vol., Item 18170 (May 1979 issue) and the like. As aminophosphonic acid,
Examples thereof include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. Others include Research Disclosure 18170 and JP-A-57-208.
554, 54-61125, 55-29883, 56-97347 and the like.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A Nos. 52-102726, 53-42730, 54-112127, 55-4024, 55-4024.
25, the same 55-126241, the same 55-65955, the same 55-69556 and the compounds described in the above-mentioned Research Disclosure 18170 and the like.

These organic and / or inorganic chelating agents are not limited to those mentioned above. Also,
You may use it in the form of an alkali metal salt or an ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ per liter of the developing solution.
Mol, more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol.

Further, as a silver stain preventing agent in the developer,
For example, JP-A-56-24347 and JP-B-56-465.
85, JP-B-62-2849, JP-A-4-36294.
2. In addition to the compounds described in JP-A-8-6215, triazines having one or more mercapto groups (for example, Japanese Patent Publication No.
No. 23830, JP-A-3-282457, and JP-A 7-1.
75178), the same pyrimidine (for example, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine, 2,4. 6
-Trimercaptopyrimidine, JP-A-9-274289
Compound, etc.), the same pyridine (for example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,
5-dimercaptopyridine, 2,4,6-trimercaptopyridine, the compounds described in JP-A-7-248587, and the same pyrazine (for example, 2-mercaptopyrazine,
2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, etc., and the same pyridazine (for example, 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-di). Mercaptopyridazine, 3,4,6-trimercaptopyridazine, etc.), the compound described in JP-A-7-175177,
The polyoxyalkylphosphonates described in US Pat. No. 5,457,011 and the like can be used. These silver stain preventing agents can be used alone or in combination of two or more, and the addition amount is preferably 0.05 to 10 mmol, and more preferably 0.1 to 5 mmol per 1 L of the developing solution.
Further, the compounds described in JP-A-61-267759 can be used as a dissolution aid. Further, if necessary, a color toning agent, a surfactant, a defoaming agent, a hardener and the like may be contained.

The preferred pH of the developer is 9.0 to 12.0.
And particularly preferably in the range of 9.0 to 11.0, and more preferably 9.5 to 11.0. As the alkaline agent used for pH adjustment, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

As the cation of the developing solution, potassium ion does not suppress the development as compared with sodium ion, and there is less jaggedness around the blackened portion called fringe. Further, when stored as a concentrated solution, the potassium salt is generally preferred because of its higher solubility. However,
In the fixer, potassium ion inhibits fixing to the same extent as silver ion.Therefore, if the potassium ion concentration in the developer is high, the potassium ion concentration in the fixer becomes high because the developer is brought in by the photosensitive material. , Not preferable. From the above, the molar ratio of potassium ion to sodium ion in the developer is preferably between 20:80 and 80:20. The ratio of potassium ion to sodium ion is a counter cation such as a pH buffering agent, a pH adjusting agent, a preservative, and a chelating agent, and can be arbitrarily adjusted within the above range.

The replenishing amount of the developing solution is 390 ml or less per 1 m ² of the light-sensitive material, preferably 325 to 30 ml, and most preferably 250 to 120 ml. The development replenisher may have the same composition and / or concentration as the development starter, or may have a different composition and / or concentration from the starter.

Ammonium thiosulfate, sodium thiosulfate and ammonium sodium thiosulfate can be used as the fixing agent of the fixing processing agent in the present invention. The amount of the fixing agent used can be changed as appropriate, but generally about 0.7 to
It is about 3.0 mol / liter.

The fixing solution in the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt which acts as a hardener, and the water-soluble aluminum salt is preferable. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, aluminum lactate and the like. These are 0.01 to 0.1 as the aluminum ion concentration in the used liquid.
It is preferably contained at 5 mol / liter. When the fixer is stored as a concentrated solution or a solid agent, it may be composed of a plurality of parts including a hardener or the like as a separate part, or may be a one-part type composition containing all components.

Preservatives (for example, sulfite, bisulfite, metabisulfite, etc., 0.0
15 mol / liter or more, preferably 0.02 mol / liter to 0.3 mol / liter, and a pH buffering agent (for example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogen carbonate, phosphoric acid, succinic acid, adipic acid, etc.). 0.1
Mol / l to 1 mol / l, preferably 0.2
Mol / liter to 0.7 mol / liter), a compound having aluminum stabilizing ability and water softening ability (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid) , Maleic acid, glycolic acid, benzoic acid, salicylic acid, Tyrone, ascorbic acid, glutaric acid, aspartic acid,
Glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and their derivatives and their salts, sugars,
0.001 mol / liter to 0.5 mol / boric acid
Liter, preferably 0.005 mol / liter to 0.
3 mol / liter).

In addition, the compounds described in JP-A-62-78551, pH adjusters (for example, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can be included. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene-based surfactants, and JP-A-57-6840.
The amphoteric surfactants described above can be mentioned, and known defoaming agents can also be used. Wetting agents include alkanolamines and alkylene glycols. Examples of fixing accelerators include alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681, JP-B-45-35754, JP-A-58-122535, and JP-A-58-1.
22536, a thiourea derivative, an alcohol having a triple bond in the molecule, a thioether compound described in U.S. Pat. No. 4,126,459, JP-A-64-4739, JP-A-1-47939.
-4739, 1-115645 and 3-1017
The mercapto compound described in No. 28, the mesoionic compound described in No. 4-170539, and thiocyanate can be included.

The pH of the fixing solution in the present invention is preferably 4.0 or higher, and more preferably 4.5 to 6.0. The pH of the fixing solution increases due to the processing solution mixed with the processing solution. In this case, it is 6.0 or less, preferably 5.7 or less for the hardening fixing solution, and 7.0 or less for the non-hardening fixing solution. Is 6.7 or less.

The replenishing amount of the fixing solution is 500 ml or less per 1 m ² of the light-sensitive material, preferably 390 ml or less, and more preferably 320 to 80 ml. The replenishing solution may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration as the starting solution.

