JP3148467B2 - Image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a silver halide photographic light-sensitive material.
More specifically, the present invention relates to an image forming method capable of obtaining a super-high contrast image with a developer containing no dihydroxybenzene-based developing agent.

[0002]

2. Description of the Related Art In the field of graphic arts,
In order to improve the reproduction of a continuous tone image or the reproduction of a line image using a halftone dot image, a super-high contrast (particularly, a gamma of 1
(0 or more) is required. As a method for obtaining high-contrast photographic characteristics, a squirrel developing method using a so-called “contagious developing effect” has been used for a long time, but has a disadvantage that a developing solution is unstable and difficult to use.

[0003] On the other hand, as a method of using a more stable developer, US Pat. Nos. 4,224,401, 4,168,977, and 4,166,742,
Nos. 4,311,781, 4,272,606
No. 4,221,857 and No. 4,332,87
No. 8, No. 4,634,661, No. 4,618,5
No. 74, No. 4,269,922, No. 5,650,
Nos. 746 and 4,681,836. This image forming system uses a surface latent image type silver halide photographic material to which a hydrazine derivative is added, in a stable MQ developer having pH of 11.2 to 12.3 (a developer in which hydroquinone and p-aminophenol are used in combination) or PQ developer (hydroquinone and 1-phenyl-3-
(A developing solution using pyrazolidones in combination), and γ is 10
Is a system that obtains a negative image with a super-high contrast exceeding that of this system.
Since it is permissible to add a high concentration of sulfite to the developer, the stability of the developer to air oxidation is dramatically improved as compared to the conventional lith developer.

[0004] With respect to the light-sensitive material for a bright room used in the plate collecting and returning steps, an ultra-high-contrast image forming method is required if, for example, a halftone original and a line drawing original are to be repeatedly turned over. For this purpose, the above-described image forming system using a hydrazine derivative is effective.
2-640, 62-235938, 62-23
No. 5939, No. 63-104046, No. 63-103
No. 235, No. 63-296031, No. 63-3145
Nos. 41 and 64-13545 disclose specific application examples.

[0005] On the other hand, it is known that enedioles such as ascorbic acid function as a developing agent, and is attracting attention as a developing agent having no ecological or toxicological problems. For example, US Pat. No. 2,688,54
No. 9 and 3,826, 654, at least pH 1
It is said that image formation is possible under two or more highly alkaline conditions. However, with these image forming methods, a high-contrast image cannot be obtained. Some attempts have been made to increase contrast in developing systems using ascorbic acid. For example, Zwicky states that when ascorbic acid is used as the only developing agent, a kind of squirrel effect is exhibited (J. Phot. Sc. 27, 185
P. (1979)), the contrast was much lower than that of the hydroquinone development system. U.S. Pat. No. T896,022 and JP-B-49-46939 disclose a system in which a bisquaternary ammonium salt and ascorbic acid are used in combination. Absent. Further, Japanese Patent Application Laid-Open No. 3-2
Nos. 49756 and 4-32838 also describe the combined effect of ascorbic acid and a quaternary salt, but the contrast of the obtained image is not sufficient. Further, Japanese Patent Application Laid-Open No. 5-88
No. 306, ascorbic acid as the only developing agent, p
It is stated that a high contrast can be obtained by keeping H at 12.0 or more, but there is a problem in the stability of the developer. In addition, using a special developer containing ascorbic acid and hydrazine derivative as main components, high sensitivity, stain,
Example of developing a low fog developing system (US Pat.
730,727), but there is no mention of improvement in contrast.

[0006]

As described above, an ultra-high contrast image forming system using a hydrazine derivative is a system using a dihydroxybenzene compound such as hydroquinone as a developing agent. There are several disadvantages from a toxicological point of view. For example, hydroquinone is an undesirable component due to its allergic expression effect, and 1-phenyl-3-pyrazolidones are components with poor biodegradability. Also, high concentrations of sulfites are associated with high C
Indicates OD (chemical oxygen demand). Further, in this image forming system, amines such as those described in U.S. Pat. No. 4,975,354 are usually used in combination, but they are not preferable in terms of toxicity and volatility. Accordingly, an object of the present invention is to provide a novel image forming method capable of obtaining a high-contrast image required in the field of graphic arts using a developing solution which does not have a problem for ecosystems and working environments. It is to provide a method.

[0007]

An object of the present invention is to provide a photographic material having at least one silver halide emulsion layer on a support and containing a hydrazine compound in the emulsion layer or other constituent layers. and after exposure, an image forming method for developing with a developing solution, a hydrazine compound as the hydrazine compound represented by the following general formula (I) used, the emulsion
Layer or other hydrophilic colloid layer,
Amine derivatives, onium salts, disulfide derivatives,
And at least one of hydroxymethyl derivatives
Contain class, and contains a developing agent represented by the following general formula (II) as a developing solution, the current content of the di-hydroxybenzene developing agent is not more than 5 × 10 ^-4 mol / l <br Image forming method, except that a developing solution containing 0.5 mol / liter or more of a carbonate buffer was used. General formula (I)

[0008]

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

[0010]

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A represents a --CO--CO-- group, a thiocarbonyl group or an iminomethylene group, and A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or Or an unsubstituted arylsulfonyl group or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2. However, R ₁ or R ₂
Has a ballast group, R ₁ or R
_It is assumed that at least one of ₂ has a group that enhances adsorption to the surface of silver halide grains, has an R ₁ trialkylammonium group, or has R ₁ has an alkylthio group (including a cycloalkylthio group) or an arylthio group. . However, when R ₁ has the following structure, the substituent R ₄ is -C
If it contains H ₂ CH ₂ O-units 3 or more, and unless containing pyridinium groups.

[0012]

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General formula (II)

[0014]

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In the formula, R ₁ and R ₂ each represent a hydroxy group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonylamino group, mercapto group or alkylthio group. P and Q represent a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group; Are bonded together with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y
Represents a group of atoms forming a 7-membered ring. Y is = O or =
Representing the N-R _3. R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group.

The hydrazine compound represented by the general formula (I) will be described in detail. In the general formula (I), R
_The aliphatic group represented by ₁ preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Also,
This alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, and a carbonamide group.

In the general formula (I), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring and the like.

