JP2873654B2 - Silver halide photographic light-sensitive material, processing method and processing agent therefor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material suitable for photolithography and capable of reproducing a super-high contrast image, a processing method and a processing agent therefor.

[0002]

2. Description of the Related Art The photoengraving process includes a process of converting a continuous tone original into a halftone image. In this process, a technique based on infectious development has been used as a photographic technique capable of reproducing an image having a super-high contrast.

The lithographic silver halide photographic light-sensitive material used for infectious development has, for example, an average particle diameter of about 0.2 μm, a narrow particle size distribution, a well-defined particle shape, and a high silver chloride content ( (At least 50 mol%) silver chloride emulsion is used. Such a lith-type silver halide photographic light-sensitive material is an alkaline hydroquinone developer having a low sulfite ion concentration,
By processing with a so-called lith type developer, an image with high contrast, high sharpness, and high resolution can be obtained. However, such a squirrel-type developer is very susceptible to air oxidation, and thus has extremely poor preservation. Therefore, it is difficult to keep development quality constant during continuous use.

[0004] On the other hand, there is known a method for quickly obtaining a high-contrast image without using a squirrel-type developer having poor preservation. For example, as disclosed in JP-A-56-106244, a hydrazine derivative is contained in a silver halide photographic light-sensitive material. According to this technique, a high-contrast image can be obtained by processing with a developer having good preservation properties and capable of rapid processing.

[0005]

However, silver halide photographic light-sensitive materials containing a hydrazine derivative have the disadvantage that they soften over time and black spots occur in unexposed areas.

An object of the present invention is to provide a silver halide photographic material containing a hydrazine derivative which softens over time,
It is an object of the present invention to provide a technical means for improving the disadvantage that black spots occur in unexposed areas.

[0007]

The constitution of the present invention which achieves the object of the present invention is as follows.

In a method for processing a silver halide photographic material having at least one silver halide emulsion layer on a support, a hydrazine derivative is contained in the silver halide emulsion layer and / or a layer adjacent thereto as a high contrast agent. A method for processing a silver halide photographic material, wherein the processing is performed in the presence of a branched cyclodextrin, a cyclodextrin polymer or a compound represented by the following general formula [I].

Formula (I) CD- (OR) _{1 wherein} CD represents a cyclodextrin residue, R represents an alkyl group, —R ¹ COOH, —R ¹ SO ₃ H, and —R ¹ NH ₂ or -N
(R ¹ ) ₂ , wherein R ¹ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and 1 represents an integer of 1 to 5. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer and / or an adjacent layer contains a hydrazine derivative as a high contrast agent, and a branched cyclodextrin And a cyclodextrin polymer or a compound represented by the above general formula [I].

In a silver halide photographic material having at least one silver halide emulsion layer on a support,
Include the silver halide emulsion layer and / or its adjacent layer with a hydrazine derivative as a toning agent and with a branched cyclodextrin, a cyclodextrin polymer, a compound represented by the above formula [I], cyclofructan or curlexarene. A silver halide photographic light-sensitive material characterized by containing as a clathrate compound.

A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer of which contains a hydrazine derivative as a high contrast agent in a silver halide emulsion layer and / or a layer adjacent thereto. A processing agent for processing a light-sensitive material, wherein the processing agent contains a branched cyclodextrin, a cyclodextrin polymer or a compound represented by the above formula (I).

Chemical ripening of a hydrazine derivative or a clathrate of a hydrazine derivative with a branched cyclodextrin, a cyclodextrin polymer or a compound represented by the above general formula [I] to form a silver halide emulsion forming a silver halide emulsion layer The above-mentioned processing method wherein the silver halide emulsion is incorporated after completion of the above.

A hydrazine derivative or an inclusion compound of a hydrazine derivative and a branched cyclodextrin, a cyclodextrin polymer or a compound represented by the above general formula (I) is chemically ripened to a silver halide emulsion forming a silver halide emulsion layer. The silver halide photographic light-sensitive material as described above, which is incorporated in a silver halide emulsion after completion of the above.

A hydrazine derivative, a branched cyclodextrin, a cyclodextrin polymer, and a compound represented by the above general formula [I]
Wherein the compound represented by the formula, a cyclofructan or an inclusion compound with curlexarene, is contained in the silver halide emulsion after completion of chemical ripening of the silver halide emulsion forming the silver halide emulsion layer. 3. The silver halide photographic light-sensitive material described in 1. above.

The present invention is based on the finding that a hydrazine derivative can form a water-soluble inclusion compound with a cyclodextrin derivative, and furthermore, the hydrazine derivative included in the inclusion compound has excellent stability and softening It is based on the finding that it is effective in preventing black spots and in generating black spots.

