JP2000181007A - Silver halide photographic sensitive material and its development processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material and its development processing method with little occurrence of stains at development processing by incorporating at least 2 kinds of specified compounds, in at least one silver halide emulsion layer formed on one side of a support. SOLUTION: This photosensitive material has at least one silver halide emulsion layer on one side of the support and contains a compound represented by the formula I: R1-O(CH2CH2O)n1(CH2)n2SO3M1 and the compound represented by formula II. In formulae I and II, R1 is an aromatic or 5-20C aliphatic group; n1 is an integer of 1-20; n2 is an integer of 0-6; M1 is an H or alkali metal atom; each of R11 and R12 is, independently, a 5-30C alkyl group; R13 is an H atom or a -CH2COOR14; R14 is the same as R11 and R12; and M2 is an alkali metal atom or ammonium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-contrast silver halide photographic light-sensitive material suitable for printing plate making and a method for developing a silver halide photographic light-sensitive material for obtaining a high-contrast image.

[0002]

2. Description of the Related Art In the production of silver halide photographic materials (hereinafter simply referred to as "photosensitive materials"), various surfactants are used as spreading agents. However, in recent years, in the trend of low replenishment and speeding up of a processing solution, a surfactant (hereinafter, also referred to as an activator) contained in a photosensitive material has flowed out into the processing solution, resulting in film surface contamination and poor fixing. And so on.

On the other hand, JP-A-5-323523,
JP-A-6-130539 discloses a technique using a sulfoalkylpolyoxyethylene-based activator, but this activator has a problem that defects are apt to occur at the time of coating.

On the other hand, as a photosensitive material used for printing plate making, a photosensitive material having ultra-high contrast photographic characteristics is widely used. To obtain such a high contrast image, US Pat.
9,929, JP-A-60-25837, JP-A-5
As disclosed in JP-A-232616 or the like, a photosensitive material containing a hydrazine derivative can be prepared using an MQ developer (a developer using a combination of p-aminophenols and hydroquinone) or PQ
There is known an image forming method in which processing is performed with a developer (a developer using a combination of 1-phenyl-3-pyrazolidones and hydroquinone). However, in these image forming methods, since hydroquinone is used as a developing agent, ecologically,
Further, there is a concern about unfavorable points in terms of toxicology, and a method for obtaining a high contrast image with a developer containing no hydroquinone has been desired.

On the other hand, US Pat. No. 5,236,816
No. 5,264,323, there is a system using ascorbic acids as a developing agent. However, this system has a drawback that the pH tends to decrease due to development processing and air oxidation, and that the fluctuation of the processing solution is large. In addition, it is necessary to incorporate a developing agent more than necessary in the developing solution or to contain a large amount of carbonate in order to suppress a fluctuation in pH of the developing solution. For this reason, there has been a problem that the salt concentration of the developing solution is increased, and the additives brought in from the photosensitive material are precipitated in the processing solution, adhere as stains, and cause a fixing failure. Therefore, there is a strong need for a photosensitive material having improved stability during coating and stability during processing, and a processing method therefor.

[0006]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a silver halide photographic light-sensitive material which is less contaminated during development and a method for processing a silver halide photographic light-sensitive material which has less influence on the environment. is there.

[0007]

The above object of the present invention is attained by the following constitutions.

(1) On one side of a support, there is provided at least one photosensitive silver halide emulsion layer, which is represented by the following general formula (I)
And a compound represented by the following formula (II):

Formula (I) R ¹ O (CH ₂ CH ₂ O) n ₁
(CH ₂ ) n ₂ SO ₃ M ^{1 In the} formula, R ¹ represents an aromatic group or an aliphatic group having 5 to 20 carbon atoms. n ₁ represents an integer of 1 to 20, n ₂ represents an integer of 0 to 6. M ¹ represents a hydrogen atom or an alkali metal atom.

[0010]

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In the formula, R ¹¹ and R ¹² may be the same or different and represent an alkyl group having 5 to 30 carbon atoms, and R ¹³ represents a hydrogen atom or a —CH ₂ COOR ¹⁴ group. R ¹⁴ has the same meaning as R ¹¹ and R ¹² , and M ² represents an alkali metal atom or an ammonium group.

(2) The silver halide photographic material as described in (1), which contains a hydrazine derivative as a contrast agent.

(3) On one side of the support, there is provided at least one photosensitive silver halide emulsion layer;
A method for developing a silver halide photographic material containing a compound represented by the following formula (A) with a developer containing a developing agent represented by the following general formula (A).

[0014]

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In the formula, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted alkylthio group. R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X is -CO
- or represents a -CS-, each M ₁ and M ₂ represents a hydrogen atom or an alkali metal atom.

(4) The developing method according to (3), wherein the line speed of the automatic developing machine is 1 m / min or more when developing with an automatic developing machine.

Hereinafter, the present invention will be described in more detail.

First, the alkyl (or aryl) polyether sulfonate-based activator represented by the general formula (I) will be described.

N ₁ is an integer of ₁ to 20, preferably 3 to 10 from the viewpoint of applicability.

The aliphatic group represented by R ¹ has 5 to 5 carbon atoms.
20 alkyl groups and alkenyl groups are preferred, and those having 8 to 12 carbon atoms are particularly preferred. The aromatic group represented by R ¹ is preferably a phenyl group substituted with an alkyl group,
Further, it may have a substituent other than the alkyl group.

The amount of the activator represented by the general formula (I) is preferably 0.1 to 10 g, more preferably 0.5 to 5 g per liter of the coating solution. The addition may be made at any time in the photosensitive material production process.

Hereinafter, specific examples of the activator represented by the general formula (I) will be shown.

[0023]

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[0024]

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Next, the sulfosuccinate-based activator represented by the general formula (II) will be described.

The alkyl group represented by R ¹¹ and R ¹² may be linear or branched, and preferably both R ¹¹ and R ¹² have 6 or more carbon atoms, more preferably 8 to 20 carbon atoms.

Even when R ¹³ represents a —CH ₂ C00R ¹⁴ group, it is preferable that all of R ¹¹ , R ¹² and R ¹⁴ have 6 or more carbon atoms.

The amount of the activator represented by the general formula (II) is from 1 × 10 ^-6 to 2 × 10 ^-2 per mol of silver halide.
Mol is preferable, and in particular, the range of 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol is preferable. The addition may be made at any time in the photosensitive material production process.

Hereinafter, specific examples of the activator represented by the general formula (II) will be shown.

[0030]

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[0031]

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The activator may be added at least one hydrophilic colloid layer on each side of the support, for example, a silver halide emulsion layer, a protective layer, an intermediate layer, an undercoat layer, and a backing layer. is there. When any one of the layers has a multilayer structure, any layer may be used, but a surface protective layer is particularly preferable.

In order to incorporate these activators into the above-mentioned photographic constituent layers, aqueous solutions are used when the activators are water-soluble, and alcohols (methanol, ethanol, etc.) and esters (ethyl acetate) are used when the activators are insoluble in water. Etc.) and ketones (acetone, methyl ethyl ketone, etc.) in a water-soluble organic solvent solution.

In a preferred embodiment of the present invention, the high-contrast photosensitive material contains a hydrazine derivative as a high-contrast agent.

Examples of the hydrazine derivative include those represented by the following general formula (H).

[0036]

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In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and G represents-
(CO) _r -group, sulfonyl group, sulfoxy group, -P
(＝ O) represents a R ₁₆ — group or an iminomethylene group, and r is 1
Or an integer of 2, wherein A ₁ and A ₂ are both a hydrogen atom or one is a hydrogen atom, and the other is a substituted or unsubstituted alkylsulfonyl group or a substituted or unsubstituted acyl group, and R is a hydrogen atom; Represents a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group or oxycarbonyl group. R ₁₆ is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group,
Represents an aryloxy group or an amino group.

Of the compounds represented by the general formula (H), those represented by the following general formula (Ha) are more preferred.