Particularly preferred as R ₁ is an aryl group. The aryl group or unsaturated heterocyclic group represented by R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, and a ureido. Group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group,
Alkyl or aryl sulfonyl group, alkyl or aryl sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, Phosphoric acid amide group, diacylamino group, imide group,
R ₂ —NH—CO—NR ₂ —CO— groups and the like are mentioned, and preferred substituents are linear, branched or cyclic alkyl groups (preferably having 1 to 20 carbon atoms), aralkyl groups (preferably alkyl groups). A monocyclic or bicyclic C1-C3 moiety, an alkoxy group (preferably having 1-20 carbon atoms), or a substituted amino group (preferably an alkyl group having 1-20 carbon atoms) An amino group), an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), And a phosphoric amide group (preferably having 1 to 30 carbon atoms).
When R ₁ is an aryl group and the substituent is an arylsulfonamide group, the group that substitutes for the aryl group of the arylsulfonamide group has —CH ₂ CH ₂
Groups containing three or more O- units or groups containing a pyridinium group are excluded from the present invention.

The alkyl group represented by R ₂ in formula (I) is preferably an alkyl group having 1 to 4 carbon atoms, such as a halogen atom, a hydroxyl group, a cyano group,
Carboxy group, sulfo group, alkoxy group, phenyl group,
A substituent such as an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, a sulfamoyl group, a nitro group, a heteroaromatic ring group, an R ₁ -NA ₁ -NA ₂ -G ₁ -group; And these groups may be further substituted.

The aryl group is preferably a monocyclic or bicyclic aryl group, for example, one containing a benzene ring. The aryl group may be substituted, and examples of the substituent are the same as those in the case of the alkyl group. As the unsaturated heterocyclic group, a 5- to 6-membered unsaturated heterocyclic group containing at least one of nitrogen, oxygen and sulfur atoms in the ring is preferable, for example, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyridyl group Group, pyridinium group,
A quinolinium group and a quinolinyl group; Pyridyl or pyridinium groups are particularly preferred. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms,
It may be substituted with a halogen atom, an aryl group or the like. The aryloxy group is preferably a monocyclic one,
Further, examples of the substituent include a halogen atom. The amino group is preferably an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms, or an arylamino group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like. The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like. The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or an aryloxycarbonyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Among the groups represented by R ₂ , when G ₁ is a —CO— group, a hydrogen atom, an alkyl group (for example, methyl, trifluoromethyl, 3-hydroxypropyl, 3 A methanesulfonamidopropyl group, a phenylsulfonylmethyl group, an aralkyl group (eg, an o-hydroxybenzyl group), an aryl group (eg, a phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.), and particularly preferably a hydrogen atom.

When G ₁ is a —SO ₂ — group, R ₂ is an alkyl group (eg, a methyl group), an aralkyl group (eg, an o-hydroxybenzyl group), an aryl group (eg, a phenyl group). Or a substituted amino group (eg, a dimethylamino group). G ₁ is -S
In the case of an O- group, preferred R ₂ include a cyanobenzyl group and a methylthiobenzyl group, and when G ₁ is a —PO (R ₂ )-group, R ₂ represents a methoxy group, an ethoxy group, a butoxy group, Phenoxy groups and phenyl groups are preferred, and phenoxy groups are particularly preferred. When G ₁ is an N-substituted or unsubstituted iminomethylene group, preferred R ₂ is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group. As the substituent for R _2, the substituents listed for R ₁ can also be applied. G _{1 in the} general formula (I) is most preferably a —CO— group.

[0023], R ₂ is be as occurring cyclization reaction to form a cyclic structure containing disrupts portion of G ₁ -R ₂ from the remainder, -G ₁ -R ₂ moiety of atoms And more specifically, those which can be represented by the general formula (a). In the general formula (a) -R ₃ -Z ₁ formula, Z ₁ is nucleophilically attacked to G _1, G ₁ -R ₃ -
A group capable of Z ₁ portion was split from the remaining molecule, R ₃ is one obtained by removing one hydrogen atom from R _2, Z ₁ is a nucleophilic attack to G _1, in G _1, R _3, Z ₁ A cyclic structure can be generated.

More specifically, Z ₁ easily undergoes a nucleophilic reaction with G ₁ when the hydrazine compound of the general formula (I) produces the next reaction intermediate by oxidation or the like, and R ₁ -N = N'- G ₁ -R ₃ -Z ₁ R ₁ -N = A group capable of splitting an N group from G ₁ , specifically, OH, SH or NHR ₄ (R ₄ is a hydrogen atom, an alkyl group, an aryl group,- COR ₅ , or —SO ₂ R ₅ ,
₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc., or a functional group which directly reacts with G ₁ such as COOH (here, OH, SH, NH
R ₄ and —COOH may be temporarily protected to generate these groups by hydrolysis of an alkali or the like), or —CO—R ₆ , —C (CNR ₇ ) —R ₆ (R ₆ , R ₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) and reacts with G ₁ by reacting with a nucleophilic agent such as a hydroxyl ion or a sulfite ion. May be a functional group capable of G ₁ ,
The ring formed by R ₃ and Z ₁ is preferably a 5- or 6-membered ring.

Among the compounds represented by the general formula (a), preferred are those represented by the general formulas (b) and (c). General formula (b)

[0026]

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[0027] In the formula, R _b ¹ ~R _b ⁴ is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), (ones preferably having 2 to 12 carbon atoms) alkenyl group, an aryl group (preferably And the like, and may be the same or different. B is an atom necessary to complete a 5- or 6-membered ring which may have a substituent, and m and n
Is 0 or 1, and (n + m) is 1 or 2.
The 5- or 6-membered ring formed by B includes, for example, a cyclohexene ring, a cyclopentene ring, a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and the like. Z ₁ has the same meaning as in formula (a). General formula (c)

[0028]

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In the formula, R _c ¹ and R _c ² represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a halogen atom, and may be the same or different. R _c ³ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. p represents an integer value of 0 to 2, and q represents 1 to 4.
R _c ¹ , R _c ² and R _c ³ may combine with each other to form a ring as long as Z ₁ is capable of intramolecular nucleophilic attack on C ₁ . R _c ¹ and R _c ² are preferably a hydrogen atom, a halogen atom, or an alkyl group, and R _c ³ is preferably an alkyl group or an aryl group. q preferably represents 1-3, p is 1 or 2 when q is 1, p is 0 or 1 when q is 2, p is 0 or 1 when q is 3, and q is 2 Or when 3 is present (CR _c
¹ R _c ² ) may be the same or different. Z ₁ has the same meaning as in formula (a).

[0030] A _1, A ₂ is substituted as hydrogen atom, the number 20 following alkylsulfamoyl Honiru or arylsulfonyl group (preferably having a carbon sum of phenylsulfonyl group or a Hammett substituent constant becomes -0.5 or more Phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a Hammett's substituent constant sum of -0.1.
A benzoyl group substituted to be 5 or more, or a linear or branched or cyclic unsubstituted and substituted aliphatic acyl group (for example, a halogen atom, an ether group,
Examples include a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group. )).
A ₁ and A ₂ are most preferably hydrogen atoms.