The fixing solution can be recycled by a known fixing solution recycling method such as electrolytic silver recovery. As the reproducing device, for example, Reclaim R-6 manufactured by Fuji Hunt Co., Ltd.
There is 0 etc. It is also preferable to remove the dye and the like using an adsorption filter such as activated carbon.

When the developing and fixing processing agent in the present invention is a liquid agent, it is preferably stored in a packaging material having a low oxygen permeability as described in, for example, JP-A-61-73147. Further, when these solutions are concentrated solutions, they are used by diluting 1 part of the concentrated solution with 0.2 to 3 parts of water so as to have a predetermined concentration.

Even when the developing treatment agent and the fixing treatment agent in the present invention are solid, the same results as the liquid agent can be obtained. However, the solid treatment agent will be described below. Known forms (powder, granule, granule, lump, tablet, compactor, briquette, plate, rod, paste, etc.) can be used as the solid agent in the present invention. These solid agents may be coated with a water-soluble coating agent or film in order to separate the components that react with each other when they come into contact with each other, or may have a plurality of layers to separate the components that react with each other. , And these may be used together.

Known coating agents and granulating aids can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrene sulfonic acid and vinyl compounds are preferred. In addition, the 48th line of column 2 to the 13th line of column 3 of JP-A-5-45805 can be referred to.

In the case of forming a plurality of layers, components that do not react even when they come into contact with each other may be sandwiched between components that react with each other and processed into tablets or briquettes. It may be packaged in the same layer structure. These methods are described, for example, in JP-A-61-259921 and JP-A-6-259921.
-16841, 4-78848, 5-93991, etc.

The bulk density of the solid processing agent is 0.5 to 6.0 g.
/ Cm ³ is preferred, especially tablets are 1.0 to 5.0 g / c
m ³ is preferred, and the granules are preferably 0.5 to 1.5 g / cm ³ .

As the method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, JP-A-4-32837, and JP-A-4-7884.
8, same 5-93991, JP-A-4-85533, same 4-
85534, 4-85535, 5-134362,
5-1997070, 5-204098, 5-22
4361, 6-138604, 6-138605,
It is possible to refer to the above 8-286329.

More specifically, rolling granulation method, extrusion granulation method, compression granulation method, crushing granulation method, stirring granulation method, spray drying method, melt coagulation method, briquetting method, roller compaction method. The Ting method or the like can be used.

The solid agent of the present invention can be adjusted in solubility by changing the surface condition (smoothness, porosity, etc.) or partial thickness, or by forming a hollow donut shape.
Further, it is possible to take a plurality of shapes in order to give different solubilities to a plurality of granules or to adjust the solubilities of materials having different solubilities. Further, a multi-layer granulated product having different compositions on the surface and inside may be used.

The packaging material for the solid agent is preferably a material having low oxygen and water permeability, and the packaging material may have a known shape such as a bag, a cylinder, or a box. In addition, JP-A-6-242
585 to 6-242588, 6-247432, 6-247448, 6-301189, 7-566.
It is also preferable to make the foldable shape as disclosed in No. 4 and No. 7-5666 to No. 7-5669 in order to reduce the storage space of the waste packaging material. These packaging materials may be provided with a screw cap, a pull top, an aluminum seal at the outlet of the treatment agent, or the packaging material may be heat-sealed, but other known materials may be used, and there is no particular limitation. do not do. Further, in terms of environmental protection, it is preferable to recycle or reuse the waste packaging material.

The method of dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. Examples of these methods include a method of dissolving and replenishing a fixed amount with a dissolving apparatus having a stirring function, and a dissolving apparatus having a dissolving portion and a portion for stocking a completed liquid as described in JP-A-9-80718. Method of melting and replenishing from stock part, JP-A-5-119454,
6-19102 and 7-261357, the processing agent is added to the circulation system of the automatic developing machine to dissolve it.
There are a method of replenishing, a method of adding a processing agent according to the processing of a light-sensitive material by an automatic developing machine having a built-in dissolution tank, and dissolving, and any other known method can be used. The processing agent may be manually added, or may be automatically opened and automatically supplied by a dissolving device or an automatic processor having an opening mechanism as described in JP-A-9-138495. From the viewpoint of the above, the latter is preferable. Specifically, a method of piercing the take-out port, a method of peeling off, a method of cutting off, a method of pushing off, and the like, JP-A-6-19102 and 6-9.
5331 and the like.

The light-sensitive material which has been developed and fixed is then washed or stabilized (hereinafter, referred to as washing including stabilizing treatment unless otherwise specified. The liquid used for these is water or washing water). That). The water used for washing may be tap water, ion-exchanged water, distilled water or stabilizing solution. The replenishing amount of these is generally 1 m ² of the light-sensitive material.
It is about 17 liters to about 8 liters, but it is also possible to replenish at a lower amount. In particular, when the replenishment amount is 3 liters or less (including 0. That is, washing with water), not only the water saving process becomes possible, but also the pipe for installing the automatic processor can be eliminated. When the washing with water is carried out with a low replenishing amount, it is more preferable to provide a washing tank for squeeze rollers and crossover rollers described in JP-A-63-18350 and JP-A-62-287252. In addition, various oxidizers (eg ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load which is a problem when washing with a small amount of water and to prevent water stains. You may combine addition and filter filtration.

[0215] As a method of reducing the replenishing amount of the washing, a multi-stage countercurrent system (for example, two stages, three stages, etc.) than the old are the known water washing replenishment rate photosensitive material 1 m ² per 200-5
0 ml is preferred. This effect can be similarly obtained by an independent multi-stage system (a method in which a new solution is individually replenished in a multi-stage washing tank without countercurrent flow).

Further, a means for preventing water stain may be added to the washing step by the method of the present invention. Known means can be used as the scale prevention means, and there is no particular limitation, but a method for adding an antifungal agent (so-called scale prevention agent), a method for energizing, a method for irradiating ultraviolet rays or infrared rays or far infrared rays, There are methods of applying a magnetic field, ultrasonic treatment, heating, and emptying the tank when not in use. These water stain preventing means may be carried out according to the processing of the light-sensitive material, may be carried out at a constant interval regardless of the use condition, or may be carried out only during a non-working period such as at night. Alternatively, it may be preliminarily rinsed with water and then replenished. Further, it is also preferable to carry out different scale preventive means at regular intervals in order to suppress the generation of resistant bacteria. The antifungal agent is not particularly limited and known ones can be used. In addition to the above-mentioned oxidizing agents, for example, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxide (for example, 2
-Mercaptopyridine-N-oxide, etc.), and may be used alone or in combination of two or more. As a method of energizing, Japanese Patent Laid-Open Nos. 3-224685 and 3-22468
7, the method of 4-16280, the same as 4-18980, etc. can be used.

