JP2001147502A - Silver halide photographic sensitive material and processing method for same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material less liable to stain in development and a processing method for the sensitive material less liable to affect the environment. SOLUTION: The silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer on one face of the substrate and contains a compound of the formula R11O(CH2CH2O) n11(CH=CHO)n21(CH2)m1 SO3M1 or a compound of the formula R12O(CH2CH2O)n12(CH=CHO)n22(CH2)m2 COOM2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material and a method for processing a silver halide photographic light-sensitive material.

[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.

[0003] In order to solve the problem described above,
Nos. 523 and 6-130539 disclose a technique using a sulfoalkylpolyoxyethylene-based activator, but have a problem that coating defects easily occur during 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, and in order to obtain such a high contrast image, US Pat.
As disclosed in JP-A Nos. 69,929, JP-A-60-25837 and JP-A-5-232616, a photographic material containing a hydrazine derivative is treated with an MQ developer (developing using a combination of p-aminophenols and hydroquinone). Solution) or a PQ 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.

In response to the above demands, US Pat. Nos. 5,236,816 and 5,264,323 disclose systems using ascorbic acids as a developing agent. In addition, there is a problem that the pH tends to decrease due to air oxidation, and the fluctuation of the processing solution is large. Therefore, the developing solution contains a developing agent more than necessary or contains a large amount of carbonate to suppress the fluctuation of the pH of the developing solution. Needed. 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 liable to be precipitated in the processing solution, and are likely to adhere as dirt or to cause poor fixing.

Therefore, a silver halide photographic light-sensitive material having improved stability during coating and stability during processing and a method for processing the same have been desired.

[0008]

SUMMARY OF THE INVENTION 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.

[0009]

The above objects of the present invention have been attained by the following items 1 to 6.

[0010] 1. On one side of the support, at least one layer
Having a photosensitive silver halide emulsion layer, and having the following general formula
A compound represented by (1) or represented by the following general formula (2)
Silver halide photography characterized by containing a compound
True photosensitive material. General formula (1) R₁₁O (CH_TwoCH_TwoO)_n11(CH = C
HO)_n21(CH_Two)_m1SO_ThreeM₁ General formula (2) R₁₂O (CH_TwoCH_TwoO)_n12(CH = C
HO)_n22(CH_Two)_m2COOM_Two Where R₁₁, R₁₂Is an alkyl having 5 to 30 carbon atoms
R represents a group₁₁And R ₁₂May be the same or different
No. n11, n12, n21 and n22 are respectively 1 to 2
Represents an integer of 0, m1 and m2 are each an integer of 0 to 6
Represent. M₁, M_TwoAre a hydrogen atom and an alkali metal atom, respectively.
Or represents an ammonium group.

2. 2. The silver halide photographic light-sensitive material as described in 1 above, comprising a hydrazine derivative as a high contrast agent.

3. In processing the silver halide photographic light-sensitive material of 1 or 2, the replenishing amount of the developing solution is 30 to 150 ml per m ^{2 of the} photographic material, and the replenishing amount of the fixing solution is 50 to 300 ml per m ^{2 of the} photographic material. A method for processing a silver halide photographic light-sensitive material.

4. Total processing time (Dry to
(Dry) is from 10 seconds to 60 seconds.

5. 5. The method for processing a silver halide photographic light-sensitive material according to the above item 3 or 4, wherein the processing is performed with a processing solution prepared from a solid processing agent.

6. 3. The method according to item 3, wherein the development is performed with a developer containing a developing agent represented by the following general formula (A).
6. The method for processing a silver halide photographic material according to 4 or 5.

[0016]

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In the formula, R ₁ and R ₂ each represent an alkyl group, an amino group, an alkoxyl group or an alkylthio group.
R ₁ and R ₂ may combine with each other to form a ring. k is 0
Or 1 and when k = 1, X represents -CO- or -C
M ₁ and M ₂ each representing S— represent a hydrogen atom or an alkali metal atom.

Hereinafter, the present invention will be described in more detail. Conventional sulfoalkyl polyoxyethylene surfactants, which are used to improve film surface contamination and poor fixing during processing of silver halide photographic materials, have the problem that coating defects tend to occur during coating. However, both the stability during coating and the stability during processing were not sufficiently satisfied.

In the present invention, by using the compound represented by the above-mentioned general formula (1) or (2), the stability at the time of coating, which cannot be achieved by a conventionally known surfactant, is obtained. It has been found that both stability during processing can be sufficiently satisfied at the same time. Further, by using the developing agent represented by the above-mentioned general formula (A) for the development processing, a processing method more excellent in environmental suitability than before can be provided.

The compounds represented by the above general formulas (1) and (2) will be described. Each of R ₁₁ and R ₁₂ represents an alkyl group having 5 to 30 carbon atoms, and is preferably an alkyl group having 8 to 12 carbon atoms from the viewpoint of improving coating properties and processing solution stability. The alkyl group may be branched or linear, and may have a substituent or may be unsubstituted.

Examples of the alkyl group represented by R ₁₁ and R ₁₂ include, for example, octyl, nonenyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 2-ethyl- Hexyl group and the like.

Each of n11, n21, n12 and n22 is an integer of 1 to 20, and preferably 3 to 10 from the viewpoints of improving coating properties and processing solution stability.

M1 and m2 each represent an integer of 0 to 6, preferably 1 to 5. From the viewpoints of improving coating properties and processing stability, the amount of the compound represented by the general formula (1) or (2) is preferably 0.1 to 1 liter per coating liquid.
10 g is preferable, and more preferably 0.5 to 5 g. The addition may be made at any time in the photosensitive material production process.