R ₁ or R _{2 in} the formula (I) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. Ballast groups are comparatively inert groups with respect to photographic properties which has a carbon number of 8 or more, can be selected for example, an alkyl group, an alkoxy group, an Rukirufeniru group from among such A Rukirufenokishi group. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (I) may have incorporated therein a group which enhances the adsorption to the surface of the silver halide grains. Examples of such adsorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazoles in U.S. Patent Nos. 4,385,108 and 4,459,347, and JP-A-59-195,233.
Nos. 59-200, 231 and 59-201, 04
No. 5, 59-201, 046, 59-201, 0
No. 47, 59-201, 048, 59-201,
No. 049, JP-A Nos. 61-170,733 and 61-2.
70,744, 62-948, 63-234,
No. 244, No. 63-234, No. 245, No. 63-23
4,246.

In the present invention, the above R ₁ or R ₂ incorporates an immobile group such as a ballast group or a polymer group or a group which enhances adsorption to the surface of silver halide grains, or a compound represented by the following general formula (1): It is preferable to use a hydrazine compound represented by X). Formula _{^{(X) (R 1) 3}} N + -R 2 -L 1 - (R 3 -L 2) m - R 4 -NHNH-G 1 -R 5 X - wherein, L ¹ is a single bond, - O- group, -S- group, -NR ⁶ -
Group, -CO- group, -SO ₂ - group, -P (O) (G
² R ⁶ ) — or a combination thereof, wherein L ² is —SO ₂ NR ⁶ —, —NR ⁶ SO ₂ NR ⁶ —, —C
ONR ⁶ -group, -NR ⁶ CONR ⁶ -group, -G ² P
^{(O) (G 2 R 6} ) NR 6 - represents a group. Where G ²
Represents a single bond, an —O— group, or an —NR ⁶ — group, and R ⁶ represents
Represents a hydrogen atom, an aliphatic group or an aromatic group. G ¹ has the same meaning as G _{1 in} formula (I), and R ⁵ is the same as G _{1 in} formula (I)
Is synonymous with R ₂ . R ¹ represents an aliphatic group or an aromatic group (three R ^1's may be the same or different);
R ² , R ³ and R ⁴ represent a divalent aliphatic group or an aromatic group. m is 0 or 1, and X ^- represents a counter anion or a counter anion moiety when forming an inner salt.

In the general formula (X), the aliphatic group represented by R ¹ preferably has 1 to 30 carbon atoms, and particularly has 1 to 20 carbon atoms, such as a linear, branched or cyclic aliphatic group. It is an alkyl group.

The aromatic group represented by R ¹ in the general formula (X) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with the aryl group.

The aliphatic group or the aromatic group represented by R ¹ may be substituted. Typical examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group and a substituted amino group. , Ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkyl or arylthio, alkyl or arylsulfonyl, alkyl or arylsulfinyl, hydroxy, halogen, cyano, sulfo, aryloxycarbonyl , An acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, an imide group, and the like. Preferred substituents include an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), and a substituted amino group (Preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 to 30 carbon atoms), Examples thereof include a ureido group (preferably having 1 to 30 carbon atoms) and a phosphoric amide group (preferably having 1 to 30 carbon atoms). These groups may be further substituted. Further, the three R ¹ in the general formula (X) may be the same or different, and may combine with each other to form a ring.

In the general formula (X), R ² , R ³ , R ⁴
The aliphatic group represented by preferably has 1 to 30 carbon atoms, and is particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. In the general formula (X), R ² ,
The aromatic group represented by R ³ or R ⁴ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with the aryl group. R
Preferred as ² is an alkyl group having 1 to 10 carbon atoms, preferred as R ³ and R ⁴ is an aryl group, and particularly preferred is a group containing a benzene ring. R
The aliphatic group or aromatic group of ² , R ³ and R ⁴ may be substituted, and typical substituents include those listed as the substituent of R ¹ .

In the general formula (X), L ¹ is a single bond, —O
— Group, —S— group, —NR ⁶ — group, —CO— group, —SO ₂
— Group, —P (O) (G ² R ⁶ ) — group or a combination thereof, preferably —SO ₂ NR ⁶ — group, —N
R ⁶ SO ₂ NR ⁶ -group, -CONR ⁶ -group, -NR ⁶ C
An ONR ⁶ — group and —G ² P (O) (G ² R ⁶ ) NR ⁶ — group are represented, particularly preferably a —CONR ⁶ — group.
Among the groups represented by L ² in the general formula (X), a particularly preferred group is a —SO ₂ NR ⁶ — group. In the general formula (X), m is preferably 1 and may be 0.

R ⁶ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom. When the compound represented by the general formula (X) is two or more of R ⁶ and G ²
, They may be the same or different.

In the general formula (X), R ¹ , R ² , R ³ , R ⁴ or R ⁵ incorporates a ballast group or a polymer commonly used in immobile photographic additives such as couplers. It may be something. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, and the like. Can be. Examples of the polymer include those described in JP-A-1-100530.
R ¹ , R ² , R ³ , R ⁴ or R ⁵ in the general formula (X) may have a group in which a group which enhances adsorption to the surface of the silver halide grain is incorporated. Examples of such adsorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups.
08 and 4,459,347, JP-A-59-19
Nos. 5,233, 59-200,231, 59-2
No. 01,045, 59-201, 046, 59-
201,047, 59-201,048, 59
-201,049, 61-170,733, 6
1-270,744, 62-948, 63-2
Nos. 34,244, 63-234,245, 63-
234,246.

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

[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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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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The hydrazine compounds used in the present invention include, in addition to those described above, RESEARCHDISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,207.
No. 4,269,929, 4,276,364
Nos. 4,278,748 and 4,385,108
Nos. 4,459,347 and 4,560,638
No. 4,478,928, British Patent 2,011,3
91B, JP-A-60-179834, JP-A-62-27
Nos. 0,948, 63-29,751, 61-17
Nos. 0,733, 61-270,744 and 62-9
No. 48, EP 217,310 or US 4,68
No. 6,167, JP-A-62-178,246, 63-63
-32,538, 63-104,047, 63
-121,838, 63-129,337, 6
3-223,744, 63-234,244, 63-234,245, 63-234,246,
Nos. 63-294,552 and 63-306,438
No., JP-A Nos. 1-100,530 and 1-105,94
No. 1, No. 1-105,943, JP-A-64-10,2
No. 33, JP-A-1-90,439, Japanese Patent Application No. 63-10 / 1988.
No. 5,682, No. 63-114, No. 118, No. 63-1
Nos. 10,051, 63-114,119, 63-
Nos. 116, 239, 63-147, 339, 63
-179,760, 63-229,163, Japanese Patent Application Nos. 1-18,377, 1-18,378, 1-
Nos. 18,379, 1-15,755, 1-16,
No. 814, No. 1-40,792, No. 1-42,615
No. 1-42,616, 1-123, 693,
Those described in JP-A-1-126,284 can be used.