Hereinafter, the present invention will be described in detail.

First, the hydrazine derivative contained in the silver halide emulsion layer and / or its adjacent layer of the silver halide photographic light-sensitive material of the present invention will be described.

The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula [H].

[0019]

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In the formula, R ₁ represents an aliphatic group, an aromatic group, or a heterocyclic group containing at least one sulfur atom or oxygen atom, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group. It represents group, an amino group, a hydrazino group, a carbamoyl group, an oxycarbonyl group or -O-R group, R represents an alkyl group or a saturated heterocyclic group, G ₁
Is a carbonyl group, a sulfonyl group, a sulfoxy group,

[0021]

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A represents a thiocarbonyl group or an iminomethylene group; A ₁ and A ₂ are each a hydrogen atom or one of a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group;
Or a substituted or unsubstituted acyl group.

In the general formula [H], the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. is there. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. The 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 [H], 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 form a heteroaryl group by condensing a monocyclic or bicyclic aryl group.

For example, a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring,
Quinoline ring, isoquinoline ring, benzimidazole ring,
Among them, there are a thiazole ring and a benzothiazole ring, and among them, those containing a benzene ring are preferable.

Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group represented by R ₁ may be substituted. Representative 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. Group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyl Oxycarbonyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group or carboxyl group, phosphoric acid amide group, diacylamino group, imide group, R ₂ -NHCONR ₂ -CO- And preferred substitution. A linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or bicyclic alkyl moiety having 1 to 3 carbon atoms), an alkoxy group ( Preferably having 1 to 20 carbon atoms, a substituted amino group (preferably having 1 carbon atom)
An amino group substituted with an alkyl group having from 20 to 20), 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 And a phosphoric acid amide group (preferably having 1 to 30 carbon atoms).

The alkyl group represented by R ₂ in the general formula [H] is preferably an alkyl group having 1 to 4 carbon atoms, such as a halogen atom, a cyano group, a carboxy group, a sulfo group, an alkoxy group, Phenyl group, acyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfo group, arylsulfo group, sulfamoyl group, nitro group, heteroaromatic ring group,

[0029]

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It may have a substituent such as a 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.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group or the like.

The aryloxy group is preferably a single ring, and the substituent includes 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. Good.

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.

As the oxycarbonyl group, one having 1 to carbon atoms
Preferred are 10 alkoxycarbonyl groups and aryloxycarbonyl groups, which 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 , preferred are
When G ₁ is a carbonyl group, a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group,
Phenylsulfonylmethyl group, aralkyl group (eg, o-hydroxybenzyl group), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, etc.) ), And a hydrogen atom is particularly preferable.

When G ₁ is a sulfonyl group, R ₂ is an alkyl group (eg, a methyl group), an aralkyl group (eg, an o-hydroxyphenylmethyl group), an aryl group (eg, a phenyl group). Alternatively, a substituted amino group (eg, a dimethylamino group) is preferable.

When G ₁ is a sulfoxy group, preferred R ₂ includes a cyanobenzyl group and a methylthiobenzyl group,

[0040]

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In the case of a group, R ₂ is a methoxy group,
An ethoxy group, a butoxy group, a phenoxy group and a phenyl group are preferred, and a phenoxy group is 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 be applied.

G in the general formula [H] is most preferably a carbonyl group.

R ₂ is such that it causes a cyclization reaction that cleaves the G ₁ -R ₂ moiety from the residual molecule to form a cyclic structure containing atoms of the -G ₁ -R ₂ moiety. And more specifically, those which can be represented by the general formula (a).

The general formula (a) -R ₃ -Z in _{1 set,} Z ₁ is nucleophilically attacked to G _1, a group capable of splitting the G ₁ -R ₃ -Z ₁ moiety from the remainder molecule , R ₃ are those obtained by removing one hydrogen atom from R ₂ , and Z ₁ attacks nucleophilicly on G ₁ ,
G ₁ , R ₃ and Z ₁ can form a cyclic structure.

More specifically, Z ₁ easily undergoes a nucleophilic reaction with G ₁ when the hydrazine compound of the general formula [H] generates the next reaction intermediate by oxidation or the like, and R ₁ -N = N -G ₁ -R ₃ -Z ₁ R ₁ -N = N- is 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 , wherein R ₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), a functional group that directly reacts with G ₁ such as COOH, etc. (wherein, -OH, -SH, -NHR _4, -COOH may be temporarily protected so as to generate these groups by hydrolysis of an alkali, etc.) a well also, or

[0048]

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(R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a hetero group or a heterocyclic group) and react with a nucleophilic agent such as a hydroxyl ion or a sulfite ion. or it may be a functional group which becomes capable of reacting with the G ₁ by.