Hereinafter, the compound represented by the general formula (1)
Although specific examples are shown, the present invention is not limited to these. 1-1: CH_Three(CH_Two)_FourCH (C_TwoH_Five) O (CH_TwoCH
_TwoO)_Three(CH = CHO) _Three(CH_Two)_ThreeSO_ThreeNa 1-2: CH_ThreeCH (C_TwoH_Five) (CH_Two)_ThreeCH (C
_TwoH_Five) O (CH_TwoCH_TwoO) (CH = CHO)_FourCH_TwoCH
_TwoSO_ThreeNa 1-3: CH_ThreeC (CH_Three)_Two(CH_Two)_ThreeCH (C_TwoH_Five)
O (CH_TwoCH_TwoO) (CH = CHO)₆(CH_TwoCH
_TwoO)_FourCH_TwoCH_TwoSO_ThreeH 1-4: CH_Three(CH_Two)_FourO (CH_TwoCH_TwoO) (CH =
CHO) (CH_TwoCH_TwoO)_Four(CH = CHO)_TwoCH_TwoC
H_TwoSO_ThreeNa 1-5: CH_Three(CH_Two)_TenO (CH_TwoCH_TwoO) (CH =
CHO) (CH_TwoCH_TwoO)_Four(CH = CHO)_TwoCH_TwoC
H_TwoSO_ThreeNa 1-6: CH_Three(CH_Two)₁₁O (CH = CHO)_Five(CH_Two
CH_TwoO)_Three(CH_Two)_ThreeSO_ThreeNa 1-7: CH_ThreeCH_TwoC (CH_TwoCH_Three)_Two(CH_Two)_FourO
(CH_TwoCH_TwoO)_Three(CH = CHO) (CH_TwoCH_TwoO)
(CH = CHO)_TwoCH_TwoCH_TwoSO_ThreeH 1-8: C_TwoH_FiveCH (CH_Three) (CH_Two)_TwoCH (CH_Three)
CH_TwoO (CH_TwoCH_TwoO)_Two(CH = CHO) (CH_TwoC
H_TwoO)_Two(CH = CHO)_Two(CH_Two)_TwoSO_ThreeNa 1-9: CH_ThreeC (CH_Three)_TwoCH_TwoC (CH_Three)_Two(C
H_Two)_ThreeO (CH = CHO) (CH_TwoCH_TwoO) (CH = C
HO)_Three(CH_TwoCH_TwoO)_Two(CH_Two)_ThreeSO_ThreeNa 1-10: CH_ThreeC (CH_Three)_TwoCH_TwoCH (CH_Three) (C
H_Two)₇O (CH = CHO) (CH_TwoCH_TwoO) (CH = C
HO)_Two(CH_TwoCH_TwoO)_Two(CH = CHO)_Two(CH_Two)
_ThreeSO_ThreeNa 1-11: CH_ThreeC (CH_Three)_TwoCH_TwoC (CH_TwoCH_Three)
(CH_Three) (CH_Two)₇O (CH = CHO) (CH_TwoCH_Two
O)_Two(CH = CHO)_Two(CH_TwoCH_TwoO)_Two(CH = C
HO) (CH_Two)_ThreeSO_ThreeNa 1-12: CH_ThreeC (CH_Three)_TwoCH_TwoC (CH_TwoCH_Three)
(CH_Three) (CH_Two)₇O (CH = CHO) (CH_TwoCH_Two
O)_Two(CH = CHO) (CH_TwoCH_TwoO)_Two(CH = CH
O)_Two(CH_Two)_ThreeSO_ThreeH 1-13: CH_ThreeC (CH_Three)_TwoCH_TwoC (CH_TwoCH_Three)
(CH_TwoCH_TwoCH_Three) (CH_Two)_ThreeCH (CH_Three) CH_TwoC
H_TwoO (CH = CHO)_Five(CH_TwoCH_TwoO)₇(CH_Two)_Five
SO_ThreeNa 1-14: CH_Three(CH_Two)₁₁O (CH = CHO)_Two(C
H_TwoCH_TwoO)_Three(CH_Two)_ThreeSO_ThreeNa 1-15: CH_Three(CH_Two)₁₁O (CH = CHO) (CH
_TwoCH_TwoO)_Two(CH = CHO)_Two(CH_TwoCH_TwoO)_Two(C
H = CHO) (CH_Two)_ThreeSO_ThreeH 1-16: CH_Three(CH_Two)₁₁O (CH_TwoCH_TwoO)_Two(C
H = CHO)_Two(CH_TwoCH_TwoO)_Two(CH = CHO) (C
H_Two)_ThreeSO_ThreeNa 1-17: CH_ThreeC (CH_TwoCH_TwoCH_Three)_TwoCH_TwoC (CH
_TwoCH_TwoCH_Three) (CH_Three) (CH_Two)_ThreeCH (CH_Three) CH_Two
CH_TwoO (CH = CHO)_Five(CH_TwoCH_TwoO)₇(CH_Two)
_FiveSO_ThreeNa 1-18: CH_ThreeC (CH_TwoCH_TwoCH_Three)_TwoCH_TwoC (CH
_Three) (CH_Three) CH_TwoCH_TwoCH_TwoCH (CH_Three) CH_TwoCH_Two
O (CH = CHO)_Five(CH_TwoCH_TwoO)_Two(CH_Two)_FiveSO
_ThreeH 1-19: CH_Three(CH_Two)₁₁O (CH = CHO)_Two(C
H_TwoCH_TwoO)_Two(CH = CHO)_Two(CH_TwoCH_TwoO)
_Two(CH = CHO) (CH_Two)_ThreeSO_ThreeNa 1-20: CH_Three(CH_Two)₁₇O (CH_TwoCH_TwoO)_Two(C
H = CHO)_Two(CH_TwoCH_TwoO)_Two(CH = CHO) (C
H_Two)_ThreeSO_ThreeNa Specific examples of the compound represented by the general formula (2) are shown below.
However, the present invention is not limited to these. 2-1: CH_Three(CH_Two)_FourCH (C_TwoH_Five) O (CH_TwoCH