The amount of the hydrazine compound to be used in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide, more preferably 1 × 10 ^-6 mol.
The range of 10 ⁻⁵ mol to 2 × 10 ⁻² mol is a preferable addition amount.

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

Further, by using a well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used to dissolve and dissolve. An emulsified dispersion can be prepared and used. Alternatively, a hydrazine compound powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used.

[0068] The silver halide photographic <br/> materials used in the present invention, a silver halide emulsion layer or other hydrophilic colloid layer, the amine derivative as a nucleation accelerator, onium salts, disulfide derivatives , or containing hydroxymethyl derivative <br/> conductors.

[0069] As A amine derivatives, for example, JP 60
-140,340, 62-50,829, 62
-222,241, 62-250,439, 6
Compounds described in 2-280,733, 63-124,045, 63-133,145, 63-286,840 and the like can be mentioned. More preferably as an amine derivative, JP-A-63-124,045, 63-133,1
Nos. 45 and 63-286,840, etc., compounds having a group adsorbing to silver halide, or JP-A-62-22
Compounds having a sum of 20 or more carbon atoms described in US Pat. No. 2,241 or the like, US Pat. No. 4,975,354, EP458P70
Examples thereof include amine compounds having an ethylene group described in No. 6A and the like, and compounds described in JP-A-62-50829. As the onium salt, a pyridinium salt, an ammonium salt or a phosphonium salt is preferable. Preferred examples of the pyridinium salt include the compounds described in Japanese Patent Application No. 5-97866. Also,
Preferred examples of the ammonium salt are described in JP-A-62-2.
Compounds described in JP-A Nos. 50,439 and 62-280,733 can be exemplified. Examples of preferred phosphonium salts are described in JP-A-61-16793.
No. 9, 62-280, 733 and the like. Examples of the disulfide derivative include compounds described in JP-A-61-198,147. Examples of the hydroxymethyl derivative include, for example, U.S. Patent Nos. 4,698,956 and 4,777,118, EP23
No. 1,850, JP-A-62-50,829 and the like, and more preferred are diaryl methacrylol derivatives .

Next, specific examples of the nucleation accelerator will be shown. However, the present invention is not limited to the following compounds.

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The optimum addition amount of these compounds varies depending on the kind thereof, but 1.0 × 1 per mole of the hydrazine compound.
0 ^-2 mol to 1.0 × 10 ² mol, preferably 1.0 × 10 ² mol
It is desirable to use in the range of 10 ^-1 mol to 5.0 × 10 mol. These compounds are suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Also, by an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. Objects can also be created and used. Alternatively, powders of these compounds can be dispersed in water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The halogen composition of the silver halide emulsion used in the present invention is not particularly limited.
An appropriate composition can be selected from silver chlorobromide, silver chloroiodobromide, silver bromoiodide, and the like, and the silver chloride content is preferably 30 mol% or more. Various methods known in the field of silver halide photographic materials can be used for preparing the silver halide emulsion used in the present invention. See, for example, Chimie et Physique by P. Glafkides.
Photographiqu ”(Paul Montel)
Publisher, 1967), GF Duffi
ne), "Phpotographic Emulsion Chemistry" (The Four
Cal Press) (published by The Focal Press, 1966)
Making and Coating Photographic Emulsio by VL Zelikman et al.
n) "(The Focal Press, 1
964) and the like.

As a method of reacting a water-soluble silver salt (aqueous silver nitrate solution) with a water-soluble halogen salt, any of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. One type of the double jet method is to maintain a constant pAg in the liquid phase in which silver halide is formed, that is, a control method.
The double jet method can also be used. Further, it is preferable to form grains by using a so-called silver halide solvent such as ammonia, thioether and tetra-substituted thiourea. More preferred are tetrasubstituted thiourea compounds, which are described in JP-A-53-82408 and JP-A-55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. According to the control double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal system and a narrow grain size distribution, and to prepare an emulsion used in the present invention. It is a useful tool for

The average grain size of the silver halide in the photographic emulsion used in the present invention is 0.5 μm or less, particularly preferably 0.1 to 0.4 μm. The silver halide grains may have a relatively wide grain size distribution, but preferably have a narrow grain size distribution, particularly 90% of the weight or number of silver halide grains.
Is preferably within ± 40% of the average particle size. (In general, such an emulsion is called a monodisperse emulsion.) The silver halide grains in a photographic emulsion may have regular crystals such as cubic or octahedral, and may be spherical or research disclographic.
osure 22534 (Jan. 1983), tabular silver halide grains having a high aspect ratio can be used. Further, those having a composite form of these crystal forms may be used. The silver halide grains may have a uniform inner or surface layer or different layers. Also, a mixture of two or more kinds of silver halide emulsions separately formed such as internal latent image type silver halide emulsion grains and surface latent image type emulsion grains described in JP-B-41-2068 is used. Is also good. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof and the like are co-present in the course of forming silver halide grains or physical ripening. Is also good. In the present invention, a silver halide emulsion particularly suitable as a light-sensitive material for line drawing and halftone dot formation is silver 1 emulsion.
It is an emulsion prepared in the presence of 10 ^-8 to 10 ^-5 mol of iridium salt or its complex salt per mol. In the above, it is desirable to add the above amount of iridium salt before the completion of physical ripening in the production process of the silver halide emulsion, particularly at the time of grain formation. The iridium salt used here is a water-soluble iridium salt or iridium complex salt, for example, iridium trichloride, iridium tetrachloride, potassium hexachloroiridium (III), hexachloroiridium (IV)
And potassium hexachloroiridium (III).

The silver halide emulsion may be a so-called unripened emulsion (primitive emulsion) which is not subjected to chemical sensitization, but may be chemically sensitized. For chemical sensitization, H. Frieser, "Die Grundlagen der Photographis
chen Prozesse mit Silver halogeniden '' Akademische
The method described in Verlagsgesswlschaft, (1968) can be used. That is, sulfur sensitization using a compound containing sulfur capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanines), reducing substances (eg, stannous salts, amines, Reduction sensitization using hydrazine derivatives, formamidinesulfinic acid, silane compounds), noble metal sensitization using noble metal compounds (for example, gold compounds and complex salts of Group VIII metals of the periodic table such as platinum, iridium and palladium) Etc. can be implemented alone or in combination. A preferred chemical sensitization method is gold sulfur sensitization.

The silver halide emulsion of the present invention preferably contains a transition metal complex. As the transition metal, R
h, Ru, Re, Os, Ir, Cr and the like.
Examples of ligands include nitrosyl and thionitrosyl bridging ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand. Ligand, selenocyanate ligand,
Terrocyanate, acid and aquo ligands. If an aquo ligand is present, it is preferred to close one or two of the ligands. Specifically, in order to contain a rhodium atom, a metal salt of an arbitrary form such as a single salt or a complex salt can be added at the time of particle preparation. Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like. Preferably, a water-soluble trivalent rhodium complex compound such as hexachlororhodium (II
I) acid or its salt (ammonium salt, sodium salt,
Potassium salt). The addition amount of these water-soluble rhodium salts is in the range of 1.0 × 10 ⁻⁶ mol to 10 × 10 ⁻³ mol per mol of silver halide. It is preferably from 1.0 × 10 ⁻⁵ mol to 1.0 × 10 ⁻³ mol, particularly preferably from 5.0 × 10 ^{−5 to} 5.0 × 10 ⁻⁴ mol.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized to a relatively long wavelength blue light, green light, red light or infrared light by a sensitizing dye. As a sensitizing dye,
Cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine thixo, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure Item 17643 IV-A (1978
Item 1831, Item X (Dec. 1979, p.43)
It is described in the literature described or cited in 7).
These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. The emulsion may contain a dye which has no spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization together with the sensitizing dye. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure Vol.
7643 (issued in December 1978), page 23, IV, section J.

In the silver halide light-sensitive material according to the present invention, the hydrophilic colloid layer may contain a water-soluble dye for various purposes as a filter dye, an antiirradiation dye or the like. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are described in German Patent 616,007 and British Patent 584,6.
No. 09, No. 1, 117, 429, JP-B-26-777
No. 7, No. 39-22069, No. 54-38129,
JP-A-48-85130, JP-A-49-99620, JP-A-49-114420, JP-A-49-129537, PB
Report No. 74175, Photographic Abstract 128 ('21), and the like.

As a binder or protective colloid which can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, proteins such as casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch, polyvinyl alcohol, Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. it can. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Brain of the Society of Scientific Photographic Japan (Bull. SOC. SCI. Pho
to. Japan) No. Enzyme-treated gelatin as described on pages 16, 30 (1966) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. Azoles,
For example, benzothiazolium salts, nitroimidazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole ( In particular, 1-phenyl-5-mercaptotetrazole, etc., mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxadolinthione, azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted ( 1,3,3a, 7) Tetraazaindenes, pentaazaindenes, and many other antifoggants or stabilizers, such as benzenesulfonic acid amides Compounds can be added. Among them, particularly preferred are benzotriazoles (for example, 5-methylbenzotriazole). Further, these compounds may be contained in the treatment liquid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chrom alum, chromnad acetate), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoinnad), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compound (1,3,5
-Triacryloyl-hexahydro-s-triazine, etc.), mucohalic acids (such as mucochloric acid, mucophenoxycyclolic acid) and the like can be used alone or in combination.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsification dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration For various purposes such as contrast enhancement, sensitization, and the like, various surfactants may be contained.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in a photographic emulsion layer or other hydrophilic colloid layers for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination;
Alternatively, a polymer having a monomer component of a combination of acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxylalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, and the like is used. Can be.

The support used in the light-sensitive material of the present invention is a flexible support of paper or synthetic paper on which an α-olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer) or the like is laminated. , Metals and the like. Among them, polyethylene terephthalate is particularly preferred. Examples of the undercoat layer to be cut for use in the present invention include an undercoat layer formed of an organic solvent containing polyhydroxybenzenes described in JP-A-9-3972 and JP-A-49-1111.
No. 8, No. 52-10490 and the like. In addition, the surface of the undercoat layer can usually be treated scientifically or physically. Examples of the treatment include a surface activation treatment such as a chemical treatment, a mechanical treatment, and a corona discharge treatment.

Next, the developer used in the present invention will be described. The developer of the present invention does not substantially contain a dihydroxybenzene-based developing agent as described above, and the main developing agent is a compound represented by the general formula (II). The developer of the present invention preferably contains a 1-phenyl-3-pyrazolidone type auxiliary developing agent and / or a p-aminophenol type auxiliary developing agent as an auxiliary developing agent.

The compound of the formula (II) which is a developing agent of the present invention will be described in detail. In the general formula (II),
R ₁ and R ₂ are each a hydroxy group or an amino group (including those having, as a substituent, an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-butyl group, a hydroxyethyl group, etc.) ), Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.),
Represents an alkoxycarbonylamino group (such as a methoxycarbonylamino group), a mercapto group, or an alkylthio group (such as a methylthio group or an ethylthio group). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

As described above, P and Q are bonded to each other,
R ₁ and R ₂ are substituted with two vinyl carbon atoms and Y is
Atoms forming a 5- to 7-membered ring with the carbon atoms that are substituted
Groups may be represented . As a specific example of the 5- to 7-membered ring ,-
_{O -, - C (R 3} ) (R 4) -, - C (R 5) =, - C
(= O) -, - N (R 6) -, - N =, include those formed by combining. Where R ₃ , R ₄ , R ₅ ,
R ₆ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group or a sulfo group may be mentioned as a substituent), or an aryl group which may be substituted having 6 to 15 carbon atoms. Represents a group (an alkyl group, a halogen atom, a hydroxy group, a carboxy group, or a sulfo group can be given as a substituent), a hydroxy group, or a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 7- membered ring.

Examples of the 5- to 7-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring and a uracil ring. And as an example of a preferred 5- to 6-membered ring,
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azacyclohexenone ring,
A uracil ring can be mentioned.

Y is a group composed of ＯO or ＮN—R ₃ . Here, R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group (eg, methyl, ethyl), an acyl group (eg, acetyl), a hydroxyalkyl group (eg, hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg, sulfomethyl, sulfoethyl), a carboxy group. Represents an alkyl group (for example, carboxymethyl, carboxyethyl). Specific examples of the compound of the general formula (II) are shown below, but the present invention is not limited thereto.

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Among them, preferred is ascorbic acid or erythorbic acid (stereoisomers). The general range of the amount of the compound of the general formula (II) used is:
The amount is from 5 × 10 ⁻³ mol to 1 mol, particularly preferably from 10 ⁻² mol to 0.5 mol, per liter of the developer.

1-phenyl-3 as an auxiliary developing agent
-Examples of pyrazolidone or a derivative thereof include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4.
-Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxylmethyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, 1-p
-Aminophenyl-4,4dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. Examples of the p-aminophenol auxiliary developing agent include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, There are methyl-p-aminophenol, p-benzylaminophenol and the like, and among them, N-methyl-p-aminophenol is preferable.
When a combination of the compound represented by the general formula (II) of the present invention and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the latter is usually used in an amount of 10 ⁻³ mol / L to 0.1%. It is preferably used in an amount of from 10 ^-3 mol / l to 0.06 mol / l, more preferably from 10 ^-3 mol / l.

[0109] In the present invention, the concentration in the developer of the di-hydroxy benzenes Ri <br/> Oh below 5 × 10 ^-4 mol / l, such included dihydroxybenzenes exactly Ikoto virtuous
Good.

The developing solution of the present invention may contain a sulfite such as sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite, sodium formaldehyde sodium bisulfite as a preservative.
Sulfite is used at 0.01 mol / l or more. If used in a large amount, silver halide emulsion grains are dissolved, causing silver stains. In addition, the amount of addition should be minimized because it also increases COD (chemical oxygen demand).

The pH of the developer used in the development processing of the present invention is preferably in the range of 10.0 to 12.0. More preferably, the range is from 10.4 to 12. pH 12.
If the value is 0 or more, stains and black spots in the non-image portion rapidly increase, which is not preferable. If the pH is 10.0 or less, a sufficient contrast cannot be obtained. Alkali agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. The developing solution of the present invention includes saccharides (for example, saccharose), oximes (for example, acetoxime) described in JP-A-60-93433,
PH buffers such as phenols (e.g., 5-sulfosalicylic acid), silicates, sodium phosphate tribasic, and potassium phosphate tribasic can be used. The concentration of the buffer was 0.
It is preferably at least 3 mol / l. Boron compounds such as boric acid and sodium metaborate are not preferred because they may react with the compound of the present invention represented by the general formula (II) and inactivate them. However, in the developer used in the present invention,
Contains 0.5 mol / l or more of a carbonate buffer.
Excluding

Development inhibitors such as potassium bromide and potassium iodide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol; and indazoles such as 5-nitroindazole Anti-foggants such as benzimidazole compounds such as sodium compounds, benzimidazole compounds such as sodium 2-mercaptobenzimidazole-5-sulfonate, and benztriazole compounds such as 5-methylbenztriazole. Research Disclosure Vol. 176 , No. 17643, Section XXI (December Issue, 1978). It may also contain an amine compound described in U.S. Pat. No. 4,269,929, JP-A-61-267759 and Japanese Patent Application No. 1-291818. Further, a color tone agent, a surfactant, a hardener and the like may be contained as necessary. The developer of the present invention includes European Patent Publication 13
No.6582, UK Patent No.95886678, US Patent No.3
Amino compounds such as alkanolamines described in Japanese Patent No. 232761 and JP-A-56-106244 can be used for the purpose of accelerating development and increasing contrast.

The fixing solution used in the present invention is an aqueous solution containing thiosulfate, and has a pH of 3.8 or more, preferably 4.2 to 4.2.
7.0. Sodium thiosulfate as fixing agent,
There are ammonium thiosulfate and the like, but ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of the fixing agent used can be changed as appropriate, and is generally about 0.1 to about 6 mol / l. The fixing solution may contain a water-soluble aluminum salt acting as a hardener, and examples thereof include aluminum chloride, aluminum sulfate, potassium alum and the like. Tartaric acid, citric acid, gluconic acid or derivatives thereof can be used alone or in combination of two or more in the fixing solution. It is effective that these compounds contain at least 0.005 mol / l per liter of fixing solution, and particularly 0.01 to 0.03 mol / l is particularly effective. The fixing solution may optionally contain a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid, boric acid), a pH adjuster (eg, sulfuric acid, ammonia), a chelating agent capable of softening hard water, Surfactants, wetting agents, fixing accelerators, and compounds described in JP-A-62-78551 can be included. Examples of the fixing accelerator include thiourea derivatives described in JP-A Nos. 45-35754, 58-122535 and 58-122536, alcohols having a triple bond in the molecule, and U.S. Pat.
Thioether compounds described in JP-A-59-59, and compounds described in JP-A-2-44355 may be used.
In addition, compounds described in JP-A-64-4739 can be used as a dye elution accelerator.

In the developing method of the present invention,
After the fixing step, it is treated with washing water or a stabilizing solution and then dried. 3 per m ^{2 of} silver halide photosensitive material
It can also be treated with less than a liter of replenishing water (zero, ie also including rinsing water) or a stabilizing solution.
That is, not only water saving processing is enabled, but also piping for installing the automatic processing machine can be eliminated. As a method for reducing the replenishing amount of washing water, a multi-stage countercurrent method (for example, 2
Stage, three stage, etc.) are known. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in a clean direction, that is, a processing solution that is not stained with the fixing solution is sequentially contacted, so that the efficiency is further improved. Washing is performed. When the washing is performed with a small amount of water, a method disclosed in JP-A-63-1
It is preferable to provide a squeeze roller and a cross-over roller washing tank described in JP-A Nos. 8350 and 62-287252. In addition, various oxidizing agents may be added or filters may be combined in order to reduce the pollution load which is a problem when washing with a small amount of water. In the water-saving treatment or the non-pipe treatment, it is preferable to apply a means for preventing the washing water or the stabilizing solution.

[0115] As means for prevention, Japanese Patent Application Laid-Open No. 60-263
No. 939, No. 60-26394.
Method using magnetic field described in No. 0, 61-13163
No. 2, JP-A-62-115154 and JP-A-62-15395.
No. 2, No. 62-220951, No. 62-209532
Can be used.
LFWest, "Water Quality Criteria" Photo.
Sci. & Eng., Vol. 9 No. 6 (1965), MWReach, "Microbi
biological Growths in Motion- picture Processing ", SM
PTE Jounal Vol.85 (1976), RODeegan, "Photo Proces
sing Wash Water Biocides ", J. Imaging Tech., Vol. 10,
No. 6 (1984), and JP-A-57-8542 and 57-542.
No. 56143, No. 58-105145, No. 57-13
No. 2146, No. 58-18631, No. 57-9753
No. 0, No. 57-157244 and the like can be used in combination. In addition, RTKreiman
J. Imaging Tech., 10 (6) p.242 (1984), isothiazolidine compounds, Research Disclosure No. 2
The compound described in Vol. 05, No. 20526 (1981, No. 4) can be used in combination as a microbiocide.
In addition, compounds such as those described in Hiroshi Horiguchi, "The Chemistry of Bactericidal and Fungicide", Sankyo Shuppan (Showa 57), "Handbook of Bacterial and Fungicide Technology", Hakuhodo, Japan Society of Bactericidal and Fungicide (Showa 61) May be included.