The ring formed by G ₁ , R ₃ and Z ₁ is preferably a 5- or 6-membered ring.

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

[0052]

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[0053] In the formula, R ¹ _b ~R ⁴ _b represents a hydrogen atom, an alkyl group (preferably those having 1 to 12 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms), 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 are 0 or 1
And (n + m) is 1 or 2.

The 5- or 6-membered ring formed by B is, for example, a cyclohexene ring, cycloheptene ring, benzene ring, naphthalene ring, pyridine ring, quinoline ring and the like.

[0055] Z ₁ has the same meaning as Z ₁ in the general formula (a).

[0056]

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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 0 or 1, and q represents an integer of 1 to 4. R _C ¹ , R _C ² and R _C ³ may be bonded to each other to form a ring as long as Z ₁ is capable of intramolecular nucleophilic attack on R _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 is preferably 1 to 3
And when q is 1, p is 0 or 1, and q is 2
When p is 0 or 1, when q is 3, p is 0 or 1.
And when q is 2 or 3, R _C ¹ and R _C ² may be the same or different. Z ₁ has the same meaning as Z ₁ in the general formula (a).

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

R ₁ or R _{2 in} the general formula [H] may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. 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 No. 1-100530.

R ₁ or R _{2 in} the general formula [H] 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, triazole groups and the like U.S. Patent Nos. 4,385,108 and 4,459,347.
No., JP-A-59-195233, JP-A-59-200231, JP-A-59-201045
No., 59-201046, 59-201047, 59-201048,
No. 59-201049, JP-A-61-170733, No. 61-270744,
No. 62-948, Japanese Patent Application No. 62-67508, No. 62-67501, No. 62-6
The groups described in 7,510 are exemplified.

In the present invention, among these, the following general formulas (Ha), (Hb), (Hc) or (Hd)
The compound represented by is preferred.

[0063]

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In the above general formula (Ha), R ₂₃ and R ₂₄
Represents a hydrogen atom, a substituted or unsubstituted alkyl group (eg, a methyl group, an ethyl group, a butyl group, a dodecyl group,
2-hydroxypropyl group, 2-cyanoethyl group, 2-chloroethyl group), substituted or unsubstituted phenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (for example, phenyl group, p-methylphenyl group, naphthyl group, α-hydroxynaphthyl group, cyclohexyl group, p-
Methylcyclohexyl group, pyridyl group, 4-propyl-2-
R ₂₅ represents a hydrogen atom, a substituted or unsubstituted benzyl group, an alkoxy group or an alkyl group (for example, a benzyl group, a p-methylbenzyl group, a methoxy group, a pyridyl group, a pyrrolidyl group, a 4-methyl-2-pyrrolidyl group); R ₂₆ and R ₂₇ each represent a divalent aromatic group (for example, a phenylene group or a naphthylene group); Y represents a sulfur atom or an oxygen atom; divalent linking group (e.g., _{-SO 2 CH 2 CH 2 NH -} , - SO
_{2 NH -, - OCH 2 SO} 2 NH -, - OCH = N-) represents, R ₂₈ is -
NR'R "or an -OR _29, R ', R" and R _{2 9} are each a hydrogen atom, a substituted or unsubstituted alkyl group (e.g. methyl group, an ethyl group, a dodecyl group), a phenyl group (e.g., phenyl , P-methylphenyl group, p-methoxyphenyl group), naphthyl group (for example, α-naphthyl group,
β-naphthyl group) or heterocyclic group (for example, pyridine,
Represents an unsaturated heterocyclic residue such as thiophene or furan or a saturated heterocyclic residue such as tetrahydrofuran or sulfolane), and R 'and R "together with a nitrogen atom form a ring (eg, piperidine, piperazine, morpholine, etc.) May be.

M and n each represent 0 or 1.
Y when R ₂₈ represents -OR ₂₉ preferably represents an ion atoms.

[0066]

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In the general formula (Hb), R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, a butyl group, a 3-aryloxypropyl group), a substituted or unsubstituted group. Substituted phenyl, naphthyl,
A cyclohexyl group, a pyridyl group, a pyrrolidyl group, a substituted or unsubstituted alkoxy group (for example, methoxy group, ethoxy group, butoxy group) or a substituted or unsubstituted aryloxy group (for example, phenoxy group, 4-methylphenoxy group) Represent.

In the present invention, each of R ⁵ and R ⁶ is preferably a substituted alkyl group (an alkoxy group or an aryl group as a substituent), and R ⁷ is preferably a hydrogen atom or an alkyl group. R ⁸ represents a divalent aromatic group (for example, a phenylene group or a naphthylene group), and Z represents a sulfur atom or an oxygen atom. R ⁹ includes a substituted or alkoxy group, a cyano group, an aryl group and the like.