[0039]

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In the formula, R ₁₁ represents an aliphatic group (octyl group, decyl group, etc.), an aromatic group (phenyl group, 2-hydroxyphenyl group, chlorophenyl group, etc.) or a heterocyclic group (pyridyl group, thienyl group, furyl group, etc.). And the like, and those further substituted with a suitable substituent are preferably used. Furthermore, it is preferred for R ₁₁ contains at least one ballast group or a silver halide adsorption accelerating group.

As the ballast group, those commonly used in immobile photographic additives such as couplers are preferable, and are relatively inert to photographic properties having 8 or more carbon atoms, for example, alkyl group, alkenyl group, Examples include an alkynyl group, an alkoxy group, a phenyl group, a phenoxy group, and an alkylphenoxy group.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula (Ha), X represents a group that can be substituted with a phenyl group, m represents an integer of 0 to 4, and when m is 2 or more, even if a plurality of Xs are the same, they are different. Is also good.

In the general formula (Ha), A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula (H), and both are preferably hydrogen atoms.

In the general formula (Ha), G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and a carbonyl group is particularly preferred.

R ₁₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, allyl group, heterocyclic group, alkoxy group, hydroxyl group, amino group, carbamoyl group or oxycarbonyl group. Preferable R ₁₂ is a substituted alkyl group in which a carbon atom substituted by G is substituted with at least one electron-withdrawing group, —COOR ₁₃ group, and —CON (R ₁₄ )
(R ₁₅ ) group. R ₁₃ represents an alkynyl group or a saturated heterocyclic group; R ₁₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; and R ₁₅ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group. , A hydroxy group or an alkoxy group. More preferably, it represents a substituted alkyl group substituted by two electron-withdrawing groups, particularly preferably three electron-withdrawing groups. The electron-withdrawing group for substituting the carbon atom substituted with G in R ₁₂ preferably has a σp value of 0.2 or more and a σm value of 0.3 or more, such as a halogen atom, a cyano group, a nitro group, and a nitroso group. Group,
Polyhaloalkyl, polyhaloaryl, alkyl or arylcarbonyl, formyl, alkyl or aryloxycarbonyl, alkylcarbonyloxy, carbamoyl, alkyl or arylsulfinyl, alkyl or arylsulfonyl, alkyl or arylsulfonyloxy Group,
It represents a sulfamoyl group, a phosphino group, a phosphine oxide group, a phosphonate ester group, a phosphonamide group, an arylazo group, an amidino group, an ammonio group, a sulfonio group, or an electron-deficient heterocyclic group.

R _{12 in the} formula (Ha) particularly preferably represents a fluorine-substituted alkyl group (monofluoromethyl, difluoromethyl, trifluoromethyl, etc.).

Specific examples of the compound represented by formula (H) are shown below, but the present invention is not limited thereto.

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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As specific examples of other preferred hydrazine compounds, see US Pat. No. 5,229,248, 4-60.
(1) to (252) described in the column.

These hydrazine compounds can be synthesized by a known method. For example, US Pat.
No. 248, 59-80 column.

The amount of the hydrazine derivative to be added may be an amount which makes the contrast high (the amount of the contrast enhancement). The optimum amount depends on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor and the like. Although different, it is generally in the range of 10 ^-6 to 10 ^-1 mole per mole of silver halide, and 10 ^-5 to 1
0 ^-2 mol is preferred.

The hydrazine derivative is added to at least one layer on the side of the silver halide emulsion layer, and is preferably a silver halide emulsion layer and / or a layer adjacent thereto, more preferably an emulsion layer. The amount of the hydrazine derivative contained in the photographic component layer closest to the support among the hydrazine derivative-containing photographic component layers is 0% of the total amount of the hydrazine derivative contained in the photographic component layer farther from the support. .2
0.8 molar equivalent, preferably 0.4 to 0.6.
Molar equivalents are more preferred. One hydrazine derivative may be used, or two or more hydrazine derivatives may be used in combination.

When the above-mentioned high contrast agent is used in the light-sensitive material to be processed, it is preferable to use a nucleation accelerator to promote the high contrast.

As the nucleation accelerator, a compound represented by the following formula (Na) or (Nb) is preferably used.

[0067]

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In the general formula (Na), R ₂₁ , R ₂₂ and R ₂₃ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an alkynyl group or a substituted or unsubstituted aryl group; R ₂₁ , R ₂₂ ,
R ₂₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds.

These compounds preferably have a diffusion-resistant group or a silver halide adsorbing group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is particularly preferable. Preferred examples of the adsorptive group include a heterocyclic group, a mercapto group, a thioether group, a selenoether group, a thione group, and a thiourea group.

Particularly preferred as the general formula (Na) are compounds having at least one thioether group as a halogen adsorbing group in the molecule.

Specific examples of the nucleation accelerator (Na) are shown below.

[0072]

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[0073]

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[0074]

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[0075]

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In the above formula (Nb), Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₂₄ represents a hydrogen atom, an alkyl group, an alkynyl group or an aryl group, but Ar and R ₂₄ may be linked to form a ring.

These compounds preferably have a diffusion-resistant group or a silver halide adsorbing group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide-adsorbing group include groups having the same meaning as the silver halide-adsorbing group of the compound represented by formula (H).

Specific compounds of the general formula (Nb) include the following.

[0079]

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[0080]

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Specific examples of other preferable nucleation promoting compounds are the compounds (2-1) to (2-20) and 6-2587 described in JP-A-6-258751.
No. 51, (3-1) to (3-6), JP-A-7-27
No. 0957, onium salt compounds described in JP-A-7-104
No. 420, a compound of the formula I, JP-A-2-103536.
No. 19, page 17, lower right column, line 18 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, and thiosulfonic acid compounds described in JP-A-1-237538.

In the present invention, the nucleation accelerator can be used in any of the photographic constituent layers on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. preferable. The optimum amount to be added varies depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor and the like, but is generally from 10 ^-6 to 10 per mol of silver halide. ^-1 mol is preferred,
Particularly, the range of 10 ^-5 to 10 ^-2 mol is preferable.

The halogen composition of the silver halide emulsion used in the light-sensitive material of the present invention is not particularly limited. However, when processing is performed with a small replenishing amount of the processing solution or when rapid processing is performed, silver chloride, 60 mol% or more is used. Silver chlorobromide containing silver chloride,
It is preferable to use a silver halide emulsion composed of silver chloroiodobromide containing 60 mol% or more of silver chloride.

The average grain size of silver halide is 1.2 μm.
m, particularly 0.3 to 0.1 μm
Is preferred. The average particle size is a commonly used and easily understood term in the photographic art. The particle diameter means a particle diameter when the particle is a spherical particle or a particle that can be approximated to a sphere. When the particle is a cubic, it is converted into a sphere, and the diameter of the sphere is defined as the particle diameter. For details of the method for determining the average particle size, see Mies, James, The Theory of the Photographic Process (CE Mees &
T. H. James: The theory of
he photographic process),
Third Edition, pp. 36-43 (1966, Macmillan "Mc
Millan "))).

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

The method of reacting the soluble silver salt with the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. A method in which grains are formed in the presence of excess silver ions (inverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. To obtain a silver halide emulsion having a nearly uniform grain size.

In the present invention, the silver halide emulsion of at least one silver halide emulsion layer contains tabular grains, and 50% of the total projected area of all grains in the emulsion layer in which the tabular grains are used. The above are preferably tabular grains having an aspect ratio of 2 or more. Particularly when the ratio of tabular grains is 60 to 7
More favorable results are obtained as the value is increased to 0% and further to 80%. The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes.

Of these tabular grains, tabular grains having a (100) plane as a main plane and having at least 50 mol% of silver chloride are preferably used, and these are described in US Pat. No. 5,264,3.
No. 37, 5,314,798, 5,320,95
No. 8, etc., and desired tabular grains can be easily obtained. In the tabular grains, silver halides having different compositions can be epitaxially grown or shelled at specific surface portions.