_TwoO)_Three(CH = CHO) _Three(CH_Two)_ThreeCO_TwoNa 2-2: CH_ThreeCH (C_TwoH_Five) (CH_Two)_ThreeCH (C
_TwoH_Five) O (CH_TwoCH_TwoO) (CH = CHO)_FourCH_TwoCH
_TwoCO_TwoNa 2-3: CH_ThreeC (CH_Three)_Two(CH_Two)_ThreeCH (C_TwoH_Five)
O (CH_TwoCH_TwoO) (CH = CHO)₆(CH_TwoCH
_TwoO)_FourCH_TwoCH_TwoCO_TwoH 2-4: CH_Three(CH_Two)_FourO (CH_TwoCH_TwoO) (CH =
CHO) (CH_TwoCH_TwoO)_Four(CH = CHO)_TwoCH_TwoC
H_TwoCO_TwoNa 2-5: CH_Three(CH_Two)_TenO (CH_TwoCH_TwoO) (CH =
CHO) (CH_TwoCH_TwoO)_Four(CH = CHO)_TwoCH_TwoC
H_TwoCO_TwoNa 2-6: CH_Three(CH_Two)₁₁O (CH = CHO)_Five(CH_Two
CH_TwoO)_Three(CH_Two)_ThreeCO_TwoNa 2-7: CH_ThreeCH_TwoC (CH_TwoCH_Three)_Two(CH_Two)_FourO
(CH_TwoCH_TwoO)_Three(CH = CHO) (CH_TwoCH_TwoO)
(CH = CHO)_TwoCH_TwoCH_TwoCO_TwoH 2-8: C_TwoH_FiveCH (CH_Three) (CH_Two)_TwoCH (CH_Three)
CH_TwoO (CH_TwoCH_TwoO)_Two(CH = CHO) (CH_TwoC
H_TwoO)_Two(CH = CHO)_Two(CH_Two)_TwoCO_TwoNa 2-9: CH_ThreeC (CH_Three)_TwoCH_TwoC (CH_Three)_Two(C
H_Two)_ThreeO (CH = CHO) (CH_TwoCH_TwoO) (CH = C
HO)_Three(CH_TwoCH_TwoO)_Two(CH_Two)_ThreeCO_TwoNa 2-10: CH_ThreeC (CH_Three)_TwoCH_TwoCH (CH_Three) (C
H_Two)₇O (CH = CHO) (CH_TwoCH_TwoO) (CH = C
HO)_Two(CH_TwoCH_TwoO)_Two(CH = CHO)_Two(CH_Two)
_ThreeCO_TwoNa 2-11: CH_ThreeC (CH_Three)_TwoCH_TwoC (CH_TwoCH_Three)
(CH_Three) (CH_Two)₇O (CH = CHO) (CH_TwoCH_Two
O)_Two(CH = CHO)_Two(CH_TwoCH_TwoO)_Two(CH = C
HO) (CH_Two)_ThreeCO_TwoNa 2-12: CH_ThreeC (CH_Three)_TwoCH_TwoC (CH_TwoCH_Three)
(CH_Three) (CH_Two)₇O (CH = CHO) (CH_TwoCH_Two
O)_Two(CH = CHO) (CH_TwoCH_TwoO)_Two(CH = CH
O)_Two(CH_Two)_ThreeCO_TwoH 2-13: CH_ThreeC (CH_Three)_TwoCH_TwoC (CH_TwoCH_Three)
(CH_TwoCH_TwoCH_Three) (CH_Two)_ThreeCH (CH_Three) CH_TwoC
H_TwoO (CH = CHO)_Five(CH_TwoCH_TwoO)₇(CH_Two)_Five
CO_TwoNa 2-14: CH_Three(CH_Two)₁₁O (CH = CHO)_Two(C
H_TwoCH_TwoO)_Three(CH_Two)_ThreeCO_TwoNa 2-15: CH_Three(CH_Two)₁₁O (CH = CHO) (CH
_TwoCH_TwoO)_Two(CH = CHO)_Two(CH_TwoCH_TwoO)_Two(C
H = CHO) (CH_Two)_ThreeCO_TwoH 2-16: CH_Three(CH_Two)₁₁O (CH_TwoCH_TwoO)_Two(C
H = CHO)_Two(CH_TwoCH_TwoO)_Two(CH = CHO) (C
H_Two)_ThreeCO_TwoNa 2-17: CH_ThreeC (CH_TwoCH_TwoCH_Three)_TwoCH_TwoC (CH
_TwoCH_TwoCH_Three) (CH_Three) (CH_Two)_ThreeCH (CH_Three) CH_Two
CH_TwoO (CH = CHO)_Five(CH_TwoCH_TwoO)₇(CH_Two)
_FiveCO_TwoNa 2-18: CH_ThreeC (CH_TwoCH_TwoCH_Three)_TwoCH_TwoC (CH
_Three) (CH_Three) CH_TwoCH_TwoCH_TwoCH (CH_Three) CH_TwoCH_Two
O (CH = CHO)_Five(CH_TwoCH_TwoO)_Two(CH_Two)_FiveCO
_TwoH 2-19: CH_Three(CH_Two)₁₁O (CH = CHO)_Two(C
H_TwoCH_TwoO)_Two(CH = CHO)_Two(CH_TwoCH_TwoO)
_Two(CH = CHO) (CH_Two)_ThreeCO_TwoNa 2-20: CH_Three(CH_Two)₁₇O (CH_TwoCH_TwoO)_Two(C
H = CHO)_Two(CH_TwoCH_TwoO)_Two(CH = CHO) (C
H_Two)_ThreeCO_TwoNa A compound represented by the above general formula (1) or general formula (2)
The material is added at least on both sides of the support at least
A hydrophilic colloid added to one hydrophilic colloid layer
As the layer, for example, a silver halide emulsion layer, a protective layer, an intermediate layer
Layer, undercoat layer, backing layer and the like. Either layer
When is a multi-layer structure, any layer may be used, but it is particularly preferable.
Or a surface protective layer.