In addition, a known water-soluble surfactant or antifoaming agent may be added to prevent unevenness of water bubbles and transfer of stains. Further, the dye adsorbent described in JP-A-63-163456 may be installed in a water washing system to prevent contamination by dyes eluted from the light-sensitive material.

A part or all of the overflow liquid from the water washing step can be mixed and used in a processing liquid having fixing ability as described in JP-A-60-235133. In addition, microbial treatment (for example, sulfur-oxidizing bacteria, activated sludge treatment, treatment with a filter supporting microorganisms on a porous carrier such as activated carbon or ceramics), or oxidization treatment with electricity or an oxidant to obtain biochemical oxygen demand Quantity (BO
D), chemical oxygen demand (COD), iodine consumption, etc. are reduced before draining, or a compound using a polymer having an affinity for silver or a sparingly soluble silver complex such as trimercaptotriazine is formed. It is also preferable from the viewpoint of conservation of the natural environment to reduce the silver concentration in the wastewater by adding silver to precipitate silver and filter the mixture with a filter.

There is also a case where a stabilizing treatment is carried out after the water washing treatment, and examples thereof include JP-A-2-201357 and JP-A-2-201357.
-132435, 1-102553, JP-A-46-4
A bath containing the compound described in 4446 may be used as the final bath of the light-sensitive material. If necessary, ammonium compounds, metal compounds such as Bi and Al, fluorescent whitening agents, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, antifungal agents, alkanolamines and surface active agents can also be used in this stabilizing bath. Agents can also be added.

Additives such as antifungal agents and stabilizers to be added to the washing and stabilizing baths may be solid agents like the above-mentioned developing and fixing processing agents.

Waste liquids of the developing solution, fixing solution, washing water and stabilizing solution used in the present invention are preferably incinerated. Also, these waste liquids are, for example, Japanese Patent Publication No. 7-83867, U.
It is also possible to dispose after concentrating and liquefying with a concentrating device such as described in S5439560.

When the replenishment amount of the processing agent is reduced, it is preferable to reduce the opening area of the processing tank to prevent the evaporation of liquid and the oxidation of air. Regarding the roller-conveying type automatic developing machine, U.S. Pat. Nos. 3,025,779 and 3,545,97.
1 and the like, and is simply referred to as a roller transport type automatic developing machine in the present specification. This automatic developing machine comprises four steps of development, fixing, washing and drying, and although the method of the present invention does not exclude other steps (for example, stopping step), it is most preferable to follow these four steps. Further, a rinsing bath may be provided between the developing and fixing and / or the fixing water washing.

In the development processing of the present invention, the time from the start of processing to the time after drying (dry to dry) is preferably 25 to 160 seconds, the development and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each solution is 25-50 degreeC is preferable and 3
0-40 degreeC is preferable. Washing temperature and time is 0-5
40 seconds or less at 0 ° C. is preferable. According to the method of the present invention,
The light-sensitive material which has been developed, fixed and washed may be dried by squeezing wash water, that is, passing through a squeeze roller.
Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the ambient conditions. Any known method can be used as the drying method, and there is no particular limitation. However, warm air drying or JP-A-4-15534, 5-2256, and 5-2.
There are heat roller drying and far infrared ray drying as disclosed in 89294, and a plurality of methods may be used in combination.

[0224]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1

<Preparation of Emulsion A> 1-liquid water 750 ml gelatin 20 g sodium chloride 3 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium benzenethiosulfonate 10 mg citric acid 0.7 g 2-liquid water 300 ml silver nitrate 150 g 3-liquid water 300 ml Sodium chloride 38 g Potassium bromide 32 g Potassium hexachloroiridium (III) (0.005% by mass KCl 20% by mass aqueous solution) 5 ml Ammonium hexachlororhodate (0.001% by mass NaCl 20% by mass aqueous solution) 7 ml Hexachloro used for 3 liquids Potassium iridium (III) (0.005 mass% KCl 20 mass% aqueous solution) and ammonium hexachlororhodate (0.001
(Mass% NaCl 20 mass% aqueous solution) was prepared by dissolving powders in KCl 20 mass% aqueous solution and NaCl 20 mass% aqueous solution, respectively, and heating at 40 ° C. for 120 minutes.

[0226] To 1 solution kept at 38 ° C and pH 4.5, 2
90% each of the liquid and 3 liquid were added simultaneously with stirring for 20 minutes to form 0.16 μm core particles. Subsequently, the following 4 liquid and 5 liquid were added over 8 minutes, and the remaining 10% amounts of 2 liquid and 3 liquid were added over 2 minutes to grow to 0.21 μm. further,
0.15 g of potassium iodide was added and aged for 5 minutes to complete grain formation. 4-Liquid Water 100 ml Silver Nitrate 50 g 5-Liquid Water 100 ml Sodium Chloride 13 g Potassium Bromide 11 g Yellow Blood Salt 5 mg Then, it was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of an anionic precipitating agent-1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide precipitated. (PH 3.
Then, about 3 liters of the supernatant was removed (first water washing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide had settled. Again, 3 liters of the supernatant was removed (second washing with water).
Repeat the same operation as the second washing once more (third washing)
The washing and desalting process was completed. To the emulsion after washing with water and desalting, 45 g of gelatin was added to adjust the pH to 5.6 and pAg to 7.5, and 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 15 mg of sodium thiosulfate and 10 mg of chloroauric acid were added. Chemically sensitized to obtain optimum sensitivity at ℃
Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene (100 mg) and proxel (trade name, manufactured by ICI Co., Ltd.) 100 mg as a preservative were added. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide, having an average grain size of 0.22 μm and a coefficient of variation of 9% was obtained. (Finally, as an emulsion, pH = 5.7, pAg = 7.5, conductivity = 40 μS
/ M, density = 1.2 to 1.25 × 10 ³ kg / m ³ , and viscosity = 50 mPa · s. )