In the method of the present invention, when rinsing with a small amount of rinsing water, it is preferable to adopt a rinsing step configuration as disclosed in JP-A-63-143548. Further, part or all of the overflow from the washing or stabilizing bath caused by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in
As described in JP-A-235133, it can also be used for a processing solution having a fixing ability, which is the preceding processing step. In the development processing in the present invention, the development time is 5 seconds to 3 seconds.
Minutes, preferably 8 seconds to 2 minutes, the development temperature is 18 ° C
-50 ° C is preferred, and 24 ° C-40 ° C is more preferred.

The fixing temperature and time are from about 18 ° C. to about 50 ° C.
5 seconds to 3 minutes at ° C is preferable, and 6 seconds to 2 minutes at 24 ° C to 40 ° C is more preferable. The temperature and time for washing (or stabilization) in which water can be sufficiently fixed within this range and the sensitizing dye can be eluted to such an extent that no residual color occurs are preferably 5 to 50 ° C. and 6 seconds to 3 minutes. , 15-40 °
C, 8 seconds to 2 minutes is more preferable. The developed, fixed and washed (or stabilized) photosensitive material is squeezed with washing water, ie, dried through a squeeze roller. Drying is carried out at about 40 ° C. to 100 ° C., and the drying time may be appropriately changed depending on the surrounding conditions, but usually about 4 seconds to 3 minutes, and particularly preferably 40 ° C. to 80 ° C. for about 5 hours. Seconds to 1
Minutes. When performing development processing for 100 seconds or less by Dry to Dry, in order to prevent development unevenness peculiar to rapid processing, a rubber-made roller as described in JP-A-63-151943 is used as a roller at the exit of the development tank. As described in JP-A-63-151944, the discharge flow rate for stirring the developing solution in the developing tank is set to 10 m / min or more. As described in the above item, it is more preferable to perform stronger stirring at least during the development processing than during the standby. For further rapid processing, it is more preferable that the configuration of the roller of the fixing tank is an opposing roller in order to increase the fixing speed. By configuring with opposing rollers, the number of rollers can be reduced,
The processing tank can be made smaller. That is, it is possible to make the self-developing machine more compact.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, the development processing method and the like, and for example, those described in the following places can be preferably used. Item The relevant place 1) Nucleation accelerator JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10, general formulas (II-m) to (II-p) ) And compound examples II-1 to II-22 and compounds described in JP-A-1-179939. 2) Silver halide emulsion and JP-A-2-97937, page 20, lower right column, line 12 to production thereof, page 21 lower left column, line 14, JP-A-2-12236, page 7, right upper column, 19 The selenium sensitization method described from line 12 to line 12 in the lower left column of page 8, and Japanese Patent Application No. 3-189532. 3) Spectral sensitizing dyes JP-A-2-12236, page 8, lower left column, line 13 to right lower column, line 4, JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left Column 20, line 20. Further, spectral sensitizing dyes described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, Japanese Patent Application Nos. 3-189532 and 3-4111064. 4) Surfactant JP-A-2-122363, page 9, upper right column, line 7 to right lower column, line 7, and JP-A-2-854424, page 2, lower left column, line 13 to page 4, right Line 18 in the bottom column. 5) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, furthermore, JP-A 1-237538 Thiosulfinic acid compounds described in the gazette. 6) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 7) Compound having an acid group JP-A-2-103536, page 18, lower left column, line 6 to page 19, upper left column, line 1. 8) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, line 15 to plasticizer, page 19, upper right column, line 15; 9) Hardener From page 5, right upper column, line 5 to page 17, JP-A-2-103536. 10) Dyes Dyes in lines 1 to 18 of the lower right column on page 17 of JP-A-2-103536, solid dyes described in JP-A-2-94638 and JP-A-3-185773. 11) Binder JP-A 2-18542, page 3, lower right column, lines 1 to 20. 12) Black potting inhibitor A compound described in US Pat. No. 4,956,257 and JP-A-1-18832. 13) Redox compounds The compounds represented by the general formula (I) (especially compounds 1 to 50) in JP-A-2-301743 and the compounds represented by the general formulas (3 to 20) described in JP-A-3-174143, pp. 3-20. R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648.14) Monomethine compound Compounds of the general formula (II) of JP-A-287532 (especially compound examples II-1 to II-26). 15) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to page 12, lower left column, and EP452772A. 16) Developing solution and developing method JP-A-2-103536, page 19, upper right column, line 16 to page 21, upper left column, line 8

[0119]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 <Preparation of developing solution> Formula (I)
A developer containing the compound of the present invention represented by I) was prepared. As a comparative example, a developer mainly containing hydroquinone was also prepared.

[0121]

[Table 1]

<Measurement of COD> According to 18 of JIS K 0102, the developer prepared in Table 1 was diluted 100-fold, and its COD (chemical oxygen demand) was measured. The results are also shown in Table 1. As can be seen from Table 1, the developing solution of the present invention shows a very low COD value of 1/10 or less as compared with a developing solution using a conventional hydroquinone-based developing agent. This is not only because the developer itself is less dangerous from an ecological and toxicological point of view, but also when the developer is processed using a well-known automatic developing machine, the water in the washing tank is reduced. This indicates that the burden on the environment derived from the developer components mixed in the bar flow, that is, the degree of pollution of the washing wastewater to the environment is low.

Example 2 <Preparation of silver halide photosensitive material> 1.5 × 10 ^-4 mol / l of 1,3-dimethyl-2
An aqueous gelatin solution containing imidazolidinethione and 7 × 10 ⁻² mol / l of sodium chloride was kept at 40 ° C., and a mixed aqueous solution of sodium chloride and sodium bromide (2 × 10 ⁻⁷ mol / mol of silver) was added to this solution. Of potassium hexachloroiridate (III) and 3 × 10 ⁻⁷ mol of rhodium hexachloride (III)) and an aqueous silver nitrate solution by a double jet method over 30 minutes.
A silver chlorobromide emulsion (silver bromide content: 30 mol%) composed of a monodisperse cube (average particle size: 0.25 μm) (coefficient of variation: 9.5%) was prepared. After completion of the particle formation, water was washed in accordance with a conventional method to remove soluble salts, and then gelatin was added, and sodium chloride, sodium bromide and sodium hydroxide were further added so that pAg = 7.5 and pH = 6.0. ,
Sodium thiosulfate was added to this emulsion at 2 × 1 per mole of silver.
0 ^-5 molar, was added 3 × 10 ^-5 mol of potassium chloroaurate light, was subjected to chemical sensitization for 40 minutes at 60 ° C..

After the chemical sensitization, the compound (a) was added at 1 × 10 ⁻³ mol per mol of silver to prepare an emulsion A. The following compound (b) was added as a sensitizing dye to Emulsion A in an amount of 5 × 10 ⁻⁴ mol per mol of silver.

[0125]

Embedded image

This emulsion was designated as A0, and the hydrazine compounds I- 67 , I- 68 and I- 70 of the general formula (I) were added in an amount of 6 × 10 ^-4 mol per mol of silver , as shown in Table 2.
And emulsions A1, A2 and A3, respectively.

Further, each emulsion contained 4 × 10 4 mol / mol of silver.
^-3 mol of any one of nucleation accelerators A- 5, A- 54 and A- 73, 4 × 10 ^-4 mol of mercapto compound represented by (c) per mol of silver, 1 mol per mol of silver × 10 ^-3 moles of 5-methylbenzotriazole, U.S. Pat.
No. 25,620, the polyethyl acrylate compound described in Production Formulation 3 is 0.8 g / m ² as a polymer latex, 40 mg / m ² is sodium p-dodecylbenzenesulfonate as a coating aid, and 1,3 is a hardening agent. 1 m of divinylsulfonyl-2-propanol
^It was added so as to be 100 mg per ² . The prepared emulsion had a dye layer having absorption from blue to green on the back surface side, and was coated on a subbed polyethylene terephthalate support at a silver amount of 3.4 g / m ² . .

[0128]

Embedded image

A gelatin layer was coated as a protective layer on the silver halide emulsion layer. The amount of gelatin in the protective layer is 1 m ²
And the protective layer contains 40 m of amorphous SiO ₂ having an average particle diameter of 3.5 μm as a matting agent in the protective layer.
g / m ^2, silicone oil 20 mg / m ^2, a p- sodium dodecylbenzenesulfonate as a coating aid 60 mg / m ^2, and the following fluorine-based surfactant 5m
g / m ² .

[0130]

Embedded image

The emulsions A0, A1, A2, A
Table 2 summarizes the samples prepared from No. 3.

[0132]

[Table 2]

<Exposure and Development> The above sample was exposed to tungsten light of 3200 ° K. for 5 seconds through an optical wedge for sensitometry, and D- 4 of the developer having the above composition (Table 1) was obtained. , D- 5
Using, after a 30-second development at 35 ° C., fixing, washing, and drying was performed. The fixer used was GR-F1 manufactured by Fuji Photo Film Co., Ltd. For this development processing, an automatic developing machine FG-680A manufactured by Fuji Photo Film Co., Ltd. was used.

The sensitivity was shown by a relative value of the reciprocal of the exposure amount giving a density of 1.5. As an index (γ) representing the contrast of an image, a point between fog + density 0.3 and a point fog + density 3.0 on the characteristic curve is connected by a straight line, and the slope of this straight line is expressed as a γ value. That is, γ = (3.0−0.3)
/ [Log (exposure to give a density of 3.0) -log (exposure to give a density of 0.3)]. The black pots were observed on a loupe for the actual portion and evaluated on a 5-point scale. “5” indicates the best level without black spots, and “1” indicates the worst level of black spots. "3" is a limit level at which the occurrence of black spots is practically allowable.

[0135]

[Table 3]

[0136] <Results> As shown in Table 3, according to the images forming method of the present invention, high sensitivity, contrast (gamma) is, pH 10 or more, it can be seen that obtained with 12 following the developing solution.

Example 3 <Preparation of silver halide light-sensitive material> In place of the sensitizing dye (compound b) of the sample of Example 1, the following compound (e) was added in an amount of 5 × 10 ^-4 mol per mol of silver. Emulsion A4 was prepared in the same manner as in Example 1 except that the emulsion was used. The hydrazine compounds I- 67 , I- 68 and I- 7 represented by the general formula (I) as shown in Table 4 were added to this emulsion.
0 and nucleation accelerators A-54 and A- 70 were prepared in the same manner as in Example 1.

[0138]

Embedded image

[0139]

[Table 4]

<Exposure and Development Processing> The above samples were subjected to the same exposure and development processing as in Example 1. The developer used was selected from the developers shown in Table 1 .
D- 4 , D- 7, D-8, and D-9 were selected.

<Results> The results obtained are shown in Table 5.

[0142]

[Table 5]

As can be seen from this table, when an image forming method using a silver halide light-sensitive material containing the compound of the present invention and a developing solution is used, a high-contrast image free from black spots and fog can be obtained with high safety. It can be obtained using a developer.

Claims (3)

(57) [Claims] 1. A photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine compound in the emulsion layer or another constituent layer, is exposed and then developed with a developing solution. in the image forming method, the hydrazine compound is represented by the following formula (I), emulsion layer or other
Amine derived as nucleation accelerator in hydrophilic colloid layer
, Onium salts, disulfide derivatives, and hydroxy
Of Shimechiru derivatives, containing a developing agent containing at least one, and the developing solution is represented by the following formula (II), the content of di-hydroxybenzene developing agent is 5 ×
An image forming method characterized in that the amount is 10 ⁻⁴ mol / l or less (excluding a developer containing a carbonate buffer of 0.5 mol / l or more). General formula (I) In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group,
Represents an alkoxy group, an aryloxy group, an amino group, a hydrazino group, a carbamoyl group, or an oxycarbonyl group, and G ₁ represents a —CO— group, a —SO ₂ — group, a —SO— group, , -CO-CO- group, thiocarbonyl group, or an iminomethylene group, A _1, A ₂ are both hydrogen atoms or one is a hydrogen atom and the other a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted Represents a substituted arylsulfonyl group or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as defined for R ₂ ,
It may be different from R ₂ . However, at least one of R ₁ or R ₂ has a ballast group, at least one of R ₁ or R ₂ has a group that enhances adsorption to the surface of silver halide grains, or R ₁ has a trialkylammonium group. Or, R ₁ has an alkylthio group (including a cycloalkylthio group) or an arylthio group. Where R
_{When 1} has the following structure, the substituent R ₄ is —CH ₂ C
Except when including the case and pyridinium group comprising H ₂ O-units 3 or more. Embedded image General formula (II) In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group,
Represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P, Q
Is a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group,
Represents a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or P and Q are bonded to each other, and two vinyl carbon atoms substituted with R ₁ and R ₂ are substituted with Y. Represents a group of atoms forming a 5- to 7-membered ring together with the carbon atoms. Y is ＯO or ＮN—R ₃
Represents R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. 2. A developer having a pH of 10.0 or higher and 12.0 or higher.
2. The image forming method according to claim 1, wherein: 3. An auxiliary developing agent comprising 1-phenyl-3-
The image forming method according to claim 1, further comprising a pyrazolidone-based compound and / or a p-aminophenol-based compound.