In order to control the photosensitive nucleus, a transition line can be provided on the surface or inside of the tabular grains.
In order to provide a transition line, fine grains of silver iodide can be present during chemical sensitization or can be formed by adding iodine ions.

The preparation of silver halide grains can be appropriately selected from acid methods, neutral methods, ammonia methods and the like. When doping a metal, it is particularly preferable to form particles under acidic conditions of pH 1 to 5.

As a silver halide solvent, for example, ammonia, a thioether, a thiourea compound, a thione compound or the like can be used to control the growth of the grains during the formation of tabular grains. As thioether compounds, 3,6,9,15, described in German Patent 1,147,845
18,21-hexoxa-12-thiatricosan, 3,
9,15-trioxa-6,12-dithiaheptadecane, 1,17-dioxy-3,9-15-trioxa-
6,12-dithiaheptadecane-4,14-dione,
1,20-dioxy-3,9,12,18-tetroxa-6,15-dithiaeicosan-4,17-dione;
7,10-dioxa-4,13-dithiahexadecane-
2,15-dicarboxamide; JP-A-56-94347
And oxathioether compounds described in JP-A-1-121847; JP-A-63-259563 and JP-A-63-30.
And a cyclic oxathioether compound described in No. 1939. Particularly, thiourea is disclosed in JP-A-53-82.
No. 408 are useful, specifically, tetramethylthiourea, tetraethylthiourea, dimethylpiperidinothiourea, dimorpholinothiourea, 1,3-
Examples thereof include dimethylimidazole-2-thione, 1,3-dimethylimidazole-4-phenyl-2-thione, and tetrapropylthiourea.

At the time of physical ripening or chemical ripening, metal salts such as zinc, lead, thallium, iridium, rhodium, ruthenium, osmium, palladium, and platinum can coexist. In order to obtain high illuminance characteristics, iridium is preferably doped in a range of 10 ^<-9> to 10 ^{< -3 >} mol per mol of silver halide. To obtain a high contrast emulsion,
It is preferable to dope rhodium, ruthenium, osmium and / or rhenium in the range of 10 ^-9 to 10 ^-3 mol per mol of silver halide.

When the metal compound is added to the particles, halogen, carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl, phenanthroline or these compounds are added to the metal. It can be coordinated in combination. The oxidation state of the metal can be arbitrarily selected from the highest oxidation level to the lowest oxidation level. Preferred ligands are described in JP-A-2-2082.
No. 2-20853, No. 2-20854, No. 2-
As the hexadentate ligands and alkali complex salts described in No. 20855, there are general sodium salts, potassium salts, cesium salts or primary, secondary and tertiary amine salts. Further, a transition metal complex salt can be formed in the form of an aquo complex. Examples of these are, for example, K ₂ [RuCl ₆ ], (NH ₄ ) ₂
[RuCl ₆ ], K ₂ [Ru (NO) Cl ₄ (SC
N)] and K ₂ [RuCl ₅ (H ₂ O)]. The Ru part can be replaced with Rh, Os, Re, Ir, Pd and Pt.

Rhodium, ruthenium, osmium and / or
Alternatively, the rhenium compound is preferably added during the formation of silver halide grains. As the addition position, there is a method of uniformly distributing the particles, or a method of forming a core-shell structure and localizing a large amount in the core portion or the shell portion.

Often, better results are obtained when a large amount is present in the shell portion. In addition to localization in a discontinuous layer configuration, a method may be used in which the abundance is continuously increased outside the particles. The addition amount is 1 per mol of silver halide.
The range of 0 ^-9 to 10 ^-3 mol can be appropriately selected.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (Rese
arch Disclosure (hereinafter referred to as RD) 1
No. 76, 17643, pp. 22-23 (December 1978)
In the literature cited or cited.

The silver halide emulsion may or may not be chemically sensitized. As a method of chemical sensitization, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. Good.

As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred are sulfur compounds contained in gelatin and various sulfur compounds such as thiosulfates, thioureas and rhodanines. And polysulfide compounds.

Known selenium sensitizers can be used as the selenium sensitizer. For example, US Pat. No. 1,623,4
No. 99, JP-A-50-71325, JP-A-60-1500
Compounds described in No. 46 and the like can be preferably used.

The light-sensitive material may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as tria Benzenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3a, 7-tetrazaindenes), pentazaindenes and the like; benzene Osuruhon acid, benzene sulfinic acid, may be added known many compounds as antifoggants or stabilizers, such as benzenesulfonic acid amide.

It is advantageous to use gelatin as a binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

As the gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

It is particularly preferable to add polysaccharides such as dextran and dextrins described in JP-A-9-304855 in order to improve rapid processing suitability.

The photographic emulsion may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxy acryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (such as vinyl acetate), acrylonitrile, olefin, styrene and the like alone or in combination, or acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid, or the like can be used.

To the photographic emulsion and the non-photosensitive hydrophilic colloid layer, an inorganic or organic hardener is added as a crosslinking agent for a hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-
Methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxy dioxane, etc.), active vinyl compounds (1,
3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N,
N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, phenoxymucochloric acid, etc.) ), Isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activated hardener and the like can be used alone or in combination. These hardeners are RD 176, 1
7643 (published December 1978), pages 26A-C.

Various other additives are used in the light-sensitive material. For example, desensitizers, plasticizers, slip agents, development accelerators, oils and the like can be mentioned.

The support used for the photosensitive material is transparent,
It may be either non-permeable but is preferably a permeable plastic support. For plastic supports,
A compound composed of a polyethylene compound (eg, polyethylene terephthalate, polyethylene naphthalate), a triacetate compound (eg, triacetate cellulose), a polystyrene compound, or the like is used. As the thickness of the support,
Preferably 50 to 250 μm, particularly preferably 70 to 2
00 μm.

To further improve the curl and curl of the support, it is preferable to perform a heat treatment after the film is formed. The most preferable is after the film formation and after the emulsion coating, but may be after the emulsion coating. The conditions of the heat treatment are preferably 45 ° C. to the glass transition temperature for 1 second to 10 days. From the viewpoint of productivity, it is preferable to set the time within one hour.

Further, it is preferable that the following compounds are contained in the constituent layers of the light-sensitive material.

(1) Solid-dispersed fine particles of a dye JP-A-7-5629, page (3) [0017] to (1)
6) Compound described on page [0042] (2) Compound having acid group JP-A-62-237445, Compound (8) described on page 11, lower left column, line 11 to page (25), lower right column, line 3 ) Acidic polymer JP-A-6-186659, page (10) [0036]-
(17) Compound described on page [0062] (4) Sensitizing dye JP-A-5-224330, (3) page [0017] to
(13) Compound described on page [0040] JP-A-6-194777, page (11) [0042]-
(22) Compound described on page [0094] JP-A-6-242533, (2) page [0015]-
(8) Compound described on page [0034] JP-A-6-337492, (3) page [0012]-
(34) Compound described on page [0056] JP-A-6-337494, (4) page [0013]-
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938, (3) page [0011] to
(16) Compound described on page [0066] (6) Hydrazine derivative JP-A-7-114126, page (23) [0111] to
(32) Compound described on page [0157] (7) Nucleation accelerator JP-A-7-114126, page (32) [0158] to
(36) Compound described on page [0169] (8) Tetrazolium compound JP-A-6-208188, page (8) [0059] to
(10) Compound described on page [0067] (9) Pyridinium compound JP-A-7-110556, (5) page [0028] to
(29) Compound described on page [0068] (10) Redox compound JP-A-4-245243, compound described on pages (7) to (22) (11) SPS support Support described in JP-A-3-54551 The above-mentioned additives and other known additives are described in, for example, RD17643 (December, 1978), 1871
6 (November 1979) and 308119 (1989)
Dec. 2012).

In the present invention, the processing is preferably carried out by employing an automatic developing machine having at least four processes of development, fixing, washing (or stabilization) and drying.

In a preferred embodiment of the developing solution used in the present invention, the developing agent represented by the formula (A) is used as the developing agent.

In the compound represented by the general formula (A),
The following general formula [A] wherein R ₁ and R ₂ are bonded to each other to form a ring
-A] is particularly preferred.

[0114]

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In the formula, R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, Represents an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

The alkyl group in the general formula (A) or the general formula [A-a] is preferably a lower alkyl group,
For example, it is an alkyl group having 1 to 5 carbon atoms, wherein the amino group is preferably an unsubstituted amino group or an amino group substituted with a lower alkyl group, the alkoxy group is preferably a lower alkoxy group, and the aryl group is a phenyl group. Alternatively, a naphthyl group is preferred, and these groups may further have a substituent, and the substituent is preferably a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group, or the like. Is mentioned.

Specific examples of the compounds represented by formulas (A) and [Aa] are shown below, but the present invention is not limited thereto.

[0118]

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[0119]

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These compounds are typically ascorbic acid or erythorbic acid and salts thereof, or compounds derived therefrom.
Alternatively, it can be easily synthesized by a known synthesis method.

The main developing agent referred to here is a compound which accounts for 50% or more by mole of the compounds capable of developing silver halide in the developing solution.

In the present invention, a developing agent represented by the general formula (A) and a 3-pyrazolidone (1-phenyl-3-
Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxylmethyl-3-pyrazolidone, 1-phenyl-4 -Ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-
Pyrazolidone, etc.), aminophenols (o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol,
Developing agents such as 2,4-diaminophenol or dihydroxybenzenes substituted with a hydrophilic group (hydroquinone monosulfonate, sodium hydroquinone monosulfonate, potassium 2,5-hydroquinonedisulfonate, dihydroxybenzoic acid, etc.); More preferably, they are used in combination. In particular, a combination of ascorbic acid or a derivative thereof with 3-pyrazolidones and a combination of ascorbic acid or a derivative thereof with 3-pyrazolidones and a dihydroxybenzene substituted with a hydrophilic group are preferably used.

When used in combination, the developing agent of 3-pyrazolidones, aminophenols or dihydroxybenzenes substituted with a hydrophilic group is usually used in an amount of 0.01 to less than 0.2 mol per liter of developer. It is preferably used in an amount.

An alkali agent (such as sodium hydroxide and potassium hydroxide) and a pH buffer (such as carbonate, phosphate, borate, boric acid, acetic acid, citric acid, and alkanolamine) are added to the developer. Is preferred. As the pH buffering agent, a carbonate is preferable, and the amount of the carbonate added is 0.1 mL per liter.
It is preferably from 2 to 1.0 mol, more preferably from 0.3 to 1.0 mol.
It is in the range of 0.6 mole.

When the developing agent represented by the formula (A) is used, it is preferable to contain a sulfite as a preservative. The preferable addition amount is 0.02 to 0.9 mol /
Liter is preferable, and particularly preferably 0.1 to 0.3 mol / liter.

Where necessary, dissolution aids (polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants ,
Antifoaming agents, antifoggants (halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (ethylenediaminetetraacetic acid or Alkali metal salts, nitrilotriacetates, polyphosphates, etc.), development accelerators (US Pat. No. 2,304,025, JP-B-47-455).
No. 41), a hardening agent (glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent.

The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5. More preferably, pH 8.
5-10.2.

As the fixing solution, those having a commonly used composition can be used. The pH of the fixing solution is generally 3 to
8 As a fixing agent, thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate;
In addition to thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, organic sulfur compounds capable of forming a soluble stable silver complex salt, which are known as fixing agents, can be used.

A water-soluble aluminum salt (aluminum chloride, aluminum sulfate, potassium alum, etc.) and an aldehyde compound (glutaraldehyde or glutaraldehyde sulfite adduct, etc.) which act as a hardener can be added to the fixing solution.

The fixing solution may optionally contain a preservative (sulfite, bisulfite, etc.), a pH buffer (acetic acid, citric acid, etc.),
Compounds such as a pH adjuster (sulfuric acid, sodium carbonate, etc.) and a chelating agent capable of softening water can be included.

In the present invention, the concentration of ammonium ion in the fixing solution is preferably 0.1 mol or less per liter of the fixing solution, particularly preferably in the range of 0 to 0.05 mol / l.

As the fixing agent, sodium thiosulfate may be used instead of ammonium thiosulfate, or ammonium thiosulfate and sodium thiosulfate may be used in combination.

It is preferable that the concentration of acetate ion in the fixing solution is less than 0.33 mol / liter. The type of acetate ion is arbitrary and can be applied to any compound that dissociates acetate ion in the fixing solution, but lithium, potassium, sodium, and ammonium salts of acetic acid and acetate are preferably used, and particularly, sodium salt, ammonium salt, and the like. Salts are preferred.
The acetate ion concentration is more preferably 0.22 mol or less, particularly preferably 0.13 mol or less per liter of the fixing solution, whereby the amount of acetic acid gas generated can be greatly reduced. Most preferred are those that are substantially free of acetate ions.

The fixing solution contains salts such as citric acid, tartaric acid, malic acid and succinic acid, and optical isomers thereof. As the salt, lithium salt, potassium salt, sodium salt, ammonium salt and the like, lithium hydrogen tartrate, potassium hydrogen, sodium hydrogen, ammonium hydrogen, ammonium potassium tartrate, sodium potassium tartrate and the like may be used. Preferred among these are citric acid, malic acid, succinic acid and salts thereof. Most preferred are malic acid and its salts.

In the present invention, it is preferable to carry out a washing treatment with washing water containing a purifying agent containing an oxidizing agent and a bactericide.

Preferred oxidizing agents include metal or nonmetal oxides, oxyacids or salts thereof, peroxides, and compounds containing organic acid systems. From the viewpoint of discharging to the drainage pipe, the oxyacid is preferably sulfuric acid, nitrous acid, nitric acid, hypochlorous acid or the like, and the peroxide is particularly preferably hydrogen peroxide solution or fentonic acid. Most preferred is hydrogen peroxide.

These oxidizing agents are preferably supplied in the form of a concentrated liquid or a solid agent from the viewpoint of distribution. As a preferred form, a concentrated solution is preferable, a concentrated solution having an oxidizing agent component of 0.1 to 10 mol / l is preferable, and particularly preferably 0.5 to 2.0 mol / l.

In the present invention, a concentrated solution or solid agent containing an oxidizing agent is supplied by mixing with washing water. As for the timing of mixing, it is possible to mix before entering the washing tank,
The concentrated liquid or solid agent and the washing water may be directly mixed in the washing tank.

The replenishment timing of the oxidizing agent-containing concentrated liquid or the solid agent and water may be replenished at a constant rate every unit time, or may be replenished according to the processing amount by detecting the processing amount of the photosensitive material.

The amount of the oxidizing agent added to the washing tank is preferably in the range of 1/2 to 10 molar equivalents, more preferably 1/2 to 3 molar equivalents, with respect to the thiosulfate brought into the photosensitive material. It is.

In the water washing of the present invention, in order to make the oxidizing agent act effectively, it is also a preferable embodiment to coexist with a compound such as a preservative or a bactericide.

The fungicide preferably used is not particularly limited as long as it does not adversely affect the photographic performance. Specific examples include thiazolylbenzimidazoles, isothiazolones and the like.
Chlorophenol type, bromophenol type, thiocyanic acid and isothianoic acid type, acid azide type, diazine and triazine type, thiourea type, alkylguanidine type, quaternary ammonium salt type, organic tin and organic zinc compound type, cyclohexylphenol type, There are various antibacterial agents and fungicides, such as active halogen compounds such as imidazole and benzimidazole, sulfamide, and chlorinated sodium isocyanurate, chelating agents, sulfites, and antibiotics represented by penicillin. In addition, L.I. E. FIG. Wes
t; Water Quality Criteria,
Photo. Sci. and Eng. , Vol9, N
o. 6 (1965): a fungicide described in JP-A-55-111
No. 942, No. 57-8542, No. 57-157244
Nos. 58-105145 and 59-126533
Various fungicides described in No. 3 etc .; "Bactericidal and Fungicide Chemistry" by Hiroshi Horiguchi, Sankyo Publishing (Showa 57), "Bacterial and Fungicide Technical Handbook", Japan Society of Bactericidal and Fungicide, Gihodo (Showa 61) Chemicals and the like as described can be used. Specific examples are shown below, but the present invention is not limited to these.

1: 5-chloro-2-methyl-4-isothiazolin-3-one 2: 2- (4-thiazolyl) -benzimidazole 3: methyl isothiocyanate 4: N- (3,5-dichlorophenyl) -N ' − (4-
Fluorophenyl) thiourea 5: 4-chloro-3,5-dimethylphenol 6: 2,4,6-trichlorophenol 7: sodium dehydroacetate 8: sulfanilamide 9: 3,4,5-tribromosalicylanilide 10: Potassium sorbate 11: benzalkonium chloride 12: 1-bromo-3-chloro-5,5-dimethylhydantoin 13: monochloroacetamide 14: monobromoacetamide 15: monoiodoacetamide 16: benzimidazole 17: cyclohexylphenol 18: 2 -Octyl-isothiazolin-3-one 19: ethylenediaminetetraacetic acid 20: nitrilo-N, N, N-trimethinephosphonic acid 21: 1-hydroxyethane-1,1-diphosphonic acid 22: ethylenediamine-N, N, N ' , '-Tetramethylenephosphonic acid 23: chlorinated sodium isocyanurate 24: 2-methyl-4-isothiazolin-3-one 25: 10,10'-oxybisphenoxyarsine 26: 1,2-benzisothiazolin-3-one 27 : Thiosalicylic acid These exemplified compounds are described in US Pat. No. 2,767,1.
No.72, No.2,767,173, No.2,767,17
Nos. 4,870,015 and British Patent 848,13
No. 0, French Patent No. 1,555,416, and the like, describe the synthesis method and examples of application to other fields. There are also commercially available products, such as Predentol ON, Permachem PD, Topside 800, Topside EG5, Topside 300, Topside 600 (all manufactured by Permachem Asia), Fineside J-700 (Tokyo Fine Chemical) Progel GXL (manufactured by ICI) under the trade name.

When the bactericide is supplied into washing water, it is preferably 0.01 to 50 g / l, more preferably 0.05 to 20 g / l. Further, when it is contained as a cleaning agent, it is 0.1 to 50 to the cleaning agent.
g / liter, more preferably 1 to 20 g / liter.

As the preservative used in the present invention, a compound having a polyalkylene oxide chain represented by the following formula (PO) is preferable.

Formula (PO) HO (CH ₂ CH ₂ O) _a
[CH (CH ₃ ) CH ₂ O] _b (CH ₂ CH ₂ O) _c H Here, a, b, and c are each a positive integer.

The compound represented by the general formula (PO) is a compound in which propylene glycol is added as a hydrophobic group and ethylene oxide is added as a hydrophilic group. Average molecular weight of 20
00-8500, polypropylene glycol (PPG)
The molecular weight is preferably from 1400 to 2400, and the ethylene oxide (EO) weight% in the total molecule is preferably about 40 to 85%, and particularly preferably, in the general formula, a + c is about 150 and b is about 30.

As such compounds, commercially available products
For example, there are "Pluronic series" nonionic surfactants manufactured by Asahi Denka Co., Ltd., and the following are specifically preferred.

[0149]

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The amount of the compound having a polyalkylene oxide chain to be added is 1 to 1000 ppm with respect to the washing water.
More preferably, it is 10 to 100 ppm, and when contained as a purifying agent, 0.01 to 10% with respect to the oxidizing agent,
Preferably it is 0.1-5%.

Examples of the preservative used in the present invention include phosphoric acid, barbituric acid, urea, acetanilide, oxyquinoline, salicylic acid, quinolinic acid and derivatives thereof, and salts thereof. And their salts.

The purifying agent according to the present invention preferably contains a chelating agent having a chelate stability constant of 0.8 to 5.0 with calcium ions. The chelate stability constant with calcium is the logarithm of the formation constant when one chelating agent binds to one calcium ion, and 20
It was measured under conditions of ° C and an ionic strength of 0.2.
Specifically, maleic acid, glycolic acid, gluconic acid,
Organic acids such as glucoheptanoic acid, tartaric acid, citric acid, succinic acid, salicylic acid, ascorbic acid, erythorbic acid, glycine, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminopolycarboxylic acids such as nitrilotriacetic acid and derivatives thereof, and the like. Salt. Gluconic acid and citric acid are preferred as organic acids, and ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid are preferred as aminopolycarboxylic acids.

These compounds are used in an amount of about 0.005 to 0.2 mol, preferably 0.005 to 1 mol per liter of washing water.
Used at ~ 0.1 mol.

When the washing time is less than 20 seconds, the effect of the present invention is remarkable, preferably less than 16 seconds, more preferably less than 12 seconds.

In the present invention, a developing and fixing replenisher prepared from a solid processing agent can be used. The solid processing agent referred to here is a powder processing agent, a tablet, a pill, a granule, or the like,
It has been subjected to moisture proof processing as required. Pastes and slurries are semi-liquid and inferior in storage stability, and have a risk of transportation, and are not included in the solid processing agents referred to in the present invention if they are regulated.

Here, the powder refers to an aggregate of fine crystal grains. Granules are obtained by adding a granulation step to powder, and refer to granules having a particle size of 50 to 5000 μm. Tablets are obtained by compressing powder or granules into a certain shape.

Among the above solid processing agents, tablets are preferably used because of high replenishment accuracy and easy handling.

In order to solidify the photographic processing agent, a concentrated liquid or a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is temporarily added to the surface of the photographic processing agent. Arbitrary means such as forming a coating layer by spraying can be adopted (JP-A-4-29136, 4-855).
Nos. 33, 4-85534, 4-85535, 4-85536 and 4-172341).

[0159] A preferable tablet production method is a method in which a powdery solid processing agent is granulated, and then a tableting step is performed. Simply mixing the solid processing agent components, the solubility and storage stability are improved over the solid processing agent formed by the tableting process,
As a result, there is an advantage that the photographic performance becomes stable.

Granulation methods for tablet formation include rolling granulation,
Known methods such as extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used.
For tablet formation, the average particle size of the obtained granules is 100 to 800 μm in that the granules are mixed and pressed and compressed, whereby the components become non-uniform, so-called segregation is unlikely to occur. It is preferable to use one, more preferably 200 to
750 μm. Further, the particle size distribution indicates that 60
% Is preferably within a deviation of ± 100 to 150 μm. Next, when pressing and compressing the obtained granules, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, a briquetting machine can be used. . The solid processing agent obtained by pressurization and compression can take any shape, but the productivity,
From the viewpoint of handleability and the problem of dust when used on the user side, a cylindrical type, so-called tablet, is preferred.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative, and the like.

A method for producing a tablet processing agent is described in, for example,
Nos. 1-61837, 54-155038 and 52-
No. 88025, British Patent No. 1,213,808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-109042 and 2-109043.
And JP-A-3-39735, JP-A-3-39939, and the like. Further, powder processing agents are disclosed in, for example, JP-A-54-133332, British Patent No. 7
No. 25,892, 729,862 and German Patent No. 3,733,861 and the like, and can be produced by a general method.

The bulk density of the solid processing agent is preferably from 1.0 to 2.5 g / cm ³ in the case of a tablet, from the viewpoint of its solubility and the effect of the object of the present invention. / C
When the strength is larger than m ³ , the strength of the obtained solid material is 2.5
If it is smaller than g / cm ³ , it is more preferable in view of the solubility of the obtained solid. When the solid processing agent is a granule or a powder, the bulk density is preferably from 0.40 to 0.95 g / cm ³ .

The solid processing agent is used at least for the developer and the fixing agent, but can be used for other photographic processing agents such as other rinsing agents. Further, it is the developer and the fixing agent that can exclude the regulation of the liquid dangerous substance. Most preferably, all the processing agents are solidified, but at least the developer and the fixing agent are preferably solidified.

The solid treating agent can be solidified only for a part of a certain treating agent, but preferably all the components are solidified. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit.
It is also desirable that the separate components are packaged in the order in which they are periodically charged repeatedly.

When the developer is solidified, it is preferable that all of the alkali agent and the reducing agent are solidified, and in the case of tablets, it is preferable to use at least three agents, most preferably one agent. Also, when the solid processing agent is divided into two or more agents,
It is preferable that the plurality of tablets and granules are packaged in the same manner.

When the fixing agent is solidified, the base agent, preservative, and hardening agent such as aluminum salt are all solidified, and in the case of tablets, at least 3 or less, most preferably 1 or 2 It is preferable to use an agent. When the solid treatment is performed by dividing into two or more agents, it is preferable that the plurality of tablets and granules are packaged in the same manner. In particular, it is preferable in terms of handling that the aluminum salt be solid.

Examples of the package of the solid processing agent include polyethylene (either high-pressure method or low-pressure method), polypropylene (either unstretched or stretched), polyvinyl chloride,
Polyvinyl acetate, nylon (stretched, unstretched), polyvinylidene chloride, polystyrene, polycarbonate, vinylon, eval, polyethylene terephthalate (PE
T), other polyesters, hydrochloride rubber, acrylonitrile-butadiene copolymer, epoxy-phosphate resins (polymers described in JP-A-63-63037, 57-3)
Synthetic polymers and pulp such as the polymer described in No. 2952).

[0169] These are preferably made of a single material, but when used as a film, the film may be laminated and adhered, or may be used as a coating layer, or may be a single layer. Further, it is more preferable to use various gas barrier films, for example, using an aluminum foil or an aluminum vapor-deposited synthetic resin between the above synthetic resin films.

In order to preserve the solid processing agent and prevent the generation of stain, the oxygen permeability of these packaging materials is 50 ml.
/ M ²・ 24hr ・ atm or less (20 ℃ ・ 65% RH
), More preferably 30 ml / m ² · 24 hr · at
m or less.

The total thickness of these laminated films or single layers is 1 to 3000 μm, more preferably 10 to 2000 μm.
m, more preferably 50 to 1000 μm.

The above synthetic resin film may be a one-layer (polymer) resin film or a laminated (polymer) resin film of two or more layers.

When the treating agent is packaged or bound or covered with a water-soluble film or binder, the water-soluble film or binder may be a polyvinyl alcohol-based, methylcellulose-based, polyethylene oxide-based, starch-based, polyvinylpyrrolidone-based, From hydroxypropylcellulose, pullulan, dextran and gum arabic, polyvinyl acetate, hydroxyethylcellulose, carboxyethylcellulose, carboxymethylhydroxyethylcellulose sodium salt, poly (alkyl) oxazoline, polyethyleneglycol base Films or binders are preferably used, and among these, polyvinyl alcohol-based and pullulan-based ones are more preferably used in view of the effect of coating or binding.

The thickness of the water-soluble film is preferably 10 to 120 μm in view of the storage stability of the solid processing agent, the dissolution time of the water-soluble film, and the precipitation of crystals in an automatic developing machine. 80 μm is preferable,
Particularly, those having a thickness of 20 to 60 μm are preferable.

The water-soluble film is preferably thermoplastic. This is because not only the heat sealing process and the ultrasonic welding process are facilitated, but also the covering effect is more excellent.

The water-soluble film had a tensile strength of 0.5 × 1.
^{0 6 ~50 × 10 6 kg /} m 2 are preferred, especially 1 × 10 ⁶
２５25 × 10 ⁶ kg / m ² , preferably 1.5 × 10 ⁶ kg / m ²
It is preferably from 10 ⁶ to 10 × 10 ⁶ kg / m ² . These tensile strengths are measured by the method described in JIS Z-1521.

A photographic processing agent packaged or bound or covered with a water-soluble film or a binder can be stored, transported,
And is packaged in moisture-proof packaging to prevent damage from atmospheric humidity, such as high humidity, rain and fog, and splashing or accidental contact with water by wet hands during handling Preferably, the moisture-proof packaging material has a film thickness of 10
A film having a moisture-proofing property, a moisture-proof packaging material is a polyethylene terephthalate, polyethylene, a polyolefin film such as polypropylene, kraft paper, wax paper, moisture-resistant cellophane which can have a moisture-proof effect with polyethylene,
It is preferably at least one selected from glass foil, metal foil such as glassine, polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate, acrylonitrile and aluminum, and a metallized polymer film. It may be a material.

The moisture-proof packaging material is made of a degradable plastic,
It is particularly preferable to use a biodegradable or photodegradable plastic.

Examples of the biodegradable plastics include those composed of natural polymers, polymers produced by microorganisms, synthetic polymers having good biodegradability, and blending of biodegradable natural polymers with plastics. And a group in which a group which is excited by ultraviolet rays and leads to cleavage is present in the main chain. Further, in addition to the polymers listed above, those having both the functions of photodegradability and biodegradability at the same time can be used favorably.

The specific representative examples are as follows.

Examples of biodegradable plastics include (1) natural polymer polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof. (2) Microbial-produced polymer PHB-PHV (3-hydroxybutyrate). Which is a copolymer of methacrylate and 3-hydroxyvalerate))
pol ", cellulose produced by microorganisms, etc. (3) Synthetic polymers with good biodegradability Polyvinyl alcohol, polycaprolactone, etc., or copolymers or mixtures thereof (4) Blending of biodegradable natural polymers to plastics Biodegradability Good natural polymers include starch and cellulose, which have been given a shape-disintegration property in addition to plastics. Photodegradable plastics include: (5) Introduction of a carbonyl group for photodisintegration, etc. Alternatively, an ultraviolet absorber may be added.

For such degradable plastics,
"Science and Industry", Vol. 64, No. 10, pp. 478-484 (1990), "Functional Materials", July 1990, 23.
~ 34 pages and the like can be used.
Also, Biopol (Biopol: manufactured by ICI), Ec
o (Eco: manufactured by Union Carbide), Eco
lite (Ecolight: Eco Plastic), Ecostar (Ecostar: St. Lawre)
commercially available decomposable plastics such as No. Starch (manufactured by Nippon Unicar) and Knuckle P (manufactured by Nippon Unicar).

The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² · 24 hr or less.
It is more preferably 5 g · mm / m ² · 24 hr or less.

The developing solution and the fixing solution are stocked in the replenishing device, and the processing solution is replenished according to the processing amount and the operating time of the automatic developing machine. When the replenisher is a liquid, it may be stocked and replenished inside or outside the replenisher, or may be stocked and replenished in the form of a concentrated solution. When the replenisher is a solid agent, the replenisher can be dissolved in the replenisher, and the replenisher can be stocked and replenished.

In view of the demand for reducing the amount of waste liquid, the present invention is processed while replenishing a fixed amount in proportion to the area of the photosensitive material. The fixing replenishment amount is 300 ml or less per m ² . Preferably, each 30 to 250 per m ²
ml. The development replenishment amount is preferably 250 ml or less per 1 m ² , more preferably 30 to 200 m ^2.
l. The fixing replenishment amount and the development replenishment amount referred to here are:
Indicates the amount to be replenished. Specifically, it is the replenishment amount of each of the developing mother liquor and the fixing mother liquor when replenishing the same liquor, and the respective amounts when the developing concentrated liquor and the fixing concentrated liquor are replenished with a solution diluted with water. The total amount of the concentrated solution and water, when replenished with a solution obtained by dissolving the solid developing agent and the solid fixing agent in water, the total amount of the respective solid processing agent volume and the volume of water, Also, it is the total amount of the solid processing agent volume and the water volume when the solid developing agent, the solid fixing agent and the water are separately replenished.

In the case of replenishment with a solid processing agent, it is preferable to represent the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water added separately. The developing replenisher and the fixing replenisher may be the same as the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine, respectively.
Different liquid or solid processing agents may be used.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably in the range of 10 to 45 ° C., and each may be separately adjusted.

When processing is carried out using an automatic developing machine from the demand for shortening the developing time, it is a preferred embodiment that the film transport speed (line speed) of the automatic developing machine is 1000 mm / min or more. Particularly preferably, 1200 mm /
min or more. Further, the total processing time (Dry to Dry) from the insertion of the leading end of the film into the automatic developing machine until it comes out of the drying zone is preferably 10 to 70 seconds. The total processing time referred to here includes the total processing time required for processing the black-and-white photosensitive material, and specifically, for example, development, fixing, bleaching, washing, stabilizing processing, drying, etc. necessary for processing. Time including all the time of the process, that is, Dr
It is the time of y to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening.
More preferably, the total processing time (Dry to Dry)
Is 30 to 60 seconds. Also, in order to stably run a large amount of photosensitive material of 100 m ² or more, the effect of the present invention was great when the washing time was less than 20 seconds.

In order to remarkably exhibit the effects of the present invention, a heat transfer material (60 to 130 ° C.) having a temperature of 60 ° C. or higher is required for the automatic developing machine.
° C heat roller, etc.) or radiating object of 150 ° C or higher (tungsten, carbon, nichrome, zirconium oxide.
Heat is emitted by passing a current directly through a mixture of yttrium oxide / thorium oxide, silicon carbide, etc., or heat is transmitted from a resistance heating element to a radiating element such as copper, stainless steel, nickel, or various ceramics to generate heat and generate infrared rays. And those having a drying zone are preferably used.

An automatic developing machine having the following method and mechanism can be preferably used.

(1) Deodorizer JP-A-64-37560, upper left column of page (2) to upper left column of page (3) (2) Waste liquid treatment method JP-A-2-64638, lower left column of page (2) to ( 5) Lower left column of page (3) Rinse bath between developing bath and fixing bath JP-A-4-313949, page (18), "0054" to
(21) "0065" (4) Water replenishment method JP-A-1-281446, (2) Lower left column to lower right column of page (5) Detecting outside air temperature and humidity to control drying air of automatic developing machine Methods JP-A-1-315745, lower right column of page (2) to lower right column of page (7) and JP-A-2-108051, lower left column of page (2) to lower left column of page (3) (6) Fixing waste liquid Silver recovery method JP-A-6-27623, page (4) "0012"-
(7) Page "0071".

[0192]

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

Example 1 (Preparation of silver halide emulsion A) Aqueous solution of silver nitrate B and water-soluble halide solution C comprising sodium chloride and potassium bromide
Was added to the solution A at a constant flow rate of pH 3.0 at 40 ° C. for 30 minutes by the double-mixing method, and 0.20 μm of silver chlorobromide (AgCl
/ AgBr = 70/30 mol%). At this time, the silver potential (EAg) was 160 mV at the start of mixing and 100 mV at the end of mixing. Subsequently, after unnecessary salts were removed by ultrafiltration, 15 g of gelatin was added per mol of silver to adjust the pH to 5.7, and the mixture was dispersed at 55 ° C. for 30 minutes. After dispersion, chloramine T was added in an amount of 4.times.10.sup.- ⁴ mol per mol of silver. The silver potential of the obtained emulsion was 190 mV (40 ° C.).

Solution A Ossein gelatin 25 g Nitric acid (5%) 6.5 ml Ion exchange water 700 ml Na [RhCl ₅ (H ₂ O)] 0.02 mg Solution B Silver nitrate 170 g Nitric acid (5%) 4.5 ml Ion exchange water 200 ml Liquid C 47.5 g of sodium chloride 51.3 g of potassium bromide 6 g of ossein gelatin 0.15 mg of Na ₃ [IrCl ₆ ] 200 ml of ion-exchanged water 200 ml of a stabilizer (ST-1) per mol of silver was added to the obtained emulsion. 5 × 10 ⁻³ mol and 8.5 × 10 ⁻⁴ mol of potassium bromide were added to adjust the pH to 5.6 and the EAg to 123 mV.
The sulfur dispersed in fine particles is converted into sulfur
^-5 mol and 1.5 × 10 ^-5 mol of chloroauric acid are added and 50
After chemical ripening at 60 ° C. for 60 minutes, ST-1 was added to 2 × 10 ⁻³ mol per mol of silver, and fog inhibitor (AF-1) was added to 3 ×
10 ^-4 mol and 1.5 × 10 ^-3 mol of potassium iodide were added. After cooling to 40 ° C., the sensitizing dyes (S-1, S-
2) was added in an amount of 2 × 10 ^-4 mol per mol of silver.

Using the emulsion thus obtained, 1 m
As the amount urging per ² becomes the following formulation, on one side on a support having subbing processed, a first layer below from the support side, a second layer,
The third layer was simultaneously coated in multiple layers, and cooled and set (emulsion formulation A).

Then, the following backing layer was coated on the undercoating layer having the antistatic layer on the opposite side at a coating speed of 200 m / m.
In a minute, cooled and set at -1 ° C., and dried on both sides simultaneously to obtain a photosensitive material sample 101.

The emulsion formulation B was exactly the same as the emulsion formulation A except that the hydrazine derivative was not contained.

(Support, Undercoat Layer) After a corona discharge of 30 W / (m ² · min) was applied to both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm), an undercoat layer having the following composition was applied to both sides. And dried at 100 ° C. for 1 minute.
The numerical values indicate the weight per 1 m ² .

2-Hydroxyethyl methacrylate / butyl acrylate / t-butyl acrylate / styrene copolymer (25/30/25/20 weight ratio) 0.5 g Surfactant A 3.6 mg hexamethylene-1,6-bis (Ethylene urea) 10 mg (Antistatic layer) After a corona discharge of 10 W / (m ² · min) was applied to a polyethylene terephthalate support provided with an undercoat layer, an antistatic layer having the following composition was applied on one side to 70 m / min.
Apply using a roll-fit coating pan and air knife at a speed of 90 ° C., dry at 90 ° C. for 2 minutes,
Heat treated at 90 ° C. for 90 seconds.

Water-soluble conductive polymer B 0.6 g Hydrophobic polymer particles C 0.4 g Polyethylene oxide compound (Mw = 600) 0.1 g Hardener E 0.1 g First layer (undercoat layer) Gelatin 0.30 g AM 0.05 g polystyrene sulfonic acid (Mw 500,000) 0.02 g 2nd layer (emulsion layer) coating solution pH 5.2 gelatin 1.0 g silver halide emulsion A 3.3 g as silver amount hydrazine derivative H-34 0.015 g hydrazine Derivative H-39 0.020 g Nucleation promoter Na-21 0.15 g 5-Nitroindazole 0.01 g 2-mercaptohypoxanthine 0.02 g Suspension polymer of colloidal silica / vinyl acetate / vinyl pivalinate (75 / 12.5 / 12.5% by weight) 1.4 g Dextran (average molecular weight 70,000) 0.1 g 4- Rucapto-3,5,6-fluorophthalic acid 0.05 g Sodium polystyrene sulfonate (average molecular weight 500,000) 0.015 g Third layer (protective layer) Gelatin 0.80 g Dextran (average molecular weight 70,000) 0.2 g Colloidal silica 0.10 g Fungicide Z 0.005 g Hardener H-1 0.07 g Polymethyl methacrylate latex (particle size 3 μm) 0.01 g (Backing layer) Gelatin 2.0 g Dye F-1 0.05 g Dye F-20 0.04 g Dye F-3 0.02 g Colloidal silica / vinyl acetate / vinyl pivalinate suspension polymer (75 / 12.5 / 12.5% by weight ratio) 0.7 g Sodium polystyrene sulfonate 0.010 g Matting agent (Monodisperse polymethyl methacrylate having an average particle size of 3 μm) 0.045 g Hardener H-1 0.0 5 g Hardener H-2 0.07 g ST-1: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene AF-1: 1-phenyl-5-mercaptotetrazole H-1: CH _{2 = CHSO 2 CH 2 CONHCH 2} CH 2 NHCOCH 2 SO 2 CH = CH 2

[0201]

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[0202]

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[0203]

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In the photosensitive material sample 101, samples 102 to 107 in which the surfactant used and the amount of the surfactant added were changed as shown in Table 1, and samples 108 to 110 in which the emulsion A used was changed to the emulsion B were prepared. .