<Preparation of Emulsion B> Liquid 1 750 ml Gelatin 20 g Sodium chloride 1 g 1,3-Dimethylimidazolidine-2-thione 20 mg Sodium benzenethiosulfonate 10 mg Citric acid 0.7 g 2 liquid water 300 ml Silver nitrate 150 g 3 liquid water 300 ml Sodium chloride 38 g Potassium bromide 32 g Potassium hexachloroiridium (III) (0.005% by mass KCl 20% by mass aqueous solution) 5 ml Ammonium hexachlororhodate (0.001% by mass NaCl 20% by mass aqueous solution) 15 ml Hexachloro used for 3 liquids Potassium iridium (III) (0.005% by mass KCl 20% by mass aqueous solution) and ammonium hexachlororhodate (0.001% by mass NaCl 20% by mass aqueous solution) are powders of KCl 2 respectively. It was prepared by dissolving in a 0 mass% aqueous solution and a 20 mass% NaCl aqueous solution and heating at 40 ° C. for 120 minutes.

To one solution kept at 38 ° C. and pH 4.5, 2
90% each of the liquid and 3 liquid were added simultaneously with stirring for 20 minutes to form 0.16 μm core particles. Then 4-hydroxy-6-methyl-1,
Add 3,3a, 7-tetraazaindene 500mg,
Subsequently, the following 4 liquid and 5 liquid were added over 8 minutes, and the remaining 10% of 2 liquid and 3 liquid were added over 2 minutes to grow to 0.18 μm. Further, 0.15 g of potassium iodide was added and aged for 5 minutes to complete grain formation. 4 liquid water 100 ml silver nitrate 50 g 5 liquid water 100 ml sodium chloride 13 g potassium bromide 11 g yellow blood salt 2 mg Then, it was washed by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of an anionic precipitating agent-1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide precipitated. (PH 3.
Then, about 3 liters of the supernatant was removed (first water washing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide had settled. Again, 3 liters of the supernatant was removed (second washing with water).
Repeat the same operation as the second washing once more (third washing)
The washing and desalting process was completed. To the emulsion after washing and desalting, 45 g of gelatin was added to adjust the pH to 5.6 and pAg to 7.5, and 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 2 mg of triphenylphosphine selenide and 1 mg of chloroauric acid were added. Addition 55
Chemical sensitization was performed to obtain optimum sensitivity at ℃, and 4-hydroxy-6-methyl-1,3,3a, 7- was used as a stabilizer.
100 mg of tetraazaindene and 100 mg of proxel as a preservative were added. Finally 70 mol% of silver chloride,
An average grain size of 0.18 μm containing 0.08 mol% of silver iodide,
A silver iodochlorobromide cubic grain emulsion having a variation coefficient of 10% was obtained.
(Finally, as an emulsion, pH = 5.7, pAg = 7.
5, conductivity = 40 μS / m, density = 1.2 × 10 ³ kg
/ M ³ , and the viscosity was 50 mPa · s. )

<Preparation of non-photosensitive silver halide grains->

1 liquid water 1 liter gelatin 20 g potassium bromide 0.9 g citric acid 0.2 g NH ₄ NO ₃ 20 g hydrogen peroxide 3.5 g sodium benzenethiosulfonate 15 mg 2 liquid water 400 ml silver nitrate 200 g 3 liquid water 400 ml bromide Potassium 140.0 g Potassium hexachlororhodium (III) (0.001 mass% aqueous solution) 4000 ml

While stirring one solution kept at 60 ° C. with Na
40 ml of OH (1N) was added, and 0.7 g of an aqueous silver nitrate solution was further added. Then 1 / of 2 and 3
Two by two were added by the control double jet method while keeping the silver potential at +24 mV over 20 minutes, and after physical ripening for 2 minutes, the other half of the second and third solutions was subjected to the same control double jet method. Was added over 20 minutes to form particles.

Then, it was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of an anionic precipitating agent-1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide precipitated.
(PH was in the range of 3.1 ± 0.2) Next, about 3 liters of the supernatant was removed (first washing with water). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide had settled. Again, 3 liters of the supernatant was removed (second washing with water). The same operation as the second water washing was repeated once (third water washing) to complete the water washing / desalting process. After washing and desalting, 45 g of gelatin was added to the emulsion to give a pH of 5.7 and pAg.
Was adjusted to 7.5, phenoxyethanol was added as a preservative, and finally 30 mol% of average silver chloride and 0.08 mol% of silver iodide were contained, and the average particle diameter was 0.8 μm and the coefficient of variation was 10%. A dispersion of unripened silver bromide tetradecahedral emulsion grain particles was obtained. (Finally, as an emulsion, pH = 5.7, pAg =
7.5, conductivity = 40 μS / m, density = 1.3 × 10 ³
It became kg / m ³ and viscosity = ³⁰ mPa · s. 1) per 1 mol of KBr in the following aqueous solutions X-1 to X-4:
Particle formation was carried out by adding potassium hexachlororhodium (III) in an amount corresponding to x10 ^-5 mol.

<Preparation of Non-Photosensitive Silver Halide Grains>

[0234]   1 liquid water 1 liter         20 g of gelatin         Sodium chloride 3.0g         1,3-Dimethylimidazolidine-2-thione 20 mg         Sodium benzenethiosulfonate 8mg   2 liquid water 400ml         Silver nitrate 100g   3 liquid water 400ml         Sodium chloride 13.5g         Potassium bromide 45.0g         Potassium hexachlororhodium (III) (0.001% by mass aqueous solution)                                                             860 ml

1st liquid, 2nd liquid and 3rd liquid kept at 70 ° C. and pH 4.5 were added simultaneously for 15 minutes while stirring,
Nuclear particles were formed. Then, the following 4 liquid and 5 liquid were added over 15 minutes. Further, 0.15 g of potassium iodide was added to complete grain formation.