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

In order to use the silver halide photographic light-sensitive material of the present invention as a high-contrast light-sensitive material, it is preferable to contain a hydrazine derivative as a high-contrast agent.

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

[0028]

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In the formula, A is an aryl group or a sulfur atom or
Represents a heterocyclic group containing at least one oxygen atom, and G represents
-(CO) r- group, sulfonyl group, sulfoxy group, -P
(= O) R₁₆-Represents a group or an iminomethylene group, and r represents
Represents an integer of 1 or 2; ₁, A_TwoAre both hydrogen atoms
Or one is a hydrogen atom and the other is a substituted or unsubstituted
Rukylsulfonyl group or substituted or unsubstituted acyl
R represents a hydrogen atom, each of which is substituted or unsubstituted
Alkyl group, alkenyl group, aryl group, alkoxy
Group, alkenyloxy group, aryloxy group, heterocycle
Oxy, amino, carbamoyl or oxycal
Represents a bonyl group. R₁₆Is substituted or unsubstituted respectively
Alkyl, alkenyl, alkynyl, aryl
Group, alkoxyl group, alkenyloxy group, alkynyl
Represents an oxy group, an aryloxy group, or an amino group.

Among the compounds represented by the general formula (H), the compound represented by the following general formula (Ha) is more preferred.

[0031]

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In the formula, R ₁₁ is 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 alkoxyl 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 for 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 are preferably both 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, alkoxyl 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 alkoxyl group. More preferably, it represents a substituted alkyl group substituted by two electron-withdrawing groups, particularly preferably three electron-withdrawing groups. G of R ₁₂
The electron-withdrawing group for substituting the carbon atom substituted with is preferably one having 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, a nitroso group, and a polyhaloalkyl. Group, polyhaloaryl group, alkyl or arylcarbonyl group, formyl group, alkyl or aryloxycarbonyl group, alkylcarbonyloxy group, carbamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, 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.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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Specific examples of other preferred hydrazine compounds are described in US Pat. No. 5,229,248, 4-6.
(1) to (252) described in column 0.

These hydrazine compounds can be synthesized by a known method. For example, US Pat.
No. 9,248, 59-80 column.

The amount of the hydrazine derivative to be added may be an amount which makes the contrast higher (the amount of the higher contrast). 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 silver halide photographic light-sensitive material of the present invention, in order to accelerate the high contrast, it is preferable to use the following nucleation accelerator.

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

[0059]

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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 and 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) will be described below.

[0064]

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[0065]

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[0066]

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[0067]

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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.

[0071]

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[0072]

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Specific examples of other preferred nucleation promoting compounds include the compounds (2-1) to (2-20) and 6-2587 described in JP-A-6-258571.
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 preferable, and a range of 10 ^-5 to 10 ^-2 mol is particularly preferable.

The halogen composition of the silver halide emulsion used in the silver halide photographic 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, It is preferable to use a silver halide emulsion composed of silver chlorobromide containing 60 mol% or more of silver chloride and 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 a 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 "published by the company).

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 form in which the soluble silver salt and the soluble halogen salt are reacted may be any one 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 having 50 mol% or more of silver chloride as a main plane are preferably used, and these are described in US Pat. No. 5,264,264.
No. 337, No. 5,314,798, No. 5,32
No. 0,958, and the like, and intended 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.

Further, 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.

During physical ripening or chemical ripening, zinc, lead,
Lium, iridium, rhodium, ruthenium, osmium
Metal, palladium, platinum, etc.
Can be. In order to obtain high illumination characteristics, iridium
10 per mole of silver logenide ^-9-10^-3In the range of moles
Preferably. To obtain a high contrast emulsion,
Rhodium, ruthenium, osmium and / or renium
10 moles per mole of silver halide^-9-10^-3Mole of
It is preferable to dope in the range.

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-2-208.
No. 2, No. 2-20853, No. 2-20854, No. 2
As the hexadentate ligand and alkali complex described in JP-A-208555, there are general sodium, potassium, cesium and 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 include K ₂ [RuCl ₆ ], (N
H 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.

It is often better to have more of these in the shell. 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 described 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.

As the selenium sensitizer, known selenium sensitizers can be used. For example, U.S. Pat.
No. 499, JP-A-50-71325 and JP-A-60-150.
No. 046, etc. can be preferably used.

The light-sensitive material can contain various compounds for the purpose of preventing fog during the manufacturing 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, aminotriazoles,
Benzotriazoles, nitrobenzotriazoles,
Mercaptotetrazole (particularly 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines,
Mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3a, 7-tetrazaindenes), pentazaindene Many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be added.

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 high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used.

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

In particular, it is preferable to add polysaccharides such as dextran and dextrin 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, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (such as vinyl acetate), acrylonitrile, olefin, styrene or 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-
Dihydroxydioxane), 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 hardeners and the like can be used alone or in combination. These hardeners are RD 176,
17643 (issued in 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 in the silver halide photographic light-sensitive material of the present invention may be either transparent or non-transmissive, but is preferably a transparent plastic support. As the plastic support, those composed of a polyethylene compound (such as polyethylene terephthalate and polyethylene naphthalate), a triacetate compound (such as triacetate cellulose), and a polystyrene compound are used. The thickness of the support is preferably 50 to 25.
0 μm, particularly preferably 70 to 200 μm.