[0069]

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In the general formulas (Hc) and (Hd), A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxide atom, and n represents 1 or 2. When n = 1, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Represents a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group, and R ₁ and R ₂ may form a ring together with a nitrogen atom. When n = 2, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, or an alkynyloxy group. , An aryloxy group, or a heterocyclic oxy group. However, when n = 2, at least one of R ₁ and R ₂ is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. Represents a group. R ₃ represents an alkynyl group or a saturated heterocyclic group. Formula (Hc) or (H-
The compound represented by d) includes a compound in which at least one H of -NHNH- in the formula is substituted with a substituent.

More specifically, A is an aryl group (eg, phenyl, naphthyl, etc.) or a heterocyclic group containing at least one sulfur atom or oxygen atom (eg,
Thiophene, furan, benzothiophene, pyran, etc.). R ₁ and R ₂ each represent a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl, trifluoroethyl, etc.), an alkenyl group (eg, allyl, butenyl, pentenyl, pentadienyl, etc.), Alkynyl group (for example,
Propargyl, butynyl, pentynyl, etc.), aryl groups (eg, phenyl, naphthyl, cyanophenyl, methoxyphenyl, etc.), heterocyclic groups (eg, pyridine, thiophene, unsaturated heterocyclic groups such as furan, tetrahydrofuran, sulfolane and the like). Such as a saturated heterocyclic residue), a hydroxy group, an alkoxy group (for example, methoxy, ethoxy,
Benzyloxy, cyanomethoxy, etc.), alkenyloxy group (eg, allyloxy, butenyloxy, etc.), alkynyloxy group (eg, propargyloxy, butynyloxy, etc.), aryloxy group (eg, phenoxy, naphthyloxy, etc.), or heterocyclic oxy A group (eg, pyridyloxy, pyrimidyloxy, etc.), and n
When = 1, R ₁ and R ₂ may form a ring (eg, piperidine, piperazine, morpholine, etc.) together with the nitrogen atom.

When n = 2, at least one of R ₁ and R ₂ is alkenyl, alkynyl, saturated heterocyclic, hydroxy, alkoxy, alkenyloxy, alkynyloxy, aryloxy or heterooxy. It represents a ring oxy group.

Specific examples of the alkynyl group and the saturated heterocyclic group represented by R ₃ include those described above.

Various substituents can be introduced into the aryl group represented by A or the heterocyclic group having at least one sulfur atom or oxygen atom. Examples of the substituent that can be introduced include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, Acyl group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamide group, arylaminothiocarbonylamino group,
Examples include a hydroxy group, a carboxy group, a sulfo group, a nitro group, and a cyano group. Of these substituents, a sulfonamide group is preferred.

In the general formulas (Hc) and (Hd), A preferably contains at least one diffusion-resistant group or a silver halide adsorption promoting group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. A ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group,
It can be selected from an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like.

The groups described in US Pat. No. 4,385,108 such as a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group are exemplified as the silver halide adsorbent accelerating group.

In the general formulas (Hc) and (Hd), -NH
H of NH—, that is, the hydrogen atom of hydrazine is a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.),
Acyl groups (eg, acetyl, trifluoroacetyl,
Ethoxycarbonyl) or an oxalyl group (eg, ethoxylyl, pyruvoyl, etc.), and may be substituted. The compounds represented by the general formulas (Hc) and (Hd) are such compounds. Including.

More preferred compounds in the present invention are the compound of the general formula (Hc) wherein n = 2 and the compound of the general formula (Hc)
-D).

In the compound of the formula (Hc) where n = 2, R ₁ and R ₂ are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, Alternatively, a compound which is an alkoxy group and at least one of R ₁ and R ₂ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, or an alkoxy group is preferable.

Representative compounds represented by the above general formula [H] are shown below.

[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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Specific examples of the hydrazine derivative used in the present invention are shown by the compounds represented by the general formulas [Ha] to [Hd]. Specific examples include the following compounds.

[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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Compounds II-7 to II-54 described in JP-A-3-174,143, page 24, upper right column to page 26, lower right column.

The hydrazine derivative used in the present invention is preferably a compound represented by the aforementioned general formula [H], but a hydrazine compound represented by the following general formula [H '] may be used.

Formula [H '] R ¹ -NH-NH-R ^{2 In} Formula [H'], R ¹ is quinolyl, pyridyl or cyclohexyl or a group represented by the following formulas (a) to (h). :

[0103]

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R ² is a hydrogen atom or a phenyl group; R ³ is a hydrogen atom, a halogen atom, an alkyl or alkoxy group having 1 to 4 carbon atoms or a sulfonamide group; R ