JPH09281627A - Silver halide photographic sensitive material and its processing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material and its processing method such that stable high contrast can be obtd. with a low replenisher amt. of a developer and that pressure fog due to contact friction with various kinds of material can be improved. SOLUTION: This silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer on a supporting body and has at least one protective layer on the emulsion layer. The silver halide emulsion layer is composed of silver halide emulsion particles chemically sensitized by a selenium and/or telluride compd. At least one of the silver halide emulsion layer and/or other hydrophilic colloid layers contain at least one kind of hydrazine deriv., and the outermost layer of a protective layer contains at least one kind of alkylpolysiloxane.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide light-sensitive material, and in a silver halide photographic light-sensitive material having an especially high pressure resistance in an image forming system exhibiting photographic characteristics of ultra-high contrast (in particular, γ is 10 or more). The present invention relates to a material and a processing method thereof.

[0002]

2. Description of the Related Art In the field of graphic arts, an image forming system showing photographic characteristics of ultra-high contrast (especially γ of 10 or more) in order to favorably reproduce a continuous tone image or a line image by a halftone image. is required.
There has been a demand for an image forming system which can develop with a processing solution having good storage stability and obtain ultra-hard photographic characteristics. One of them is U.S. Pat. Nos. 4,166,742 and 4,16.
8,977, 4,221,857, 4,22
4,401, 4,243,739, 4,27
Nos. 2,606 and 4,311,781, a surface latent image type silver halide photographic light-sensitive material containing a specific acylhydrazine compound is added to a sulphite preservative.
A system has been proposed which forms a super-high contrast negative image in which [gamma] exceeds 10 by processing with a developer containing 5 mol / liter or more and having a pH of 11.0 to 12.3. This new image forming system can use only silver chlorobromide with a high silver chloride content in conventional ultra-high contrast image formation, but can also use silver iodobromide and silver iodochlorobromide. There is. Another characteristic is that the conventional squirrel developing solution can contain only a very small amount of a sulfite preservative, but can contain a large amount of a sulfite preservative, so that it has relatively good storage stability. However, a developer having a pH of 11 or more is easily oxidized by air, is unstable, and cannot withstand long-term storage or use.

Therefore, there has been a demand for a system having ultra-high contrast and good processing stability. For example, JP-A-7-24435
0, JP-A-7-248563, JP-A-7-27095
7, Japanese Patent Application No. 6-66505 and Japanese Patent Application No. 6-25015
9 and the like, a hydrazine compound having a peculiar structure is used, and a promoter is incorporated into the light-sensitive material.
With a developing solution having an H of less than 11.0, a system having an ultrahigh contrast and good processing stability is possible.

On the other hand, by chemically sensitizing a silver halide emulsion with a selenium or tellurium compound, it is advantageous for high contrast in a developing solution having a pH of less than 11.0, but disadvantageous for pressure resistance. became. The silver halide photographic light-sensitive material is a contact portion between various devices and the light-sensitive material during handling such as manufacturing processes such as coating, drying, and processing, and handling such as photographing, development processing, printing, and transportation in projection.
Alternatively, pressure fog often occurs in the light-sensitive material due to contact friction between the light-sensitive material such as dust and fiber dust or contact friction between the photographic light-sensitive materials such as between the surface of the light-sensitive material and the back surface. As a means for improving such a change in concentration due to pressure, a method of incorporating a plasticizer such as a polymer latex or a polyhydric alcohol, a method of reducing the silver halide / gelatin ratio of the silver halide emulsion layer,
Known methods are to thicken the protective layer, to add a lubricant or colloidal silica to the protective layer, and to relax the pressure before reaching the silver halide grains. British Patent No. 738,
No. 618, heterocyclic compounds, Nos. 738,637, alkyl phthalates, Nos. 738,689, alkyl esters, and US Pat. No. 2,960,404, polyhydric alcohols. 121,060, carboxyalkyl cellulose, JP-A-49-5017, paraffin and carboxylate, JP-B-53-28086.
The publication discloses a method using an alkyl acrylate and an organic acid. However, the method of adding a plasticizer reduces the mechanical strength of the emulsion layer, so the amount of the plasticizer used is limited. If the silver halide / gelatin ratio is reduced, the development progress is delayed, and the suitability for rapid processing is impaired. Having.
Polyhydroxybenzene compounds have been introduced into silver halide photographic light-sensitive materials containing hydrazine derivatives for various purposes. US Pat. No. 4,332,108, US Pat. No. 4,385,108, US Pat. 377,634
JP-A-62-21143 discloses a technique for preventing pressure sensitization.

At present, in the printing industry, it is strongly desired to reduce the replenishment amount of the developing solution from the viewpoint of the environment.
However, when the thickness of the protective layer is increased, the maximum concentration is lowered under low replenishment, and therefore, it is necessary to reduce the thickness of the protective layer. At that time, pressure fog becomes a problem, and it has been desired to achieve both performance stability under low replenishment and pressure resistance.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material which can stably obtain a high contrast property under a low replenishment of a developing solution and has improved pressure fog due to contact friction with various substances. It is to provide a material and a processing method thereof.

[0007]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and at least one protective layer above the emulsion layer. In, the silver halide emulsion consists of silver halide emulsion grains chemically sensitized with a selenium and / or tellurium compound, and in at least one layer of the silver halide emulsion layer and / or another hydrophilic colloid layer, This has been achieved by a silver halide photographic light-sensitive material characterized by containing at least one hydrazine derivative and one or more alkylpolysiloxanes in the outermost layer of the protective layer.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula (N). General formula (N)

[0009]

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In the formula, R ₁ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₂ represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group,
Represents an aryloxy group, an amino group or a hydrazino group, G ₁ represents a —CO— group, a —SO ₂ — group, a —SO— group,

[0011]

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Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein both A ₁ and A ₂ are hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

In the general formula (N), the aliphatic group represented by R ₁ is preferably a substituted or unsubstituted linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 1 to 30 carbon atoms. . In the general formula (N), R
_The aromatic group represented by ₁ is a monocyclic or bicyclic aryl group, for example, a benzene ring or a naphthalene ring. The heterocyclic group represented by R ₁ is a monocyclic or bicyclic aromatic or non-aromatic heterocycle, which may be condensed with an aryl group to form a heteroaryl group. Examples thereof include a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring and a benzothiazole ring. R ₁
Are preferably aryl groups. R ₁ may be substituted, and typical examples of the substituent include an alkyl group (including an active methyl group), an alkenyl group, an alkynyl group, an aryl group, a group including a heterocycle, and a quaternized nitrogen atom. A group containing a heterocycle containing, for example, a pyridinio group,
A hydroxy group, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit),
Aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, urethane group, carboxyl group, imide group,
Amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group-containing group, quaternary ammonio group-containing group, mercapto group, (alkyl , Aryl, or heterocycle) thio group,
(Alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group, sulfamoyl group, acylsulfamoyl group, (alkyl or aryl) sulfonylureido group, (alkyl or aryl) sulfonylcarbamoyl group, halogen atom, cyano A nitro group, a phosphoric acid amide group, a group having a phosphate ester structure, a group having an acylurea structure, a group having a selenium atom or a tellurium atom, a group having a tertiary sulfonium structure or a quaternary sulfonium structure.
Preferred substituents are linear, branched or cyclic alkyl groups (preferably having 1 to 20 carbon atoms), aralkyl groups (preferably having 1 to 20 carbon atoms), and alkoxy groups (preferably having 1 to 20 carbon atoms). 20), substituted amino group (preferably having 1 to 20 carbon atoms), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms) ), A ureido group (preferably having 1 to 30 carbon atoms), a carbamoyl group (preferably having 1 to 30 carbon atoms), a phosphoric amide group (preferably having 1 to 30 carbon atoms) and the like. .

In the general formula (N), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 10 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example, a benzene ring. Is included. As the heterocyclic group, at least one nitrogen, oxygen,
And a 5- to 6-membered ring compound containing a sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, a pyridyl group, a pyridinio group, a quinolinio group,
There is a quinolinyl group. Pyridyl or pyridinio groups are particularly preferred. Alkoxy group has 1 to 8 carbon atoms
And the aryloxy group is preferably a monocyclic one, and the amino group is preferably an unsubstituted amino group, or an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a heterocyclic amino group. . R ₂ may be substituted, and preferred examples of the substituent include those exemplified as the substituent of R ₁ . Preferred among the groups represented by R ₂ are hydrogen atom, alkyl group (eg, methyl group, trifluoromethyl group, difluoromethyl group, 2-carboxytetrafluoroethyl group) when G ₁ is —CO— group. Group, pyridiniomethyl group, 3-
Hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (eg, o-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methane) Sulfonamidophenyl group, o-carbamoylphenyl group, 4-cyanophenyl group, 2-hydroxymethylphenyl group, etc.), and particularly preferably a hydrogen atom or an alkyl group. When G ₁ is a —SO ₂ — group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group). Alternatively, a substituted amino group (eg, a dimethylamino group, etc.) and the like are preferable. When G ₁ is a —COCO— group, R ₂ is preferably an alkoxy group, an aryloxy group or an amino group,
In particular, a substituted amino group (eg, 2,2,6,6-tetramethylpiperidin-4-ylamino group, propylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl) -3-pyridinioamino group) is preferred. R ₂ may also be such as to cause a cyclization reaction that cleaves the G ₁ -R ₂ moiety from the residual molecule to form a cyclic structure containing atoms of the -G ₁ -R ₂ moiety. For example, Japanese Patent Application Laid-Open No. 63-2
No. 9751 and the like.

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
A phenylsulfonyl group substituted so as to have a value of 0.5 or more; an acyl group having 20 or less carbon atoms (preferably a benzoyl group or a substituent having a sum of Hammett's substituent constants of -0.5 or more); A benzoyl group or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group; ))). A hydrogen atom is most preferable as A ₁ and A ₂ .

The substituents of R ₁ and R _{2 in} the general formula (N) may be further substituted, and preferred examples thereof include those exemplified as the substituents of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, ...
, Etc. may be substituted multiple times, and preferred examples also include those exemplified as the substituent of R ₁ .

R ₁ or R ₂ of the general formula (N) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inactive to photographic properties, such as an alkyl group, an aralkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group. You can choose from. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (N) may have an adsorptive group adsorbing to silver halide incorporated therein. Examples of such adsorbing groups include alkylthio, arylthio, thiourea, thioamide, mercapto heterocyclic, and triazole groups, which are described in U.S. Pat. Nos. 4,385,108 and 4,459,347; No. 195233, No. 59-200231, No. 59-201045, No. 59-201046, No. 5
Nos. 9-201047, 59-201048, 59
-201049, JP-A-61-170733, and 6
1-270744, 62-948, 63-23
No. 4244, No. 63-234245, No. 63-234
No. 246. These adsorbing groups to silver halide may be precursors. As such a precursor, JP-A-2-285
No. 344.

R ₁ or R ₂ in the general formula (N) may contain a plurality of hydrazino groups as a substituent. At this time, the compound represented by the general formula (N) is a multimer with respect to the hydrazino group. And specifically, for example, JP-A-64-861.
34, JP-A-4-16938, JP-A-5-1970.
The compounds described in No. 91 are mentioned.

Next, in the present invention, a particularly preferred hydrazine derivative will be described. R ₁ is particularly preferably a substituted phenyl group, a ballast group through a sulfonamide group, an acylamino group, a ureido group, or a carbamoyl group, an adsorption group to silver halide, a group containing a quaternary ammonio group,
A group containing a repeating unit of an ethyleneoxy group, alkyl,
It may be substituted with an aryl or heterocyclic thio group, a group capable of dissociating in an alkaline developing solution (carboxyl group, sulfo group, acylsulfamoyl group, etc.), or a hydrazino group capable of forming a multimer. preferable. R ₁ is most preferably a phenyl group substituted with a benzenesulfonamide group, and the substituent of the benzenesulfonamide group preferably has any of the groups described above. G ₁ is preferably a -CO- group or a -COCO- group, and particularly preferably a -CO- group. In R ₂ , G ₁ is -CO-
When it is a group, a hydrogen atom, a substituted alkyl group or a substituted aryl group (the substituent is preferably an electron-withdrawing group or an o-hydroxymethyl group), and when G ₁ is a -COCO- group, a substituted amino group is particularly preferable. preferable.

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

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3]

[0025]

[Table 4]

[0026]

[Table 5]

[0027]

[Table 6]

[0028]

[Table 7]

[0029]

[Table 8]

[0030]

[Table 9]

[0031]

[Table 10]

[0032]

[Table 11]

[0033]

[Table 12]

[0034]

[Table 13]

[0035]

[Table 14]

[0036]

[Table 15]

As the hydrazine derivative used in the present invention, the following hydrazine derivative is preferably used in addition to the above-mentioned ones. The hydrazine derivative used in the present invention can also be obtained by various methods described in the following patents.
Can be synthesized. A compound represented by (Chemical Formula 1) described in JP-B-6-77138.
Compounds described on pages 4 and 4. Compounds represented by the general formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication. JP-A-6
Compounds represented by formulas (4), (5) and (6) described in JP-A-230497, specifically, compounds 4-1 to 4 described on pages 25 and 26 of the same publication. -1
0, compounds 5-1 to 5-42 on pages 28 to 36,
And compounds 6-1 to 6 described on pages 39 and 40.
-7. General formula (1) described in JP-A-6-289520
And compounds represented by formula (2), specifically, compounds 1-1) to 1-17) and 2-1) described on pages 5 to 7 of the same publication. Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. JP-A-6-3139
A compound represented by Chemical Formula 1 described in No. 51, specifically, a compound described on pages 3 to 5 of the same publication. JP-A-7-561
Compounds represented by general formula (I) described in No. 0, specifically, Compounds 1-1 to 1-3 described on pages 5 to 10 of the same publication
8. 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. JP-A-7-10442
Compounds represented by General Formula (H) and General Formula (Ha) described in No. 6, specifically Compounds H-1 to H-44 described on pages 8 to 15 of the same publication. A compound described in Japanese Patent Application No. 7-191007 characterized by having 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) ), General formula (B), general formula (C), general formula (D),
Compounds represented by formulas (E) and (F), specifically, compounds N-1 to N-30 described in the publication. Japanese Patent Application 7
-191007, compounds represented by formula (1), specifically, compounds D-1 to D-5 described in the publication.
5.

The hydrazine derivative 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 cellosolve. It can be used by dissolving it in Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine derivative of the present invention may be added to any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other hydrophilic colloid layer. It is preferably added to the emulsion layer or the hydrophilic colloid layer adjacent thereto.

The addition amount of the hydrazine derivative of the present invention is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol, based on 1 mol of silver halide.
X10 ^{-5 to} 5 × 10 ^-3 mol is most preferred.

The silver halide photographic light-sensitive material of the present invention comprises
It is preferable that the silver halide emulsion layer or other hydrophilic colloid layer contains a nucleation accelerator such as an amine derivative, an onium salt, a disulfide derivative, and a hydroxymethyl derivative. As the amine derivative, for example, JP-A-60-140340, JP-A-62-50829,
62-222241, 62-250439, 62-280733, 63-124045, 6
The compounds described in 3-133145, 63-286840 and the like can be mentioned. The amino derivative is more preferably JP-A-63-124045 and 63-
Compounds having a group capable of adsorbing to silver halide described in JP-A-133145 and JP-A-63-286840, or compounds having a total carbon number of 20 or more described in JP-A-62-222241. As an onium salt,
Ammonium salts or phosphonium salts are preferred. Examples of preferable ammonium salts include JP-A-62-250.
The compounds described in No. 439, No. 62-280733 and the like can be mentioned. Further, examples of preferable phosphonium salts include JP-A-61-167939 and JP-A-6-167939.
The compounds described in 2-280733 and the like can be mentioned. Examples of the disulfide derivative include the compounds described in JP-A No. 61-198147. Examples of hydroxymethyl derivatives include, for example, U.S. Pat. Nos. 4,693,956 and 4,777,118.
No. EP, 231,850, JP-A No. 62-50829 and the like can be mentioned, and a diarylmethanol derivative is more preferable.

As a particularly useful nucleation accelerator, Japanese Patent Application No.
General formulas (IV) to (VII described in No. 103,272)
I) compounds, odorically IV-1 to IV-36, V-1 to
V-22, VI-1 to VI-36, VIII-1 to VIII-41, and the general formula (A) described in the patent.
To (D), odorically A-101 to A-14
7, exemplified compounds A-201 to A-255 can be mentioned. The specific compound examples will be shown below. However, the present invention is not limited to the following compounds.

[0043]

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The optimum addition amount of these compounds varies depending on the kind, but 1.0 × per mol of the hydrazine compound.
It is preferably used in the range of 10 ⁻² mol to 1.0 × 10 ² mol. These compounds are dissolved in a suitable solvent (H ₂ O, alcohols such as methanol and ethanol, acetone, dimethylformamide, methyl cellosolve, etc.) and added to the coating solution. Two or more of these compounds may be used in combination.

In the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention, silver chloride, silver chlorobromide, silver bromide, silver iodochlorobromide or silver iodobromide is used as the silver halide. However, silver chlorobromide and silver iodochlorobromide having a silver chloride content of 50 mol% or more are preferable. Silver iodide content is 3 mol%
Or less, more preferably 0.5 mol% or less. The shapes of silver halide grains are cubic, tetrahedral, octahedral,
Any of an irregular shape and a plate shape may be used, but a cube is preferable. The average grain size of silver halide is preferably 0.1 μm to 0.7 μm, more preferably 0.2 to 0.5 μm,
It is preferable that the coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is 15% or less, more preferably 10% or less, with a narrow particle size distribution. The silver halide grains may have a uniform inner layer and a different surface layer, or may have different layers. The photographic emulsion used in the present invention is described in P.
Chifie et Physique Photographique (Paul by Glafkides
Montel, 1967), GF Dufin, Photographic Emu
lsion Chemistry (The Forcal Press, 1966), V.
Making and Coating Photographic by L. Zelikman et al
It can be prepared using the method described in Emulsion (The Focal Press, 1964) and the like.

As the 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. Method of forming grains in excess of silver ions (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, 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. More preferred are tetra-substituted thiourea compounds.
No. 08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinthione. According to the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and the silver halide used in the present invention is easy to produce. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016, JP-B-48-3689.
No. 5,163,364, a method in which the addition rate of silver nitrate or alkali halide is changed in accordance with the grain growth rate, or a method disclosed in British Patent No. 4,242,44.
No. 5, JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow the solution quickly within a range not exceeding the critical saturation.

The silver halide emulsion of the present invention is chemically sensitized with a selenium and / or tellurium compound. The chemical sensitization method may be used alone or in combination with known methods such as a sulfur sensitization method and a noble metal sensitization method. When used in combination, for example, sulfur sensitizing method and selenium sensitizing method, sulfur sensitizing method and tellurium sensitizing method, gold sensitizing method and selenium sensitizing method, gold sensitizing method and tellurium sensitizing method, Examples thereof include sulfur sensitization method, gold sensitization method and selenium sensitization method, sulfur sensitization method, gold sensitization method and tellurium sensitization method.

Known selenium compounds can be used as the selenium sensitizer used in the present invention. That is, usually, an unstable type and / or an unstable type selenium compound is added, and the emulsion is stirred at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-1.
No. 3489, Japanese Patent Application No. 2-130976, 2-229
Compounds described in JP-A Nos. 300, 3-121798 and the like can be used. In particular, it is preferable to use the compounds represented by formulas (VIII) and (IX) in Japanese Patent Application No. 3-121798.

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 silver halide grains. Regarding the formation rate of silver telluride in a silver halide emulsion, see Japanese Patent Application No.
It can be tested by the method described in No. 146739.
Specifically, US Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patents 235,211 and 1,121,496. No. 1,295,462, No. 1,396,696
No., Canadian Patent No. 800,958, Japanese Patent Application No. 2-333.
No. 819, No. 3-53693, No. 3-131598.
No. 4-129787, J. Chem. Soc. Chem. Comm.
un., 635 (1980), 1102 (1979), 645 (1979), J. Che
m. Soc. Perkin. Trans., 1,2191 (1980), edited by S. Patai, T
he Chemistry of Organic Serenium and Tellurium Com
The compounds described in pounds, Voll (1986) and Vol2 (1987) can be used. In particular, the compounds represented by formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 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 10 ⁻³
Use about moles. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

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. Known compounds can be used as the sulfur sensitizer.Examples include sulfur compounds contained in gelatin, and various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines. Can be used. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ^-5 to 10 ^-3 mol.

Examples of the noble metal sensitizer used in the present invention include gold, platinum and palladium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide. About 10 ^-7 to 10 ^-2 mol per mol of silver halide is used. Can be used.

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 formation of silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method described in European Patent (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, those having chemical sensitization, Those with different conditions) may be used in combination.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention contain at least one metal selected from rhodium, rhenium, ruthenium, osmium and iridium in order to achieve high contrast and low fog. Preferably. This content is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol, more preferably in the range of 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, per mol of silver. Two or more of these metals may be used in combination. These metals can be uniformly contained in the silver halide grains, and those described in JP-A-63-29603, JP-A-2-306236, JP-A-3-167545, and JP-A-4-167545 can be used.
No. 76534, No. 6-110146, Japanese Patent Application No. 4-68
As described in JP-A No. 305 and the like, the particles can be contained in the particles with a distribution.

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 a halogen, amines, oxalate, etc. as a ligand, for example, hexachlorodium (II
I) complex salt, hexabromorhodium (III) complex salt, hexaammine rhodium (III) complex salt, trizalatrodium (II
I) Complex salts and the like. These rhodium compounds are
It is used by dissolving it in water or an appropriate solvent, but it is generally used to stabilize the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.), or halogenation. A method of adding an alkali (for example, KCl, NaCl, KBr, 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.

The addition amount of these rhodium compounds is preferably in the range of 1 × 10 ^-8 mol to 5 × 10 ^-6 mol, and particularly preferably 5 × 10 ^-8 mol to 1 × 1 mol, per mol of silver halide.
0 ^-6 mol. The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. .

Rhenium, ruthenium and osmium used in the present invention are disclosed in JP-A-63-2042 and JP-A-1.
Nos. -285941 and 2-20852 and 2-208
No. 55, etc. in the form of a water-soluble complex salt. Particularly preferred is a six-coordinate complex represented by the following formula. [ML _6] ^- _n wherein M represents Ru, Re or Os,, n is 0,
Represents 1, 2, 3 or 4. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Preferred ligands include halide ligands, cyanide ligands, cyanide ligands, nitrosyl ligands, thionitrosyl ligands, and the like. 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 (CN) ₆ ] ^-4 (Ru (CO) ₃ Cl ₃ ) ^-2 (Ru (CO) Cl ₅ ) ^-2 (Ru (CO) Br ₅ ) ^-2 (OsCl ₆ ) ^-3 (OsCl ₅ (NO)) ^-2 [O (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 to 1 × 10 ⁻⁵ mol is preferable, and the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol is particularly preferable. The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. . To incorporate these compounds into the silver halide grains by adding them during the formation of silver halide grains, a metal complex powder or Na
A method in which an aqueous solution dissolved together with Cl and KCl is added to a water-soluble salt or a water-soluble halide solution during grain formation, or a silver salt is added as a third solution when the halide solutions are simultaneously mixed. There are a method of preparing silver halide grains by a three-liquid simultaneous mixing method, a method of charging a necessary amount of an aqueous solution of a metal complex into a reaction vessel during grain formation, and the like. In particular, a method in which a powder or an aqueous solution dissolved together with NaCl and KCl is added to a water-soluble halide solution is preferable. To add to the surface of the particles, a necessary amount of an aqueous solution of the metal complex may be added to the reaction vessel immediately after the particles are formed, or during or after physical ripening, or at the time of chemical ripening.

As the iridium compound used in the present invention, various compounds can be used, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalliteridium, hexacyanoiridium and the like.
These iridium compounds are used after being dissolved in water or a suitable solvent. However, a method generally used to stabilize the solution of the iridium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, bromic acid, hydrofluoric acid) is used. Etc.) or alkali halides (eg KCl,
NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide.

The silver halide grains in the present invention may be doped with another heavy metal salt. In particular, K ₄ [Fe (C
N) ₆ ] is advantageously performed. Further silver halide grains used in the present invention, cobalt, nickel, palladium, platinum, gold, thallium, copper,
It may contain metal atoms such as lead and chromium. The amount of the metal is preferably 1 × 10 ^-9 to 1 × 10 ^-4 mol per mol of silver halide. In addition, in order to contain the above metal, a single salt,
It can be added as a double salt or a metal salt in the form of a complex salt when the particles are prepared.

As the alkali polysiloxane contained as a slip agent in the protective layer of the light-sensitive material of the present invention, an alkyl polysiloxane represented by the general formula (S) is preferably used. General formula (S)

[0063]

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In the formula, R ₁ represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, and R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom, an aliphatic group or an aryl group. . Here, the aliphatic group preferably represents an alkyl group, a cycloalkyl group, an alkoxyalkyl group, an arylalkyl group, an aryloxyalkyl group or a glycidyloxyalkyl group. n and m represent an integer of 0 to 2500. More preferably, R _{1 to} R ₅ represent a methyl group. Among the compounds of general formula (S), those having a kinematic viscosity of 1 or more and 10000 or less are preferable. Particularly preferably, it is 5 or more and 5000 or less. The kinematic viscosity (υ) here is expressed by the equation υ = η / ρ. In the formula, η at 25 ° C. represents the viscosity of the fluid, and ρ represents the density. The coating amount of the slip agent of the present invention is 0.01 to 1.0, preferably 0.05 to 1.0 by weight ratio with respect to the outermost binder layer. Especially 0.01-
It is preferably 0.2 g / m ² . In the light-sensitive material of the present invention, when the protective layer is composed of two or more layers, it is preferable that the outermost layer thereof contains at least one alkylpolysiloxane.

The method of adding the slip agent of the present invention may be any method, but it is usually added to the coating solution for the outermost layer as it is, or if it is insoluble in water, it is dissolved in an organic solvent in advance and added. Alternatively, it may be prepared in advance as a dispersion in an aqueous dispersion or a hydrophilic colloid solution and added to the outermost layer coating solution. When used as a dispersion, it is preferable to use various surfactants as a dispersant to form a fine dispersion. Preferred dispersants are dodecylbenzene sulfonic acid, p-nonylphenoxybutane sulfonic acid, α-sulfosuccinic acid dioctyl ester or N.
-Methyl oleoyl taurine and other sodium salts. Examples of the organic solvent include alcohols (eg, methanol, ethanol, propanol, etc.), esters (eg, acetic acid methyl, ethyl, butyl ester, formic acid methyl, ethyl, propyl ester, etc.),
Examples thereof include amides (dimethylformamide, dimethylacetamide, etc.). When the slip agent is dispersed, it is better to use a hydrophilic colloid, and gelatin is particularly effectively used. As a dispersion method, for the hydrophilic colloid layer, using a supersonic liquid homogenizer or a pulp homogenizer in the presence of a suitable dispersant,
It is preferable to disperse so that the particle size is 0.05 to 10 μm.

Specific examples of the slip agent used in the present invention are shown below, but the present invention is not limited thereto. a) Silicone oil KF- manufactured by Shin-Etsu Chemical Co., Ltd.
96L 1.0 b) Shin-Etsu Chemical Co., Ltd. silicone oil KF-
96 10 c) Shin-Etsu Chemical Co., Ltd. Silicone oil KF-
96 100 d) Shin-Etsu Chemical Co., Ltd. Silicone oil KF-
96 1000 e) Silicone oil KF- manufactured by Shin-Etsu Chemical Co., Ltd.
96 3000 f) Shin-Etsu Chemical Co., Ltd. Silicone oil KF-
96H 10000 g) Shin-Etsu Chemical Co., Ltd. Silicone oil KF-
410

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[0068]

[Chemical 6]

[0069]

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[0070]

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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. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hexoxonol dye, and the like can be used. Useful sensitizing dyes used in the present invention are described, for example, in RESEARCH DISCLOSURE Item 17643 IV-A (Dec. 1978, p. 23) and Item 1831X (Aug. 1979, p. 437). Has been described. 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, A) for an argon laser light source, (I) -1 to (I)-described in JP-A-60-162247.
No. 8, compound I-1 to I-28 described in JP-A-2-48653, compound I-1 to I-13 described in JP-A-4-330434, U.S. Pat.
Compounds of Example 1 to Example 14 described in No. 331,
Compounds 1 to 7 described in West German Patent 936,071,
B) Compounds I-1 to I-38 described in JP-A-54-18726 and I-1 to I-3 described in JP-A-6-75322 for a helium-neon laser light source.
5 and I described in JP-A-7-287338.
-1 to I-34, C) Dyes 1 to 20 described in JP-B-55-39818 and I-1 to I-37 described in JP-A-63-284343 for an LED light source.
Compound and I-described in JP-A-7-287338.
1 to I-34, D) semiconductor laser light sources, compounds I-1 to I-12 described in JP-A-59-191032, and I-1 described in JP-A-60-80841. To the compound I-22, JP-A-4-335342
Compounds I-1 to I-29 described in
Compounds I-1 to I-18 described in JP-A No. 9-192242, E) a tungsten and xenon light source of a plate-making camera are represented by the general formula [I] described in JP-A-55-45015 ( 1) to (19), compounds I-1 to I-97 described in Japanese Patent Application No. 7-346193 and 4-A to 4 described in JP-A-6-242547.
Compounds of -S, compounds of 5-A to 5-Q, compounds of 6-A to 6-T and the like are advantageously selected.

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, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. 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
Section J on page 3, IV, or the aforementioned JP-B-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. 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. Solvents of tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide, alone or It may be dissolved in a mixed solvent and added to the emulsion. Also,
As disclosed in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is dispersed in an emulsion. To Japanese Patent Publication Nos. 44-23389 and 4
As disclosed in 4-27555, 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 coexistent to be added as an aqueous solution to the emulsion. Method, U.S. Pat. No. 3,822,135,
A method of adding an aqueous solution or colloidal dispersion in which a surfactant coexists into an emulsion as disclosed in Japanese Patent No. 4,006,025 and the like, JP-A-53-
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-102733 and JP-A-58-105141, and JP-A-51-746.
As disclosed in No. 24, it is also possible to use a method of dissolving a dye using a compound which causes red shift and adding the solution into an emulsion. Also, ultrasonic waves can be used for the solution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention at any step of emulsion preparation which has been found to be useful so far. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, and JP-A-58-184142.
As disclosed in the specifications of JP-A No. 60-196,749, the start of chemical ripening during the silver halide grain forming step and / or before the desalting, during the desilvering step and / or after the desalting. Previous period, Japanese Patent Application Laid-Open No. 58-113920
As disclosed in the specification of JP-A No. 195/1992, it may be added at any time during the process immediately before or during chemical ripening, at any time after the chemical ripening and before coating until the emulsion is coated. . No. 4,225,666.
As disclosed in the specification of JP-A-58-7629 and the like, the same compound may be used alone or in combination with a compound having a different structure, for example, during grain formation step and chemical ripening step or completion of chemical ripening step. It may be added dividedly, for example, after the chemical aging, or before the chemical aging or during the process and after the completion, or the compound and the combination of the compounds may be added in different types. Good.

The addition amount of the sensitizing dye of the present invention varies depending on the shape, size, halogen composition, method and degree of chemical sensitization of silver halide grains, kind of antifoggant and the like, but per mol of silver halide. It can be used at 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol. For example, when the size of the silver halide grains is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains. An addition amount of 0.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

Gelatin is preferably used as the binder of the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, but other hydrophilic colloids can be used, and they can be used in combination with gelatin. You can also For example, gelatin derivatives, graft polymers of gelatin and other polymer compounds, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate and starch derivatives, polyvinyl. Multiple synthetic hydrophilic polymer substances such as alcohols, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. are used. be able to. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used. In the present invention, the coating amount of gelatin as a binder is such that the amount of gelatin in the entire hydrophilic colloid layer on the side having the silver halide emulsion layer is 3 g / m ² or less (preferably 1.0 g / m ^2).
˜3.0 g / m ² ) and the total amount of gelatin in the total hydrophilic colloid layer on the side having the silver halide emulsion layer and the total hydrophilic colloid layer on the opposite side is 6.0 g / m ² or less. , Preferably 2.0 to 6.0 g / m ² .

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%, more preferably 90 to 1%.
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. After immersing in water for 1 minute, the swollen thickness (Δd) was measured, and the swelling ratio (%) = Δ
It is calculated by the following formula: d ÷ d ₀ × 100.

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.

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

Polyhydroxybenzene compounds described in JP-A-3-39948, page 10, lower right line, line 11 to page 12, lower left line, line 5. Specifically, 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, compound I-
Compounds 1 to I-26.

Antifoggants described in JP-A-2-103536, page 17, lower right, line 19 to page 18, upper right, line 4;

Polymer latices described in JP-A-2-103536, page 18, lower left line 12 to lower left line 20, same page.

Matting agents, slip agents and plasticizers described in JP-A-2-103536, page 19, upper left line 15 to page 19, upper right 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 on page 2, lower right line 2 to page 10, lower right line, and the 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 described in JP-A-2-294638 and Japanese Patent Application No. 3-185773.

JP-A-2-12236, page 9, upper right corner 7
The surfactant described in the third line from the line on the lower right side of the same page. JP 2
PEG-based surfactants described in JP-A-103536, page 18, lower left line, line 4 to lower left line, line 7; JP-A-3-399
No. 48, page 12, lower left line, line 6 to page 13, lower right line, line 5 fluorine-containing surfactants. Specifically, compounds VI-1 to VI-15 described in the publication.

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

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

Hereinafter, processing agents such as a developer and a fixing solution and a processing method in the present invention will be described. However, needless to say, the present invention is not limited to the following description and specific examples.

For the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used.

The developer used in the present invention (hereinafter, both the development starting solution and the development replenisher are collectively referred to as a developer).
The developing agent used for (1) is not particularly limited, but preferably contains dihydroxybenzenes, ascorbic acid derivatives, and hydroquinone monosulfonic acid salts, and may be used alone or in combination. Further, in terms of developing ability, dihydroxybenzenes and ascorbic acid derivatives and 1-phenyl-3-
Combinations of pyrazolidones or combinations of dihydroxybenzenes and ascorbic acid derivatives with p-aminophenols are preferred. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone and methylhydroxine, and hydroquinone is 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 and the like as p-aminophenol-based developing agents used in the present invention. Among them, N-methyl-p-aminophenol is preferable.

The dihydroxybenzene type developing agent is usually preferably used 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 used in an amount of 0.05 mol / l to 0.6 mol / l, preferably 0.23 mol / l. It is preferable to use 0.5 to 0.5 mol / l and the latter in an amount of 0.06 mol / l or less, preferably 0.03 to 0.003 mol / l.

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

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.). These specific examples are shown below, but the present invention is not limited thereto. As a buffer used in the developer when developing the photosensitive 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), tertiary phosphorus Acid salts (eg, sodium salt, potassium salt) and the like are used, and preferably, carbonate and boric acid are used. The amount of buffer, especially carbonate, used is preferably at least 0.1 mol / l, in particular 0.2 to 1.5 mol / l.

Examples of the preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. Sulfite is more than 0.2 mol / l, especially 0.3
It is used in an amount of at least mol / l, but if it is added in too large an amount, it causes silver contamination in the developing solution.
Desirably, it is mol / liter. Particularly preferably,
0.35-0. Mol / l. As the preservative of the dihydroxybenzene-based developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite. Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably 0.05 to 0.10. In molar ratio to the dihydroxybenzene-based developing agent. 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,
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and 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, mercapto compounds, indazole compounds, benzotriazole compounds, and benzimidazole compounds can be used as antifoggants or black pepper.
It may be contained as an inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2- Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4 -Thiadiazole-2
-Thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. The amount of these additives is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of the developer.

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 and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids 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, acyelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, 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, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid,
1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, etc.
Compounds described in 5-67747, 57-102624, and JP-B-53-40900 can be exemplified.

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) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. In addition to the above, Research Disclosure 18170 and JP-A-57-20855.
4, ibid 54-61125, ibid 55-29883, ibid 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 and 55-40.
25, 55-126241, 55-65955, 55-69556 and the above-mentioned Research Disclosure 18170.

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

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-4-362942
And triazines having at least one mercapto group (for example, Japanese Patent Publication No. Hei 6-23830,
282457, compounds described in JP-A-7-175178), and pyrimidines (eg, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-diamino-2,4-dimercapto) Pyrimidine, 2,4,6-trimercaptopyrimidine and the like pyridine (for example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,5-dimercaptopyridine, 2,4,6-trimercaptopyridine, The compounds described in Kaihei 7-248587) and the same pyrazines (eg, 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-dimercaptopyridazine, 3,4,6-trimercaptopyridazine, etc.), compounds described in JP-A-7-175177, polyoxyalkyl phosphonates described in U.S. Pat. be able to. These silver stain inhibitors can be used alone or in combination of two or more, and the addition amount is preferably 0.05 to 10 mmol, more preferably 0.1 to 5 mmol, per liter of the developer. Further, 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 preferable pH of the developer is 9.0 to 12.0.
And more preferably less than 11.0 (particularly preferably 9.5 or more and less than 11.0). As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, 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. Furthermore, when storing as a concentrated solution, the potassium salt is preferred because of its high solubility. However,
In the fixer, potassium ions inhibit fixation to the same extent as silver ions, so if the potassium ion concentration in the developer is high, the potassium ion concentration in the fixer will increase due to the developer being brought in by the photosensitive material. Is not preferred. From the above, it is preferable that the molar ratio of potassium ion to sodium ion in the developer is 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 replenishment amount of the developing solution is 3 per 1 m ² of the light-sensitive material.
It is 90 ml or less, preferably 325 to 30 ml, and most preferably 180 to 120 ml. The development replenisher has the same composition and //
Alternatively, it may have a concentration, or may have a composition and / or concentration different from that of the starting solution.

Ammonium thiosulfate, sodium thiosulfate, and ammonium ammonium 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 is generally about 0.7 to 0.7.
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 hardening agent, and the water-soluble aluminum salt is preferable. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are 0.01 to 0.1 as the aluminum ion concentration in the used liquid.
It is preferably contained at 5 mol / l. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts including a hardening agent or the like as a separate part, or may be a one-part composition including all components.

Preservatives such as sulfites, bisulfites, metabisulfites, etc.
15 mol / l or more, preferably 0.02 mol / l to 0.3 mol / l), pH buffer (for example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogencarbonate, phosphoric acid, succinic acid, adipic acid, etc.) 0.1
Mol / l to 1 mol / l, preferably 0.2
Mol / l to 0.7 mol / l), a compound having an aluminum stabilizing ability or a 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, tiron, ascorbic acid, glutaric acid, aspartic acid,
Glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and their derivatives and their salts, saccharides,
0.001 mol / liter to 0.5 mol / boric acid
Liter, preferably 0.005 mol / l to 0.
3 mol / l).

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 surfactants, and JP-A-57-6840.
The amphoteric surfactants described above can be used, and known antifoaming agents can also be used. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681, JP-B-45-35754, JP-B-58-122535, and JP-B-58-1.
22536, thiourea derivatives, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat.
739, ibid. 1-159645 and ibid. 3-101728.
And the mesoionic compound and thiocyanate described in 4-1-170539.

The pH of the fixing solution in the present invention is 4.0 or higher, preferably 4.5 to 6.0. In the fixer, the pH rises due to the mixing of the developer with the processing, but in this case,
It is 6.0 or less, preferably 5.7 or less for a hardened fixer, and 7.0 or less, preferably 6.0 or less for a non-hardened fixer.
7 or less.

The replenishing amount of the fixing solution is 5 per 1 m ² of the light-sensitive material.
The amount is 00 ml or less, 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 and used by a known fixing solution recycling method such as electrolytic silver recovery. As a reproducing apparatus, for example, there is a Reclaim R-60 manufactured by Fuji Hunt. It is also preferable to remove dyes and the like by using an adsorption filter made of activated carbon or the like.

The light-sensitive material that 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.). Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing solution. The replenishment amount is generally about 17 liters to about 8 liters per 1 m ² of the light-sensitive material, but the replenishment amount can be smaller. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. If washing with a low replenishment volume,
It is more preferable to provide a washing tank for squeeze rollers and crossover rollers described in JP-A Nos. 63-18350 and 62-287252. Various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

As a method of reducing the replenishment amount of water washing, a multi-stage countercurrent system (for example, two-stage, three-stage) has been known for a long time, and the replenishment amount of water washing is 200 to 50 per 1 m ² of the light-sensitive material.
Milliliters are 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 using countercurrent).

Further, a means for preventing water stain may be added to the washing step by the method of the present invention. As the scale prevention means, known means can be used, and there is no particular limitation. There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. In addition to the oxidizing agents described above, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxide (for example,
-Mercaptopyridine-N-oxide, etc.) and may be used alone or in combination of two or more. As a method for energizing, Japanese Patent Application Laid-Open Nos.
7, 4-16280, 4-18980 and the like.

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

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 (eg, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramics), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain biochemical oxygen demand. Amount (BO
D) Compounds that reduce the chemical oxygen demand (COD), iodine consumption, etc. before draining, or filters that use a polymer having affinity for silver, or compounds that form poorly soluble silver complexes such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment that the silver concentration in the wastewater is reduced by, for example, adding silver to precipitate silver and filtering 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.
JP-A-132435, JP-A-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. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, antifungal agents, alkanolamines and surface active agents. 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.

It is preferable to incinerate the waste liquid of the developing solution, the resting solution, the washing water and the stabilizing solution used in the present invention. These waste liquids are, for example, Japanese Patent Publication No. 7-83867, U.S. Pat.
It is also possible to concentrate and liquefy or solidify with a concentrating device as described in S5439560 and the like for disposal.

When the replenishing 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. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and are simply referred to as roller transport type automatic developing machines in this specification. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. further,
A rinsing bath may be provided between development and fixing and / or between fixing and washing with water.

In the development processing of the present invention, dry to dry is 25
~ 160 seconds is preferable, development and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each solution is 25 to 50 ° C.
Is preferable, and 30 to 40 ° C. is preferable. The washing temperature and time are preferably 0 to 50 ° C. and 40 seconds or less. According to the method of the present invention, the photosensitive material which has been developed, fixed and washed with water may be squeezed with washing water, that is, dried 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 surrounding conditions. Any known drying method can be used, and there is no particular limitation. However, hot air drying, JP-A-4-15534, and JP-A-5-22-22 can be used.
56 and 289294, heat roller drying, drying by far infrared rays, and the like, and a plurality of methods may be used in combination.

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 liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water with respect to 1 part of the concentrated liquid so as to have a predetermined concentration.

Although the development processing agent and the fixing processing agent in the present invention can obtain the same results as the liquid agent even when they are solid, the description of the solid processing agent will be given below. The solid preparation in the present invention may be in a known form (powder, granule, granule, lump, tablet, compactor, briquette, plate, rod, paste, etc.). These solid agents may be coated with a water-soluble coating agent or film to separate components that react with each other upon contact, or may separate components that react with each other in a multilayer structure. These may be used in combination.

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

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

The bulk density of the solid processing agent is 0.5 to 6.0 g / cm.
³ are preferred, particularly tablets preferably 1.0 to 5.0 g / cm ^3, the granules is 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-62-259921, JP-A-4-15641, JP-A-4-16841, JP-A-4-32837, and JP-A-4-7884.
8, 5-93991, JP-A-4-85533, 4-
85534, 4-85535, 5-134362,
5-197070, 5-204098, 5-22
4361, 6-138604, 6-138605,
Reference may be made to Japanese Patent Application No. 7-89123.

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 in 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, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material of 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 shape, a cylindrical shape, or a box shape. Also, Japanese Patent Laid-Open No. 6-242 is disclosed.
85-the same 6-242588, the same 6-247432, the same 6
-247448, Japanese Patent Application No. 5-30664, and Japanese Patent Application Laid-Open No. 7-5
It is also preferable to make the foldable shape as disclosed in 664 and 7-5666 to 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 known methods can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and a dissolving device having a dissolving portion and a portion for storing a completed solution as described in Japanese Patent Application No. 7-235499. Dissolve in
Method of replenishing from stock section, JP-A-5-11945
No. 4, 6-19102, and No. 7-261357, a method of adding a processing agent to the circulation system of an automatic developing machine to dissolve and replenish it, and processing a photosensitive material with an automatic developing machine having a dissolution tank. Depending on the method, a treatment agent may be added and dissolved, and any other known method may be used. Also, the treatment agent may be charged manually,
The solvent may be automatically opened and automatically charged by a dissolving agent apparatus having an opening mechanism as described in Japanese Patent Application No. 7-235498 or an automatic processor, and the latter is preferable from the viewpoint of working environment. More specifically, a method of piercing through the outlet, a method of peeling, a method of cutting out, a method of pushing out, and a method described in JP-A-6-19102, 6
-95331.

[0138]

EXAMPLES The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited to these examples.

Example 1 <Preparation of emulsion N-1> 1-liquid water 650 ml gelatin 20 g sodium chloride 2.4 g 1,3-dimethylimidazolidine-2-thio 16 mg sodium benzenesulfonate 6.4 mg 2-liquid water 576 ml silver nitrate 150 g 3-liquid water 517 ml Sodium chloride 34 g Potassium bromide 31 g Ammonium hexachloroiridium (III) 125 ml (0.001% aqueous solution) Potassium hexachlororhodium (III) 6 ml (0.001% aqueous solution)

90% each of the 2nd and 3rd liquids were simultaneously added to the 1st liquid kept at 42 ° C. and pH 4.5 for 20 minutes with stirring to form core particles. Subsequently, the following 4 solutions and 5 solutions were added over 8 minutes, and then 2 and 3 solutions were added.
The remaining 10% of the liquor was added over 2 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4-liquid water 200 ml Silver nitrate 50 g 5-liquid water 200 ml Sodium chloride 13 g Potassium bromide 10 g Potassium hexacyanoferrate (II) (0.1% aqueous solution) 10 ml

After that, 3 g of Compound A was used per 1 mol of silver, followed by washing with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH 5.7, pAg adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide (selenium sensitizer) 1.5 mg, sodium benzenethiosulfonate 8
mg and 2 mg of sodium benzenesulfinate were added and chemically sensitized at 55 ° C. so as to obtain the optimum sensitivity. Further, as a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-
100 mg of tetrazaindene, phenoxyethanol as a preservative, and finally containing 70 mol% of silver chloride,
A silver chloroiodobromide cubic emulsion A having an average grain size of 0.25 μm was obtained. <Preparation of coating sample> Emulsion A with sensitizing dye 3.8 × 10 ⁻⁴
Spectral sensitization was performed by adding mol / mol Ag. Further KB
r3.4 × 10 ⁻⁴ mol / mol Ag, compound 3.2 × 1
0 ⁻⁴ mol / mol Ag, compound 8.0 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol A
g, citric acid 3.0 × 10 ⁻³ mol / mol Ag, compound 1.0 × 10 ⁻⁴ mol / mol Ag, compound 6.0 ×
10 ⁻⁴ mol / mol Ag, 200 mg / m ^{2 of} a water-soluble latex represented by Compound C, and 2% methyl acrylate.
-200 mg of latex copolymer of acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoxyethyl methacrylate (weight ratio 88: 5: 7)
m ² , 200 mg / m ^{2 of} polyethyl acrylate dispersion,
20 wt% of colloidal silica having a particle diameter of 10 mμ was added to gelatin, and 4 wt% of a compound was added to gelatin. The pH of the solution was adjusted to 5.6 with citric acid. A thickness of 10 is obtained by applying the undercoat layer first layer and the second layer on both sides thereof, as described in Example 1 of JP-A-6-317866.
Ag3.7g / m ² on a polyester support 0Myu, was applied so as to gelatin 1.6 g / m ^2. A protective layer upper layer and a protective layer lower layer having the following compositions were coated thereon, and a UL layer having the following composition was coated thereunder. Protective layer Upper layer Gelatin 0.3 g / m ² Phenoxyethanol 100 ppm (per coating solution) Silica matting agent with an average of 3.5 μm 25 mg / m ² Sliding agent (gelatin dispersion) in Table 9 50 mg / m ² Colloidal with a particle size of 10 to ²⁰ μm Silica 30 mg / m ² compound 5 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² compound 20 mg / m ² compound B Added so that the viscosity was 15 cp. Protective layer Lower layer Gelatin 0.5 g / m ² Phenoxyethanol 100 ppm (per coating solution) Compound 15 mg / m ^2, 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² Polyethyl acrylate latex 150 mg / m ² Compound B Viscosity 20 cp Was added. UL layer Gelatin 0.5 g / m ² phenoxyethanol 100 ppm (per coating solution) Polyethyl acrylate latex 150 mg / m ² compound 40 mg / m ² compound (10) 10 mg / m ² compound B It was added so that the viscosity was 30 cp.