Thereafter, it was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of an anionic precipitating agent-1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide precipitated.
(PH was in the range of 3.2 ± 0.2) Next, about 3 liters of the supernatant was removed (first washing with water). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide had settled. Again, 3 liters of the supernatant was removed (second washing with water). The same operation as the second water washing was repeated once (third water washing) to complete the water washing / desalting process. After washing and desalting, 45 g of gelatin was added to the emulsion to give a pH of 5.7 and pAg.
Was adjusted to 7.5, phenoxyethanol was added as a preservative, and finally the average silver chloride content was 30 mol% and silver iodide content was 0.08 mol%, the average particle size was 0.45 μm, and the variation coefficient was 10%. A dispersion of unripened silver iodochlorochlorobromide cubic milk particles was obtained. (Finally, as an emulsion, pH = 5.7, pAg
= 7.5, electric conductivity = 40 μS / m, density = 1.3 to 1.
The viscosity was 35 × 103 kg / m ³ and the viscosity was 50 mPa · s. <Preparation of non-photosensitive silver halide grains->

(Preparation of 1st Solution) Aqueous solution 1 containing 0.6 g of KBr and 1.1 g of gelatin having an average molecular weight of 15,000.
300 mL was kept at 35 ° C. and stirred.

(Addition 1) 24 mL of an aqueous Ag-1 solution (containing 4.9 g of AgNO3 in 100 mL) and X-1
Aqueous solution (containing 4.1 g of KBr in 100 mL) 2
4 mL and 24 mL of G-1 aqueous solution (containing 100 g of gelatin having an average molecular weight of 15,000 in 100 mL) were added by a triple jet method at a constant flow rate for 30 seconds.

Thereafter, 1.3 g of KBr was added, and the temperature was raised to 75 ° C. After the aging step for 12 minutes after the temperature was raised, G-2 aqueous solution (trimellitic anhydride was added to 100 mL of an aqueous solution of alkali-treated ossein gelatin at 50 ° C. and pH 9.0 for reaction, and then left 300 ml (containing 12.7 g of gelatin obtained by removing trimellitic acid) was added, and then disodium 4,5-dihydroxy-1,3-disulfonate monohydrate was added to 2.
1 g and 0.002 g of thiourea dioxide were sequentially added at intervals of 1 minute.

(Addition 2) Next, an Ag-2 aqueous solution (100
22.1 g of AgNO3 is contained in mL) 157 mL
And an X-2 aqueous solution (15.5 g of KBr in 100 mL)
Containing) was added by the double jet method over 14 minutes. At this time, the addition of the Ag-2 aqueous solution accelerated the flow rate so that the final flow rate was 3.4 times the initial flow rate, and the addition of the X-2 aqueous solution increased the pAg of the bulk emulsion solution in the reaction vessel to 8.3. I went to keep it.

(Addition 3) Next, an Ag-3 aqueous solution (10
32.0 g of AgNO3 is contained in 0 mL) 329 m
L and an X-3 aqueous solution (21.5% of KBr in 100 mL).
g, containing 1.6 g of KI) by the double jet method
Added over 7 minutes. At this time, the addition of the Ag-3 aqueous solution accelerated the flow rate so that the final flow rate was 1.6 times the initial flow rate, and the addition of the X-3 aqueous solution increased the pAg of the bulk emulsion solution in the reaction vessel to 8.3. I went to keep it.

(Addition 4) Further, an Ag-4 aqueous solution (10
Contains 32.0 g of AgNO3 in 0 mL) 156 m
L and an X-4 aqueous solution (22.4% of KBr in 100 mL).
g) was added by the double jet method over 17 minutes. At this time, the Ag-4 aqueous solution was added at a constant flow rate, and the X-3 aqueous solution was added so that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 8.3.

Then, 0.0025 g of sodium benzenethiosulfonate and an aqueous solution of G-3 (containing 12.0 of alkali-treated ossein gelatin in 100 mL) 12
5 mL was added sequentially at intervals of 1 minute.

Next, 43.7 g of KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.0, and
73.9 g of AgI fine particles (containing 13.0 g of AgI fine particles having an average particle diameter of 0.047 μm in 100 g) was added.

(Addition 5) Two minutes later, 249 mL of an Ag-4 aqueous solution and an X-4 aqueous solution were added by the double jet method. At this time, the Ag-4 aqueous solution was added at a constant flow rate for 16 minutes, and the X-4 aqueous solution was added so that the pAg was kept at 9.10.

(Addition 6) Subsequently, for 10 minutes, addition was carried out so that the pAg of the bulk emulsion in the reaction vessel was 7.5.

After that, desalting was carried out by an ordinary flocculation method, and then water, NaOH and alkali-treated ossein gelatin were added with stirring, and the pH was adjusted to 56 ° C.
It was adjusted to be 5.8 and pAg 8.9.

The obtained particles had an equivalent circle diameter of 1.0 μm, a particle thickness of 0.10 μm and an average AgI content of 3.94.
Mol%, tabular silver halide grains having parallel (111) planes as main planes, and the variation coefficient of equivalent-circle diameter of all grains was 24%.

[0249]

[Chemical 54]

Preparation of coating sample A polyethylene terephthalate film support consisting of a moistureproof layer undercoating containing vinylidene chloride on both sides as shown below was coated in a UL layer / emulsion layer / protective layer lower layer / protective layer upper layer configuration. To prepare a sample. The preparation method, coating amount and coating method of each layer are shown below.