In order to further improve the curl and curl of the support, it is preferable to perform a heat treatment after forming the film. 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 preferred that the compounds described below 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 No. 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]-
(13) Compound described on page [0040] JP-A-6-194777, page (11) [0042]-
(22) Compound described on page [0094] JP-A-6-242533, page (2) [0015]-
(8) Compound described on page [0034] JP-A-6-337492, (3) page [0012]-
Compound described on page (34) [0056] JP-A-6-337494, page (4) [0013]-
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938, (3) page [0011]-
(16) Compound described on page [0066] (6) Hydrazine derivative JP-A-7-114126, page (23) [0111] to
(32) Compound described in [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]-
(29) Compound described in [0068] (10) Redox compound JP-A-4-245243, compound described in 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.

[0105]

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In the formula, R ₃ is 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 alkoxyl 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 formula (A) or the formula [Aa]
The alkyl group in is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms. The amino group is preferably an unsubstituted amino group or an amino group substituted with a lower alkyl group, and the alkoxyl group is preferably a lower alkyl group. An alkoxyl group is preferable, and a phenyl group or a naphthyl group is preferable as the aryl group. These groups may further have a substituent, and the substituent is preferably a hydroxyl group, a halogen atom, an alkoxyl group, a sulfo group. , A carboxyl group, an amide group, a sulfonamide group and the like.

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

[0109]

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[0110]

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These compounds are typically ascorbic acid or erythorbic acid and salts thereof, or compounds derived therefrom, and are commercially available or can be easily synthesized by known synthesis methods.

The main developing agent referred to here is a compound which accounts for 50% or more by mole of the compound 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-one) are used.
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 and 3-pyrazolidones, and a combination of ascorbic acid or a derivative thereof, 3-pyrazolidones and dihydroxybenzenes 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 (sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) 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.

If 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 Its alkali metal salts, nitrilotriacetates, polyphosphates, etc.) and development accelerators (U.S. Pat. No. 2,304,025, JP-B-47-45).
No. 541), 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 and known as a fixing agent can be used.

A water-soluble aluminum salt (aluminum chloride, aluminum sulfate, potassium alum, etc.) and an aldehyde compound (glutaraldehyde or a sulfurous acid adduct of glutaraldehyde, etc.) 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, and particularly preferably in the range of 0 to 0.05 mol / l.

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

The concentration of acetate ions in the fixing solution is preferably less than 0.33 mol / l. 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 of citric acid, tartaric acid, malic acid, succinic acid and the like, 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 drainage pipes, the oxyacids include sulfuric acid,
Nitrous acid, nitric acid, hypochlorous acid and the like are preferable, and as the peroxide, hydrogen peroxide solution and fentonic acid are particularly preferable. Most preferred is hydrogen peroxide.

These oxidizing agents are preferably supplied in the form of a concentrate or a solid agent from the viewpoint of physical 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, the concentrated liquid or solid agent containing the oxidizing agent is mixed with the washing water and supplied. The mixing may be performed before entering the washing tank, or 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 replenished according to the processing amount by detecting the processing amount of the photosensitive material.

The amount of the oxidizing agent to be added to the washing tank is preferably in the range of 1/2 mol to 10 mol equivalents, and particularly preferably in the range of 1/2 mol to 3 mol 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 bactericide 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 thereto. 1: 5-chloro-2-methyl-4-isothiazoline-3-
On 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 For these exemplified compounds, see US Pat. No. 2,767,
No. 172, No. 2,767,173, No. 2,76
No. 7,174, No. 2,870,015, British Patent No. 848,130, and French Patent No. 1,555,416 describe synthesis methods and examples of application to other fields. I have. Some are commercially available, and Predentol O
N, Permachem PD, Topside 800, Topside EG5, Topside 300, Topside 600
(The above are manufactured by Permachem Asia Co., Ltd.), Fine Side J-
700 (manufactured by Tokyo Fine Chemical Company) ProzelGX
L (manufactured by ICI Company).

When the bactericide is supplied into the washing water, it is preferably 0.01 to 50 g / l, more preferably 0.05 to 20 g / l. When contained as a detergent, 0.1 to 50 g based on the detergent.
/ 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_TwoCH_TwoO) a
[CH (CH_Three) CH_TwoO] b (CH _TwoCH_TwoO) cH Here, a, b, and c are each a positive integer.

The compound represented by the general formula (PO) is a compound obtained by adding propylene glycol as a hydrophobic group and ethylene oxide 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) mass% in the total molecule is preferably about 40 to 85%, and particularly preferably, a + c is about 150 and b is about 30 in the general formula.

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.

[0139]

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The compound having a polyalkylene oxide chain is added in an amount of 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%.

The preservatives used in the present invention include phosphoric acid, barbituric acid, urea, acetanilide, oxyquinoline, salicylic acid, quinolinic acid and derivatives thereof, and salts thereof, preferably salicylic acid 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 rinsing time is less than 20 seconds, the effect of the present invention is remarkable, preferably when the rinsing time is less than 16 seconds, and more preferably when the rinsing time is 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 means an aggregate of fine crystals. Granules are obtained by adding a granulation step to powder, and refer to granules having a particle size of 50 to 5000 μm. A tablet is obtained by compressing powder or granules into a certain shape.

Among the above-mentioned 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 solution or a fine powder or a 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. Any means such as forming a coating layer by spraying can be adopted (Japanese Patent Laid-Open Nos. 4-29136 and 4-85).
No. 533, No. 4-85534, No. 4-85535,
4-85536 and 4-172341).

A preferred tablet production method is a method in which a powdery solid processing agent is granulated and then subjected to a tableting step to form the tablet. 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. Furthermore, powder processing agents are described in, for example, JP-A-54-133332, British Patent Nos. 725,892 and 729,862, and German Patent No. 3,733,861 as described in general methods. Can be manufactured.

The bulk density of the above-mentioned solid processing agent is preferably 1.0 to 2.5 g / cm ³ in the case of a tablet from the viewpoint of solubility and the effect of the object of the present invention, and is preferably 1.0 g to 1.0 g. / 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 granules or powder, the bulk density is preferably 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).