The support of 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 Phenoxyethanol 100 ppm (per coating solution) Sodium dodecylbenzenesulfonate 80 mg / m ² Compound (11) 40 mg / m ² Compound (12) 20 mg / m ² Compound (13) 90 mg / m ² 1 , 3-divinylsulfonyl-2-propanol 60 mg / m ² polymethylmethacrylate fine particles (average particle size 5.0 μm) 30 mg / m ² compound 120 mg / m ² compound B Added so that the viscosity was 25 cp. Conductive layer Gelatin 0.1 g / m ² Phenoxyethanol 100 ppm (per coating solution) Sodium dodecylbenzene sulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 200 mg / m ² Compound B viscosity Was 30 cp.

[0143]

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[0144]

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[0145]

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<Exposure / Development Processing> (1) Evaluation of Photographic Performance The above sample was exposed to xenon flash light having an emission time of 10 ⁻⁴ sec through a step wedge through an interference filter having a peak at 633 nm to obtain a Fuji photographic film. Using an FG-680AG automatic developing machine manufactured by Co., Ltd., development (3
(5 ° C., 30 seconds), fixing, washing with water, and drying. As the developing solution and the fixing solution, the developing solution and the fixing solution having the following compositions were used.

Developer Formulation (Developer A) Potassium hydroxide 40.0 g Diethylenetriamine / pentaacetic acid 2.0 g Potassium carbonate 60.0 g Sodium metabisulfite 70.0 g Potassium bromide 7.0 g Hydroquinone 40.0 g 5-Methylbenzo Triazole 0.35 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g 2-mercaptobenzimidazole-5-sodium sulfonate 0.3 g 3- (5-mercaptotetrazol-1-yl) benzene Sodium sulfonate 0.1 g Sodium erythorbate 6.0 g Diethylene glycol 5.0 g pH 10.65

Fixer Formula (Fixer A) Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulphate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 Add water to 3 liters

The sensitivity is shown by the relative value of the reciprocal of the exposure amount that gives a density of 1.5, and the higher the value, the higher the sensitivity. As the index (γ) representing the contrast of the image, the point of fog + density 0.3 on the characteristic curve is fog + density 3.
The points of 0 were connected by a straight line, and the slope of the straight line was represented as a γ value. That is, γ = (3.0−0.3) / [log (exposure amount giving density 3.0) −log (exposure amount giving density 0.3)], and the higher the γ value, the harder the photograph. It is a characteristic. (2) Evaluation of Pressure Fog Under the conditions of 25 ° C. and 60% RH, the load was changed with a polystyrene material and the surface of the sample was rubbed, and then development processing was carried out, and evaluation was carried out in five stages. "5" represents the best level without the occurrence of pressure fog, and "1" represents the worst level of pressure fog and represents the worst quality. “3” is the limit level at which the occurrence of pressure fog is practically allowable. (3) PD (actual skill density) Here, the term “actual skill density” means that a SG-608 (manufactured by Dainippon Screen Co., Ltd.) is used to output a 175 lpi test pattern to the above sample, and the 49% halftone dot of the test pattern is The solid density at the exposure amount (current value) that completed 49% on the sample was defined as the practical density PD. (4) Evaluation of running stability Fatigue liquid A-1 Fuji Photo Film Co., Ltd. automatic processor FG-680AG
The developer A and the fixer A described above are put in the
The replenishment amount per m ² is 160 mL for the developer and 26 for the fixer.
Treated with 0 mL. At this time, the temperatures of the developing solution and fixing solution were 35 ° C. and 34 ° C., respectively, and the developing time was set to 30 seconds. The treatment of 100 m ² per day was performed for 4 days. Fatigue solution A-2 Fuji Photo Film Co., Ltd. automatic processor FG-680AG
The developer A and the fixer A described above are put in the
The replenishment amount per m ² is 160 mL for the developer and 26 for the fixer.
Treated with 0 mL. At this time, the temperatures of the developing solution and the fixing solution were 35 ° C. and 34 ° C., respectively, and the developing time was set to 30 seconds. A treatment of 5 m ² per day was performed for 75 days.

Sample No. Preparation of Sample Nos. 10 and 11 Sample Nos. 10 and 11 were used except that emulsions N-2 and N-3 were used, respectively. Sample No. 10 and 11 were created. Preparation of Comparative Emulsions (N-2, N-3) In order to adjust the sensitivity, the addition amount of potassium hexachlororhodium (III) acid (0.001% aqueous solution) in the three liquids of Emulsion N-1 was adjusted.

Sample No. Preparation of Sample No. 12 except that the compound of the paint sample was removed.
Sample No. 12 was created.

Sample No. Preparation of Sample No. 13 except that a comparative compound (liquid paraffin) was used as a slip agent. Sample N in exactly the same way as 1-7
o. 13 was created.

The results are shown in Table A.

[0154]

[Table 16]

[0155]

[Table 17]

<Results> It can be seen that the samples of the present invention have remarkably improved pressure fog, have ultra-high contrast (γ ≧ 10), and show little variation in sensitivity and gradation even when treated with a fatigue solution.
No. In the sample of which the amount of applied gel of the protective layer is increased from the sample of No. 8, the variations in sensitivity, gradation, and PD in the fatigue solution are large, and No. From the comparison of samples 9 to 11, it can be seen that the adjustment by the sensitivity of the emulsion causes a great loss of sensitivity in order to bring the pressure property to a practical level. No. From the 12 samples, the ultrahigh contrast (γ
It does not become ≧ 10). That is, it is understood that the present invention makes it possible to obtain a silver halide light-sensitive material capable of stably obtaining a high contrast property under a low replenishment of a developing solution and having an improved pressure fog.

Example 2 The photosensitive material prepared in Example 1 was developed under the conditions of Example 1 using the following developing solution B instead of the developing solution A used in Example 1. Developer formulation (processing solution B) Potassium hydroxide 35.0 g Diethylenetriamine / pentaacetic acid 2.0 g Potassium carbonate 40.0 g Sodium metabisulfite 40.0 g Potassium bromide 3.0 g Hydroquinone 25.0 g 5-Methylbenzotriazole 0 0.08 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-1-thioxo-4- (1H) -quinazolinone 0.04 g 2 -Sodium mercaptobenzimidazole-5-sulfonate 0.15 g Sodium erythorbate 3.0 g Diethylene glycol 20.0 g pH 10.5 Fatigue solution B-1 Fuji Photo Film Co., Ltd. automatic processor FG-680A
The developing solution B and the fixing solution B were put in G, and the amount of replenishment per 1 m ^{2 of} the light-sensitive material was 320 mL for both development and fixing. At this time, the temperatures of the developing solution and the fixing solution were 35 ° C. and 34 ° C., respectively, and the developing time was set to 30 seconds. 1
The treatment of 100 m ² per day was performed for 2 days. Further, the same result was obtained even when the fixing solution was subjected to processing with the replenishing amount of fixing fixed at 160 mL per 1 m ² of the light-sensitive material while recovering silver by using Reclaim R-60 manufactured by Fuji Hunt. Fatigue solution B-2 Fuji Photo Film Co., Ltd. automatic processor FG-680A
The developing solution B and the fixing solution B were put in G, and the amount of replenishment per 1 m ^{2 of} the light-sensitive material was 320 mL for both development and fixing. At this time, the temperatures of the developing solution and the fixing solution are each 3
The temperature was 5 ° C. and 34 ° C., and the developing time was set to 30 seconds. The treatment of 5 m ² per day was performed for 40 days. Further, the same result was obtained even when the fixing solution was subjected to processing with the replenishing amount of fixing fixed at 160 mL per 1 m ² of the light-sensitive material while recovering silver by using Reclaim R-60 manufactured by Fuji Hunt. <Results> Even if the developing solution B and the fixing solution B were used, the results of Example 1 were obtained.
The same result was obtained.

Example 3 Similar results were obtained using the following solid processing agents for replenishment of development and fixing. For the dissolution and replenishment of the solid processing agent, a dissolution replenishing device having an automatic opening mechanism for the processing agent packaging material, which is disclosed in Japanese Patent Application Nos. 7-235499 and 7-23598, was used. At this time, the same results were obtained even when the solid processing agent was used as the tank mother liquor. Further, the fixing solution is recovered by silver using Reclaim R-60 manufactured by Fuji Hunt Co., Ltd., and the replenishment amount of fixing is 16 per 1 m ² of the light-sensitive material.
Similar results were obtained when the treatment was performed with 0 mL. The fatigue solution was prepared in the same manner as in Example 1.

The composition of the solid developer is shown below. Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (bulk powder) 63.0 g Sodium sulfite (bulk powder) 46.0 g Potassium carbonate 62.0 g Hydroquinone (briquette) 40.0 g Diethylenetriamine to be briquetted together -Pentaacetic acid 2.0 g 5-methylbenzotriazole 0.35 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g 2-mercaptobenzimidazole-5-sulfonic acid sodium salt 0.3 g 3- ( 5-Mercaptotetrazol-1-yl) Sodium benzenesulfonate 0.1 g Sodium erythorbate 6.0 g Potassium bromide 6.6 g Dissolve this in water to 1 L. pH 10.65

Here, in the raw material form, the bulk powder was used as it was as a general industrial product, and the beads of the alkali metal salt were commercial products. If the raw material is briquette, it is pressed and compressed using a briquetting machine to give an irregular length of 4 to 6
A rugby ball shape having a size of about mm was prepared, crushed and used. For minor components, each component was blended before briquetting. 10 L 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, a dissolution and replenishment device having an automatic opening mechanism disclosed in Japanese Patent Application Nos. 7-235499 and 7-235498 was used. <Results> The same results as in Example 1 were obtained using the above developing solution and fixing solution.

Example 4 A polyester support having a thickness of 175 .mu.m obtained by coating the sample of Example 1 described above with Example 1 of JP-A-6-317866 with a first layer and a second layer of an undercoat layer, and JP-A-6-316. -31
The undercoat layer first layer and second layer described in Example 3 of 7866 were applied on a polyester support having a thickness of 100 μ or 175 μ, which was applied on both sides, to prepare and evaluated under the conditions of Example 1. <Results> The same results as in Example 1 were obtained using the above support.

Example 5 The sample of the above Example 1 was coated on a support shown below to prepare, and evaluated under the conditions of Example 1. [Manufacturing method of support] (1) Preparation of contact product of trimethylaluminum and water In a glass container having an inner volume of 500 ml and purged with argon,
Copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) 17.8 g (71
Millimol), 200 ml of toluene and 24 ml (250 mmol) of trimethylaluminum were added and the reaction was carried out at 40 ° C. for 8 hours. Then, toluene was distilled off under reduced pressure at room temperature from the solution obtained by removing the solid component, and the molecular weight of the contact product was measured by the freezing point depression method.
It was 0. (2) Production of styrene-based polymer In a reaction vessel having an internal volume of 2 liters, 950 ml of purified styrene
And 50 ml of p-methylstyrene, 5 mmol of the catalytically purified product obtained in (1) above as an aluminum atom, 5 mmol of triisobutylaluminum, 0.025 of pentamethylcyclopentadienyl titanium trimethoxide.
Polymerization reaction was carried out at 90 ° C. for 5 hours using mmol. After completion of the reaction, the product was decomposed with sodium hydroxide in methanol to decompose the catalyst component, repeatedly washed with methanol, and dried to obtain 308 g of a polymer. The polymer obtained had a co-syndiotactic structure and a p-methylstyrene unit of 9.
It was confirmed by ¹³ C-NMR that it contained 5 mol%. The weight average molecular weight is 438,000, and the weight average molecular weight /
The number average molecular weight was 2.51.

(3) Production of support The styrene-based polymer obtained in (2) was depressurized at 150 ° C. and dried, and then pelletized by a vented single-screw extruder, and the pellets were heated in hot air at 130 ° C. Crystallized with stirring. The content of styrene monomer in the crystallized pellets was 1,100 ppm. Next, the pellets were extruded by a device having a T-die attached to the tip of an extruder having a filter therein. The melting temperature at this time was 300 ° C. This molten sheet is vertically oriented at 110 ° C for 3.5
The film was stretched 4 times in the transverse direction at 120 ° C. and heat-treated at 240 ° C. for 10 seconds in a fixed tension state for 20 seconds with 5% restricted shrinkage. The thickness of the obtained film was 100 μm, and haze was 1.
It was 0%.

Both sides of the obtained syndiotactic polystyrene (SPS) support were subjected to glow discharge treatment under the following conditions. Four rod-shaped electrodes having a hollow section which becomes a refrigerant channel and has a cylindrical shape with a cross section of 2 cm in diameter and 150 cm in length were fixed in an insulating plate shape at intervals of 10 cm. Fix this electrode plate in the vacuum tank,
15cm away from this electrode surface and face it 2
The axially stretched film was run and the speed was controlled so that surface treatment was performed for 2 seconds. Immediately before the film passes through the electrode, the heating roll is arranged so that the film makes 3/4 round contact with the heating roll with a temperature control of 50 cm, and the thermocouple thermometer is placed on the film surface between the heating roll and the electrode zone. The film surface temperature was controlled at 115 ° C. The pressure in the vacuum chamber was 0.2 Torr, and the partial pressure of H ₂ O in the atmospheric gas was 75%. The discharge frequency was 30 kHz, the output was 2500 W, and the treatment intensity was 0.5 kV · A · min / m ² . Before the support after the discharge treatment was wound up, the support was brought into contact with a cooling roll having a temperature controller having a diameter of 50 cm and wound up so that the surface temperature became 30 ° C. Then, an undercoat layer having the following composition was applied on both sides.

<Undercoat layer> Deionized alkali-treated gelatin (isoelectric point 5.0) 10.0 parts by weight water 24.0 〃 methanol 961.0 〃 salicylic acid 3.0 〃 described in JP-A-51-3619 Example 1 Polyamide-epichlorohydrin resin 0.5 〃 Described in Japanese Examined Patent Publication No. 3-27099 Nonionic surfactant Compound I-13 1.0 〃 This coating solution was applied at 10 ml / m ² using a wire bar,
It was dried at 115 ° C. for 2 minutes and wound up. <Results> Samples of the present invention and comparative samples were prepared in the same manner as in Example 1 except that the above-mentioned support was used, and treated in the same manner as in Example 1, and the same results as in Example 1 were obtained. .

[0166]

As described above, according to the present invention, a silver halide photographic light-sensitive material which can stably obtain a high contrast property under a low replenishment of a developing solution and has improved pressure fog due to contact friction with various substances, and a method thereof. A processing method can be provided.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and at least one protective layer on the emulsion layer,
The silver halide emulsion consists of a silver halide emulsion chemically sensitized with a selenium and / or tellurium compound, and in at least one layer of the silver halide emulsion layer and / or another hydrophilic colloid layer, at least one kind of A silver halide photographic light-sensitive material containing a hydrazine derivative and one or more alkylpolysiloxanes in the outermost layer of the protective layer. 2. A silver halide emulsion layer or at least one other hydrophilic colloid layer contains at least one nucleation accelerator selected from amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives. The silver halide photographic light-sensitive material according to claim 1. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the protective layer is composed of two or more layers, and the outermost layer thereof contains one or more alkylpolysiloxanes. 4. A method of processing a silver halide photographic light-sensitive material, which comprises developing the silver halide photographic light-sensitive material according to claim 1, 2 or 3 with a developer having a pH of less than 11.0.