<Emulsion Layer> Emulsion A and Emulsion B were mixed as shown in Table 1, and sensitizing dye (SD-1) 5.7 × 10 ⁻⁴ mol / mol Ag was added for spectral sensitization. . Further, KBr 3.4 × 10 ⁻⁴ mol / mol Ag compound (Cpd-1) 2.0 × 10 ⁻⁴ mol / mol Ag compound (Cpd-2) 2.0 × 10 ⁻⁴ mol / mol Ag compound (Cpd -3) 8.0 × 10 ⁻⁴ mol / mol Ag 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag hydroquinone 1.2 × 10 ^-2 mol / mol Ag citric acid 3.0x10 ^-4 mol / mol Ag Hydrazine derivative of the present invention (Cpd-4) Amount shown in Table 1 Nucleation accelerator (Cpd-5) 6.0x10 ^-4 Mol / mol Ag The compound represented by the general formula (A) of the present invention Amount shown in Table 1 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 90 mg / m ² colloidal silica (particle size 10 nm) 15% by weight based on gelatin Aqueous latex (Cpd-6) 200 mg / ^{m 2} of polyethyl acrylate latex 150 mg / ^{m 2} latex copolymer of methyl acrylate and 2-acrylamido-2-methylpropane sulfonic acid sodium salt and 2-acetoxyethyl methacrylate (weight ratio 88: 5: 7) 150mg / m ² core-shell type latex (core: styrene / butadiene copolymer (weight ratio 37/63) shell: styrene / 2-acetoxyethyl acrylate (weight ratio 84/16) core / shell ratio = 50/50) 150 mg / m ² Compound (Cpd-7) 4% by mass was added to the total gelatin on the side having the emulsion layer, and the pH of the coating solution was adjusted to 5.6 using citric acid. The emulsion layer coating solution thus prepared was coated on the following support as shown in Table 1 for theoretical silver coating amount and gelatin coating amount.

<Protective Layer Upper Layer> Gelatin 0.3 g / m ² Irregular silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (Cpd-8) (gelatin dispersion) 20 mg / m ² Particle size 10 to 20 nm Colloidal silica (Snowtex C manufactured by Nissan Chemical Industries, Ltd.) 30 mg / m ² compound (Cpd-9) 50 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² compound (Cpd-10) 20 mg / m ² compound (Cpd -11) 20 mg / m ² Compound represented by General Formula (A) of the present invention Amount shown in Table 1 Preservative (Proxel (trade name, manufactured by ICI Co., Ltd.)) 1 mg / m ²

<Lower layer of protective layer> Gelatin 0.5 g / m ² non-photosensitive silver halide grain (shown in Table 1) 0.1 g / m ² compound (Cpd-12) 15 mg / m ² 1,5-dihydroxy- 2-benzaldoxime 10 mg / m ² polyethyl acrylate latex 150 mg / m ² compound (Cpd-13) 3 mg / m ² preservative (proxel) 1.5 mg / m ²

<UL layer> Gelatin 0.5 g / m ² non-photosensitive silver halide grain 0.3 g / m ² polyethyl acrylate latex 150 mg / m ² compound (Cpd-14) 10 mg / m ² compound (Cpd-20 ) 5 mg / m ² preservative (proxel) 1.5 mg / m ²

The viscosity of the coating liquid for each layer was adjusted by adding a thickener represented by the following structure (Z).

[0256]

[Chemical 55]

The sample used in the present invention has a back layer and a conductive layer having the following compositions. <Back layer> Gelatin 3.3 g / m ² non-photosensitive silver halide grain 0.3 g / m ² compound (Cpd-15) 40 mg / m ² compound (Cpd-16) 20 mg / m ² compound (Cpd-17) 90 mg / m ² compound (Cpd-18) 40 mg / m ² compound (Cpd-19) 26 mg / m ² compound (Cpd-20) 5 mg / m ² 1,3-divinylsulfonyl-2-propanol 60 mg / m ² polymethyl Methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² liquid paraffin 78 mg / m ² calcium nitrate 20 mg / m ² preservative (proxel) 12 mg / m ² compound (Cpd-7) For the total gelatin on the side having the back layer To 4 mass%

<Conductive Layer> Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m ² Preservative (proxel) 0.3 mg / m ²

[0259]

[Chemical 56]

[0260]

[Chemical 57]

[0261]

[Chemical 58]

<Support> A biaxially stretched polyethylene terephthalate support (thickness: 100 μm) was coated with the first and second subbing layers having the following compositions on both sides.

<Undercoat layer 1 layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μm) 0.05 g Compound (Cpd -21) 0.20 g colloidal silica (Snowtex ZL: particle size 70 to 100 nm, manufactured by Nissan Chemical Industries, Ltd.) 0.12 g Water was added to 100 g Further, 10% by mass of KOH was added to adjust pH = 6. The coating solution was dried at a temperature of 180 ° C. for 2 minutes and the dry film thickness was 0.
It was applied so as to have a thickness of 9 μm.

<Second Layer of Undercoat Layer> Gelatin 1 g Methylcellulose 0.05 g Compound (Cpd-22) 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Proxel 3.5 × 10 ^{− 3} g acetic acid 0.2 g water was added 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm.

[0265]

[Chemical 59]

<Coating Method> On the support provided with the above-mentioned undercoat layer, first, from the side closer to the support as the emulsion surface side, 4 layers of UL layer, emulsion layer, lower layer of protective layer and upper layer of protective layer were formed in the order of 35 layers. Simultaneous multi-layer coating while adding the hardener solution by the slide bead coater method while maintaining at ℃
C.), the conductive layer and the back layer are applied in this order from the side closer to the support to the side opposite to the emulsion side, while simultaneously applying a hardening agent solution by the curtain coater method, and a cold air set zone ( 5 ° C). The coating liquid exhibited sufficient setting properties when it passed through each setting zone. Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions. In addition, after applying the back surface side, it was conveyed in a state in which there was no contact with the roller and the rest until winding. The coating speed at this time was 200 m / min.

<Drying conditions> After setting, the product was dried with a drying air of 30 ° C. until the water / gelatin mass ratio reached 800%, and
Drying 0 to 200% with a dry air of 35 ° C. and 30% RH, blowing the air as it is, and 30 seconds after the surface temperature reaches 34 ° C. (which is regarded as the end of drying), 48 ° C. and 2% RH
Air for 1 minute. At this time, the drying time is from dry start to water / gelatin ratio of 800% for 50 seconds, 800 to 20
It takes 35 seconds for 0% and 5 seconds for 200% to the end of drying.

This photosensitive material was wound up at 25 ° C. and 55% RH,
Then, cut in the same environment, and conditioned for 8 hours at 25 ° C 50% RH in a barrier bag conditioned for 6 hours, then at 25 ° C 50
The sample shown in Table 1 was prepared by sealing with cardboard that had been conditioned at% RH for 2 hours. When the humidity in the barrier bag was measured, it was 45%. In addition, the film surface pH of the obtained sample on the emulsion layer side was 5.5 to 5.8, and the film surface pH on the back side was 6.0 to 6.0.
It was 6.5. The absorption spectra of the emulsion layer side and the back layer side were as shown in FIG.

Evaluation was carried out by the following methods. <Sensitometry> The obtained sample was exposed to xenon flash light with an emission time of 10 ⁻⁶ seconds through an interference filter having a peak at 667 nm and a step wedge. Then, using the developing solution (A) and the fixing solution (B) having the following formulations, processing was carried out under the developing conditions of 35 ° C. and 30 ″ using an FG-680AG automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.).

Developer (A) The composition per liter of the concentrated liquid is shown. Potassium hydroxide 60.0 g Diethylenetriamine / pentaacetic acid 3.0 g Potassium carbonate 90.0 g Sodium metabisulfite 105.0 g Potassium bromide 10.5 g Hydroquinone 60.0 g 5-Methylbenzotriazole 0.53 g 4-Hydroxymethyl-4- Methyl-1-phenyl-3-pyrazolidone 2.3 g Sodium 3- (5-mercaptotetrazol-1-yl) benzenesulfonate 0.15 g 2-Mercaptobenzimidazole-5-sodium sodium salt 0.45 g Sodium erythorbate 9. 0 g diethylene glycol 7.5 g pH 10.79 In use, the mother liquor was 1 part water to 2 parts of the above concentrate.
The pH of the mother liquor was 10.65 when diluted at a ratio of 1 part, and the replenisher was diluted at a ratio of 3 parts of water to 4 parts of the above concentrate, and the pH of the replenisher was 10.62.

Fixer (B) Prescription The prescription for 1 L of the concentrated liquid is shown. Ammonium thiosulfate 360 g Ethylenediamine ・ tetraacetic acid ・ 2Na ・ dihydrate 0.09 g Sodium thiosulfate / 5-hydrate 33.0 g Sodium metasulfite 57.0 g Sodium hydroxide 37.2 g Acetic acid (100%) 90.0 g Tartaric acid 8.7 g Sodium gluconate 5.1 g Aluminum sulphate 25.2 g pH 4.85 In use, dilute at a ratio of 2 parts of water to 1 part of the above concentrated solution. The pH of the solution used is 4.8.

The gamma (γ) at the optical densities of 0.3 to 3.0 is ((3.0-0.3) / log (density 3.0
Exposure amount) -log (exposure amount which gives a density of 0.3)).

<Evaluation of Storage Stability> In order to predict the change in photographic performance due to long-term storage of the biosensitive material, the biosensitive material was tested with 50
The sensitivity variation (ΔS1.5) was measured when the forced thermotreatment was performed for 5 days under the conditions of ° C and 65% RH. As the sensitivity value (S1.5), the logarithmic value of the exposure amount giving a density of 1.5 was used. ΔS1.5 (storage stability) = − (S1.5 (thermosensitive photosensitive material) −S1.5 (fresh sensitive material)) When the sensitivity is increased, ΔS1.5 shows a positive value. The sensitivity variation with respect to the fresh sensitive material needs to be 0.10 or less for practical use, and is preferably 0.05 or less.

<Evaluation of Practical Density> An image setter FT-R5055 manufactured by Dainippon Screen Co., Ltd. was used to output a test step while changing the light amount at 175 lines / inch, and the development processing was performed under the above processing conditions. The _Dmax portion when exposed at an LV value at which the halftone dot was 50% was measured and defined as the practical density. The net% and the practical skill density are Ma
It was measured using a cbeth TD904.

The results obtained are shown in Table 1. Concentration 0.3
It can be seen that the sample of the present invention having a gamma at 3.0 or more of 5.0 or more and containing the compound of the general formula (A) of the present invention has a high practical concentration and is excellent in storage stability. . On the other hand, the sample having a gamma of less than 5.0 is inferior in practical concentration to the sample of the present invention.

[0276]

[Table 1]

Example 2 An experiment similar to that of Example 1 was conducted using the following solid developer (C) and solid fixing agent (D). As in Example 1, the sample having the constitution of the present invention was good. It showed excellent performance.

[0278]     Solid developer (C) prescription   Sodium hydroxide (beads) 99.5% 11.5g   Potassium sulfite (bulk powder) 63.0g   Sodium sulfite (bulk powder) 46.0 g   62.0 g of potassium carbonate   Hydroquinone (briquette) 40.0g Briquette all at once   Diethylenetriamine / pentaacetic acid 2.0g   5-methylbenzotriazole 0.35 g   4-hydroxymethyl-4-methyl-1-phenyl                         -3-pyrazolidone 1.5g   4- (N-carboxymethyl-N-methylamino)                 -2,6-dimercaptopyrimidine 0.2 g   3- (5-mercaptotetrazol-1-yl)                         Sodium benzenesulfonate 0.1g   Sodium erythorbate 6.0 g   Potassium bromide 6.6g   Dissolve this in water to make 1 liter.   pH 10.65

Here, in the raw material form, the bulk powder was used as it was as a general industrial product, and the alkali metal salt beads were commercially available products. When the raw material form was briquette, it was used after being pressed and compressed into a plate shape using a briquetting machine and then crushed. For minor components, each component was blended before briquetting. 10 liters of the above treatment agent was filled in a foldable container made of high-density polyethylene, and the outlet was sealed with an aluminum seal. For dissolution and replenishment, JP-A-9-80718 and JP-A-9-1
A dissolution replenisher with an automatic opening mechanism as disclosed in 38495 was used.

Solid Fixing Agent (D) Formulation A Agent (Solid) Ammonium thiosulfate (Compact) 125.0 g Anhydrous sodium thiosulfate (bulk powder) 19.0 g Sodium metabisulfite (bulk powder) 18.0 g Anhydrous sodium acetate (raw powder) Powder) 42.0 g Agent B (liquid) Ethylenediamine / tetraacetic acid / 2Na / 2-hydrate 0.03 g Tartaric acid 2.9 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g Sulfuric acid 2.1 g Dissolve in water to make 50 ml. . Fixer (D) was prepared by dissolving agents A and B in water and adjusting the solution to 1 liter. The pH was 4.8.