[0159] 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 single layer (polymer) resin film or a laminated (polymer) resin film of two or more layers.

When the treating agent is wrapped 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, Hydroxypropyl cellulose type,
Film or binder composed of pullulan, dextran or gum arabic, polyvinyl acetate, hydroxyethylcellulose, carboxyethylcellulose, carboxymethylhydroxyethylcellulose sodium salt, poly (alkyl) oxazoline or polyethylene glycol base Agents are preferably used, and among them,
Especially those of polyvinyl alcohol type and pullulan type,
It is more preferably used from the viewpoint 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 tensile strength of the water-soluble film was 4.9 × 1
0 ⁶ ~4.9 × 10 ⁷ Pa, more preferably a preferably ^{9.8 × 10 6 ~2.45 × 10 8} Pa, particularly preferably ^{1.47 × 10 7 ~9.8 × 10 7} Pa It is. These tensile strengths are measured by the method described in JISZ-1521.

Also, photographic processing agents packaged or bound or coated with a water-soluble film or binder can be used during storage, transport and handling to prevent atmospheric humidity such as high humidity, rain and fog, and In order to prevent damage from sudden contact with water due to splashing or wet hands, it is preferable that the film is wrapped with a moisture-proof packaging material, and the moisture-proof packaging material is preferably a film having a thickness of 10 to 150 μm. Polyethylene film such as polyethylene terephthalate, polyethylene, polypropylene, moisture-proof packaging material, kraft paper, wax paper, moisture-resistant cellophane, glassine, polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide Polycarbonate, acrylonitrile and metal foils such as aluminum, metallized poly Preferably at least one selected from over the film, or may be a composite material using the same.

The moisture-proof packaging material is made of a degradable plastic,
In particular, it is also 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 and 3 -Bio-Valerate)).
pol ", microbial-produced cellulose, 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.

With respect to such a degradable plastic,
"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 operation 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 indicate 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 additional replenishing water. 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 performed using an automatic developing machine from the demand for shortening the developing time, it is a preferable 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 exert the effects of the present invention, a heat transfer material (60 to 130 ° C.) having a temperature of 60 ° C. or more is required for the automatic developing machine.
° C heat roller, etc.) or radiant object with 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 page (5) Lower left column (3) Rinse bath between developing bath and fixing bath JP-A-4-313949 (18), p.
(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".

[0180]

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 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 C solution Chloride 47.5 g of sodium 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 The obtained emulsion was added with a stabilizer (ST-1) of 1.5 × 10 5 per mol of silver. ^-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).

Thereafter, 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.

In addition, except that no hydrazine derivative is contained,
A silver halide emulsion B was prepared in exactly the same manner as in the preparation of the silver halide emulsion A described above. (Support, undercoat layer) 30 W / (m) on both surfaces of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm).
After a corona discharge of ² min), an undercoat layer having the following composition was applied on both sides and dried at 100 ° C. for 1 minute. The numerical value is 1 m ²
Indicates the weight per hit.

2-Hydroxyethyl methacrylate / butyl acrylate / t-butyl acrylate / styrene copolymer (25/30/25/20 mass 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 Second 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-34 015 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 mass) 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 Compound of general formula (1) or (2) Shown in the column of activator in Table 1 (Backing layer) Gelatin 2.0 g Dye F-1 0.05 g Dye F-2 0.04 g Dye F-3 0.02 g Suspended polymer of colloidal silica / vinyl acetate / vinyl pivalinate (75 / 12.5 /12.5% by mass) 0.7 g Sodium polystyrene sulfonate 0.010 g Matting agent (monodisperse poly of average particle size 3 μm) Chill methacrylate) 0.045 g hardener H-1 0.05 g Hardener H-2 0.07g ST-1: 4- hydroxy-6-methyl-l, 3,3
a, 7- tetrazaindene AF-1: 1-phenyl-5-mercaptotetrazole _{H-1: CH 2 = CHSO} 2 CH 2 CONH (CH 2) 2 N
HCOCH ₂ SO ₂ CH = CH ₂

[0187]

Embedded image

[0188]

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[0189]

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Coating samples 101 to 110 were prepared by changing the surfactants used in the above photographic material samples and the amounts thereof added, and the emulsions used at that time as shown in Table 1.

The applicability (occurrence of coating failure) during sample preparation was evaluated as follows. << Coating Failure >> The coating properties of coating samples 101 to 110 at the time of coating were evaluated in five ranks as follows. Rank 5 is the best, and rank 3 or higher is a level that can withstand practical use. 1: Unable to apply coating liquid with uniform film thickness on base 2: When 100,000 m ^{2 is} applied, coating defects occur at 10 or more places 3: When 100,000 m ^{2 is} applied, coating is performed at 2 or more places and less than 10 places Defect generation 4: One coating defect was generated at 100,000 m ² coating. 5: No coating defect was generated. Table 1 shows the evaluation of the obtained coating properties.

After wedge exposure was performed using these samples, development processing was performed under the following processing conditions 1 and 2 to evaluate the characteristics, and the coated samples 101 to 110 were processed under the processing conditions 1. The results obtained are shown in Table 2 as samples 201 to 210, and the results obtained by treating the applied samples 101 to 110 under processing condition 2 are shown in Table 3 as samples 301 to 310. (Processing condition 1) (Process) (Temperature) (Time) Current image 35 ° C 30 seconds Fixed 35 ° C 20 seconds Rinse room temperature 20 seconds Squeeze / dry 50 ° C 30 seconds Total 100 seconds (Processing condition 2): Rapid It is an example of processing.

(Process) (Temperature) (Time) Current image 38 ° C. 15 seconds Fixing 37 ° C. 15 seconds Water washing Normal temperature 15 seconds Squeeze / Drying 50 ° C. 15 seconds Total 60 seconds Each treatment liquid formulation is as follows. Developing solution HQ (per liter of working solution) Pure water 224 ml Diethylenetriaminepentaacetic acid / sodium pentasodium 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-methylbenzotriazole 0 0.21 g 1-phenyl-4-methyl-4-hydroxylmethyl-3-pyrazolidone (dimesone S) 0.85 g hydroquinone 20 g potassium hydroxide 18 g It was dissolved according to the formulation to make a total amount 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 (start 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 Sulfuric acid brings the pH of the working solution to 5.4 And adjust as follows
Finished to liters. Fixing solution (replenisher: 2x 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 to make the pH of the working solution 5.2 Adjust to 5
Finished to 00 ml. For 1 liter of washing water and tap water, the following purification agent 8.8m
1 was added to a washing tank to obtain washing water. (Preparation of Purifying Agent) Pure water 800 g Salicylic acid 0.1 g 35 mass% hydrogen peroxide water 171 g Pluronic F-68 3.1 g Hoksite F-150 15 g Diethylenetriaminepentaacetic acid / 5 sodium 10 g Make up to 1 liter with pure water.

The blackening ratio of the photosensitive material was adjusted to 8%. (Amount of Replenishment of Processing Solution) The developing / fixing replenisher, the purifying agent, and the tap water for dilution of the above-mentioned formulation were directly replenished to the developing tank, the fixing tank, and the washing tank under the following conditions.

[0195] The following evaluation was performed using each developed sample. (Running Experiment) The developing solution, the fixing solution, and the washing water prepared by the above-mentioned formulation were filled 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, dirt in the washing tank, and dirt on the film (adhesion of dirt) were evaluated. << Sensitivity and γ >> A photosensitive material sample is subjected to wedge exposure using a semiconductor laser having a wavelength of 633 nm, and the processing solution and the automatic developing machine LD-T1060 (described above), the developing solution, the fixing solution, and washing with water and oxidizing agent are purified. The developing treatment was carried out under the above conditions using the 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. << dirt of the washing tank >> After operating under the above conditions, dirt due to the scale of the washing tank after running for one week is visually determined,
It was 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 are covered with scale, and the scale is floating in the solution. 2: The roller and the washing tank are scaled, but there is no suspended matter in the solution. 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 conditions, stains attached to the film after one week of running were evaluated visually by a total of five levels. Rank 5 is the best, and rank 3 or higher is a level that can withstand practical use.

Table 1 shows the preparation contents of Samples 101 to 110.
Tables 2 and 3 show the results obtained after the treatment.

[0198]

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[0199]

[Table 1]

[0200]

[Table 2]

[0201]

[Table 3]

From Table 1, it can be seen that the sample of the present invention containing the compound represented by the general formula (1) or (2) according to the present invention has improved coatability as compared with the comparative sample. It is clear. Furthermore, as is clear from Tables 2 and 3, by adding the compound represented by the general formula (1) or (2) according to the present invention, a large number of sheets were processed with low replenishment without deterioration in sensitivity and gamma. After that, it can be seen that the performance deterioration is small, and the stains on the water washing layer and the photosensitive material are also small. In addition, by adding the compound according to the present invention described above, even in rapid processing, the sensitivity and gamma are not deteriorated, and even after a large number of sheets are processed with low replenishment, the performance deterioration is small, and the washing layer is stained and exposed to light. It is clear that the material is less contaminated.

Example 2 The coating samples 101 to 110 produced in Example 1 were used in Example 1.
Exposure was performed in the same manner as described above, and the evaluation was performed using the evaluation method described in Example 1 except that the following processing conditions and processing liquid formulations were used.
Table 4 shows samples 401 to 410 processed under processing condition 1, and Table 5
Samples 501 to 51 processed under processing condition 2 (rapid processing)
Indicates 0. (Processing conditions) Using a developing solution and a fixing solution having the following compositions, an automatic developing machine GR-26 was used to adjust the specific surface area of the developing tank to 8 cm ² /
It was modified so as to have a liter (definition of specific surface area: described in paragraph No. 0085 of JP-A-7-77782) and rapidly processed under the following conditions. After dissolving the tablets with a dissolution mixer, the development and fixing were finished so that 25 tablets would be 1 liter. <Processing liquid formulation> (1) Replenishment developing tablet (D-SR) Preparation of granulated A parts (per liter of liquid used) Diethylenetriamine pentaacetic acid / 5 sodium salt 1.00 g Sulfite 0.25 mol 8-mercaptoadenine 0.06 g 5-methylbenzotriazole 0.27 g Potassium bromide 4.72 g 1-Phenyl-5-mercaptotetrazole 0.03 g Dimezone S 1.1 g Sodium erythorbate (A-1) 35.6 g Isoelite P (Saltwater Port Sugar Refining Co., Ltd.) 20 g D-mannitol (Kao Co., Ltd.) 4 g The above ingredients were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator.
The granulated product was dried at 40 ° C. for 2 hours in a fluidized-bed dryer to obtain a granulated product A part.

Production of granulated B parts (per liter of liquid used) Carbonate 1.0 mol D-mannitol (Kao Corporation) 5 g Lithium hydroxide 3.4 g The above materials were mixed in a commercially available bantam mill for 30 minutes. Then, after granulating at room temperature for 10 minutes with a commercially available stirring granulator, the granulated product is dried at 40 ° C. for 2 hours with a fluidized-bed drier to obtain granulated product B.
Got the parts.

The mixture obtained by thoroughly mixing the above-mentioned parts A and B for 10 minutes is mixed with the machine UD / DFE 30-4.
9. Using a 0 tableting machine (manufactured by Masina Co., Ltd.)
Filling with 83 g, 25 tablets having a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting at 1.5 ton / m ² . (2) Supplementary fixing tablet Preparation of granulated A parts (1 liter of liquid used) Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium bisulfite 10 g Sodium acetate 40 g Isoelite P (Salt Water Port Refining Co., Ltd.) 5 g Pine flow (trade name: Matsutani Chemical) 8 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator, and the granulated product was dried in a fluidized tank. Granules A dried at 40 ° C for 2 hours
Got the parts.

Production of granulated B parts (per liter of liquid used) 10 g of boric acid 3 g of tartaric acid 18 g of sodium hydrogen sulfate 37 g of aluminum sulfate / 18 hydrate 37 g of pine flow (trade name: Matsutani Chemical) 4 g The above material was placed in a commercially available bantam mill. After mixing for 30 minutes and further granulating at room temperature for 10 minutes with a commercially available stirring granulator, the granulated product is dried at 40 ° C. for 2 hours in a fluidized-bed drier to obtain granulated product B.
Got the parts.

The above parts A and B are thoroughly mixed for 10 minutes, and the resulting mixture is extracted from a machine UD / DFE30 ~
25 tablets with a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting at 1.5 ton / m ² using a 40 tableting machine at a filling amount of 11.0 g per tablet.

At the start of running and after running (this
In the light, after running, 1 m of photosensitive material^TwoHit
120 ml of developer, 150 ml of fixer and 150 ml of water
While refilling, replace one unexposed sample and one
Treat each other (20m per day ^TwoEach for 10 days)
After treatment. ) Developed obtained in
About the sample of PDA-65 (manufactured by Konica Corporation,
The blackening density is measured with a digital densitometer) and further examples
As in the case of No. 1, dirt was evaluated.

The obtained results are shown in Tables 4 and 5 below. still,
Before and after the run in the table, at the start of running,
Indicates after running.

[0210]

[Table 4]

[0211]

[Table 5]

From Table 4, it was found that the sample of the present invention did not stain the film or the washing tank even in the system using the solid processing agent. It is apparent that the sample of the present invention also shows excellent effects such as less soiling of the film and less soiling of the washing tank as compared with the comparative sample.

Example 3 Exposure and development were carried out in the same manner as in Example 1 except that the developing solution of the samples 101 to 110 of Example 1 was changed to the AQ developer having the following formulation, and the photographic characteristics were evaluated. did. Table 6
Samples 601 to 61
0 and Table 7 show samples 701 to 710 as samples processed under processing condition 2 (rapid processing). AQ developer Diethylenetriaminepentaacetic acid / 5 sodium 1 g Sodium sulfite 30 g Potassium carbonate 53 g Potassium hydrogen carbonate 17 g 1-Phenyl-4-methyl-4-hydroxylmethyl-3-pyrazolidone 1.5 g 1 water of sodium erythorbate (A-1) 40 g of 1-phenyl-5-mercaptotetrazole 0.025 g of potassium bromide 4 g of 5-methylbenzotriazole 0.21 g of 5,5-dihydroxybenzoic acid 5 g of 8-mercaptoadenine 0.07 g of potassium hydroxide was added, and pH 9.8 was added. To 1 liter. The results are shown in Tables 6 and 7. In the table, before and after the run means before and after the running, respectively.

[0214]

[Table 6]

[0215]

[Table 7]

As compared with the results of Example 1, the effect of the present invention is such that ascorbic acid derivative such as erythorbic acid represented by the aforementioned general formula (A) or [A-a] is used instead of hydroquinone. It can be seen that in a system using a developing solution containing, an even more excellent effect can be obtained.

[0219]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having few coating defects during coating and a method for processing a silver halide photographic light-sensitive material having little stain on a washing water tank and a film surface during development processing. Was.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/30 G03C 5/30 5/31 5/31 5/395 5/395

Claims (6)

[Claims] At least one layer of a support is provided on one side of a support.
Having a light-sensitive silver halide emulsion layer, and having the following general formula
A compound represented by (1) or represented by the following general formula (2)
Silver halide photography characterized by containing a compound
True photosensitive material. General formula (1) R₁₁O (CH_TwoCH_TwoO)_n11(CH = C
HO)_n21(CH_Two)_m1SO_ThreeM₁ General formula (2) R₁₂O (CH_TwoCH_TwoO)_n12(CH = C
HO)_n22(CH_Two)_m2COOM_Two [Wherein, R₁₁, R₁₂Is an alkyl having 5 to 30 carbon atoms
R₁₁And R ₁₂May be the same or different
No. n11, n12, n21 and n22 are respectively 1 to 2
Represents an integer of 0, m1 and m2 are each an integer of 0 to 6
Represent. M₁, M_TwoAre a hydrogen atom and an alkali metal atom, respectively.
Or represents an ammonium group. ] 2. The silver halide photographic light-sensitive material according to claim 1, which contains a hydrazine derivative as a high contrast agent. 3. The processing of the silver halide photographic light-sensitive material of claim 1 or 2, wherein the replenishment amount of the developer is 30 to 150 ml per 1 m ^{2 of the} photographic material, and the replenishment amount of the fixing solution is 1 m. ^A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed at 50 to 300 ml per ² pieces. 4. The processing time of the photosensitive material (Dry to
4. The method according to claim 3, wherein (Dry) is from 10 seconds to 60 seconds. 5. The method for processing a silver halide photographic material according to claim 3, wherein the processing is performed with a processing solution prepared from a solid processing agent. 6. The developing treatment using a developing solution containing a developing agent represented by the following general formula (A):
6. The method for processing a silver halide photographic material according to 4 or 5. Embedded image [Wherein, R ₁ and R ₂ each represent an alkyl group, an amino group, an alkoxyl group or an alkylthio group. R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, when k = 1, X represents -CO- or -CS-, each M ₁ and M ₂ represents a hydrogen atom or an alkali metal atom. ]