After subjecting these samples to wedge exposure, the samples were developed under the following conditions to evaluate the respective characteristics.

[0206] When the number of seconds for development was changed, the ratio was changed at this ratio.

The treatment liquid formulations are as follows.

Developing solution HQ (per liter of working solution) Pure water 224 ml Diethylenetriaminepentaacetic acid / 5 sodium 1.0 g Potassium sulfite 12.54 g Sodium sulfite 42.58 g Potassium bromide 4 g Borate 8 g Potassium carbonate 55 g Diethylene glycol 40 g 5-methyl Benzotriazole 0.21 g 1-Phenyl-4-methyl-4-hydroxylmethyl-3-pyrazolidone (dimesone S) 0.85 g Hydroquinone 20 g Potassium hydroxide 18 g Dissolved according to the formulation to make a total volume of 400 ml. When used, it is mixed with 600 ml of pure water to make 1 liter. The pH of the working solution was adjusted to 10.4.

Fixing solution (starting solution: per liter of working solution) Sodium thiosulfate 200 g Sodium sulfite 22 g Sodium gluconate 5 g Trisodium citrate dihydrate 12 g Citric acid 12 g And finished to 1 liter.

Fixing solution (replenisher: 2-fold concentrated solution) Sodium thiosulfate 200 g Sodium sulfite 22 g Sodium gluconate 5 g Trisodium citrate dihydrate 12 g Citric acid 12 g Sulfuric acid has a pH of 5.2. And finished to 500 ml.

Rinse Water [0211] A solution obtained by adding 8.8 ml of the following purifying agent to 1 liter of tap water was placed in a rinsing tank to prepare rinsing water.

(Preparation of Purifying Agent) Pure water 800 g Salicylic acid 0.1 g 35% by weight aqueous hydrogen peroxide 171 g Pluronic F-68 3.1 g Hoksite F-150 15 g Diethylenetriaminepentaacetic acid / 5 sodium 10 g Finished to 1 liter with pure water .

(Blackening ratio of photosensitive material) 8% (Replenishment amount of processing solution) The developing / fixing replenisher, the purifying agent and the tap water for dilution of the above-mentioned formulation were respectively charged into a developing tank, a fixing tank and a washing tank as follows. Replenished directly on condition.

[0214] The following evaluation was performed using each developed sample.

(Running Experiment) The developing solution, the fixing solution, and the washing water prepared according to the above-mentioned formulation were used in an automatic developing machine LD-T1060.
(Manufactured by Dainippon Screen Mfg. Co., Ltd.). In this state, each photosensitive material was processed for 30 m ² per day and run for one week. The sensitivity, γ, coating failure, dirt in the washing tank, and adhesion of dirt to the film were evaluated.

<< Sensitivity and γ >> The photosensitive material sample was 633 nm
Wedge exposure is performed using the semiconductor laser described above, and the developing treatment is performed under the above-described conditions using the processing solution, the automatic developing machine LD-T1060 (described above), the developing solution, the fixing solution, the washing water, and the oxidizing agent-containing cleaning agent. And the sensitivity was determined. At this time, the sensitivity of the sample 101 was expressed as a relative value assuming 100. Further, γ was determined from the slope of the characteristic curve giving densities 1 and 3.

<< Stains in Washing Tank >> After operating under the above conditions, stains due to water stains in the washing tank after running for one week were visually judged and evaluated on a five-point scale. Rank 5 is the best, and rank 3 or higher is a level that can withstand practical use.

1: Both the roller and the washing tank wall have scales and the scale floats in the liquid. 2: The rollers and the wash tank have scales but no floating matter in the liquid. 3: The roller is slimy, but no scale is attached to the washing tank. 4: A part of the roller is slimy. 5: No scale is generated.

<< Film Stain >> After operating under the above-mentioned conditions, the stain adhered to the film after one week of running was comprehensively visually evaluated in five stages. Rank 5 is the best, and rank 3 or higher is a level that can withstand practical use.

The results are summarized in Table 1.

[0221]

[Table 1]

The sample of the present invention is excellent in any of the evaluations.

Example 2 Compounds I and II were prepared according to Samples 101 to 106 of Example 1.
A sample was prepared in which the addition amount of A was changed, and the developing solution was used in the following formulation A
The photographic characteristics were evaluated by changing Q, developing conditions and line speed (samples 201a to 208).

AQ Developer Diethylenetriaminepentaacetic acid / pentasodium 1 g Sodium sulfite 30 g Potassium carbonate 53 g Potassium hydrogen carbonate 17 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Sodium erythorbate monohydrate 40 g 1-phenyl-5-mercaptotetrazole 0.025 g potassium bromide 4 g 5-methylbenzotriazole 0.21 g 2,5-dihydroxybenzoic acid 5 g 8-mercaptoadenine 0.07 g Potassium hydroxide was added to adjust the pH to 9.8. And finished to 1 liter. Table 2 shows the results.

[0225]

[Table 2]

The sample of the present invention is excellent in any of the items.

[0227]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which causes less stains on a washing water tank and a film surface during development processing and a method for processing a silver halide photographic light-sensitive material which has less influence on the environment.

Claims (4)

[Claims] 1. A support having at least one photosensitive silver halide emulsion layer on one side of a support, comprising a compound represented by the following general formula (I) and a compound represented by the following general formula (II) A silver halide photographic light-sensitive material comprising: Formula (I) R ¹ O (CH ₂ CH ₂ O) n ₁ (CH ₂ ) n ₂
SO ₃ M ^{1 wherein} R ¹ represents an aromatic group or an aliphatic group having 5 to 20 carbon atoms. n ₁ represents an integer of 1 to 20, n ₂ represents an integer of 0 to 6. M ¹ represents a hydrogen atom or an alkali metal atom. [Formula 1] [Wherein, R ¹¹ and R ¹² may be the same or different and represent an alkyl group having 5 to 30 carbon atoms, and R ¹³ represents a hydrogen atom or-
Represents a CH ₂ COOR ¹⁴ group. R ¹⁴ has the same meaning as R ¹¹ and R ¹² , and M ² represents an alkali metal atom or an ammonium group. ] 2. The silver halide photographic light-sensitive material according to claim 1, which contains a hydrazine derivative as a contrast agent. 3. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on one side of a support and containing a compound represented by the formula (I),
A development processing method characterized by performing development processing with a developer containing a developing agent represented by the following general formula (A). Embedded image [Wherein, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group. R ₁ and R ₂ may combine with each other to form a ring. k
Represents 0 or 1, and when k = 1, X represents -CO- or -C
M ₁ and M ₂ each representing S— each represent a hydrogen atom or an alkali metal atom. ] 4. The developing method according to claim 3, wherein the line speed of the automatic developing machine is 1 m / min or more when the developing processing is performed by the automatic developing machine.