Ammonium thiosulfate (compact) was prepared by spray-drying a flake product which was compressed under pressure with a roller compactor and crushed into irregularly shaped chips of about 4 to 6 mm, which were then blended with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. 10 liters of each of the agents A and B were filled in a foldable container made of high-density polyethylene, and the outlet of the agent A was sealed with an aluminum seal. The mouth of the agent B container was sealed with a screw cap. For dissolution and replenishment, a dissolution replenishing device having an automatic opening mechanism disclosed in JP-A-9-80718 and JP-A-9-138495 was used.

Example 3 Instead of the developer (A) of Example 1, the following developer (E) was used.
When an experiment similar to that of Example 1 was conducted by using, the photosensitive material having the constitution of the present invention showed good performance as in Example 1.

The composition of the developer (E) per liter of concentrated solution is shown below. Potassium hydroxide 105.0 g Diethylenetriamine / pentaacetic acid 6.0 g Potassium carbonate 120.0 g Sodium metabisulfite 120.0 g Potassium bromide 9.0 g Hydroquinone 75.0 g 5-Methylbenzotriazole 0.25 g 4-Hydroxymethyl-4- Methyl-1-phenyl-3-pyrazolidone 1.35 g 4- (N-carboxymethyl-N-methylamino) -2,6-dimercaptopyrimidine 0.3 g 2-mercaptobenzimidazole-5-sodium sulfonate 0.45 g Sodium erythorbate 9.0 g Diethylene glycol 60.0 g pH 10.7 In use, 1 part of the above concentrate is diluted with 2 parts of water. The pH of the solution used is 10.5

Example 4 With the developer (A) of Example 1, a scanner film HL manufactured by Fuji Photo Film Co., Ltd., which has a blackening rate of 20% per day, was used in an amount of 50 cc per size (50.8 cm × 61 cm).
By processing 20 sheets of large size while replenishing and running this for 6 days a week for 15 consecutive weeks, a small amount of film was processed to reduce the sulfite concentration to 1/3. A liquid was obtained. Using the developer (A) of Example 1, a scanner film HL manufactured by Fuji Photo Film Co., Ltd., which has a blackening rate of 80% per day, was prepared in a large size (5
0.8cm x 61cm) 300 large size sheets are processed while replenishing the used solution with 50cc, and this is continuously performed for 4 days. By processing a large amount of film, the pH drops to 10.2 and the bromine ion concentration increases. A developer having an increased value was obtained.

The same experiment as in Example 1 was conducted using the above-mentioned fatigue developing solution or a developing solution in the middle of fatigue. As in Example 1, the photosensitive material having the constitution of the present invention had good performance. showed that.

Example 5 When the image quality of the light-sensitive material of the present invention of Example 1 was evaluated by the following method, good performance was obtained.

Example 6 In Examples 1 to 5, the developing temperature was 38 ° C. and the fixing temperature was 37.
When the treatment was carried out by setting the temperature to 20 ° C. and the developing time to 20 seconds, the same results as in Examples 1 to 5 were obtained, and the effects of the present invention were not lost.

[Embodiment 7] In the first to fifth embodiments, the automatic developing machine is FG-680AS manufactured by the same company.
The same result was obtained even when the same processing was performed by setting the conveyance speed of the photosensitive material to a linear velocity of 1500 mm / min using.

Example 8 Imagesetter FT-R manufactured by Dainippon Screen Co., Ltd.
Instead of using 5055, Agfagewald Co., Ltd.
Select Set 5000, Avantra 25, or Accuset 1000, Dreb 450 or Drev 800, manufactured by Cytex Co., Rhino 630, Quasar, Hercules Elite, or Cigna Setter, manufactured by Heidel Co., Fuji Photo Film ( Lux Setter RC-5600V or Laxel F
When the same evaluation was performed using either one of -9000 or Panther Pro 62 manufactured by Prepress Co., Ltd., the same effect was obtained with the sample of the present invention.

[Brief description of drawings]

FIG. 1 shows absorption spectra of an emulsion layer side and a back layer side of a photographic light-sensitive material according to an embodiment of the present invention.

[Explanation of symbols]

The vertical axis shows the absorbance (0.1 interval) and the horizontal axis shows 350 nm
To 950 nm. The solid line shows the absorption spectrum on the emulsion layer side, and the broken line shows the absorption spectrum on the back layer side.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
In a characteristic curve shown on an orthogonal coordinate axis containing a surfactant represented by the following general formula (A) and having unit lengths of logarithmic exposure amount (x axis) and optical density (y axis), an optical density of 0.
A silver halide photographic light-sensitive material having a characteristic curve in which a gamma at 3 to 3.0 is 5.0 or more. [Chemical 1] In the formula, R represents a substituted or unsubstituted alkyl group,
_af represents a perfluoroalkylene group. W represents a hydrogen atom or a fluorine atom, and La represents _a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent group formed by combining these. One of A and B is a hydrogen atom and the other is-.
Represents L _b -SO ₃ M, M represents a cation. L _b is
It represents a single bond or a substituted or unsubstituted alkylene group. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the compound of the general formula (A) is a compound represented by the following general formula (B). [Chemical 2] In the formula, R ¹ represents a substituted or unsubstituted alkyl group having 6 or more carbon atoms in total, but R ¹ is not an alkyl group substituted with a fluorine atom. R _f represents a perfluoroalkyl group having 6 or less carbon atoms, ^one of X ¹ and X ² represents a hydrogen atom, the other represents SO ₃ M, and M represents a cation. n represents an integer of 1 or more. 3. The silver halide photographic light-sensitive material according to claim 1, wherein in the general formula (B), R _f is a perfluoroalkyl group having 2 to 4 carbon atoms. 4. The method according to claim 1, which contains a hydrazine compound.
3. The silver halide photographic light-sensitive material as described in any one of 3 above. 5. The silver halide photographic light-sensitive material according to claim 1, wherein the film surface pH on the emulsion layer side is 6.0 or less.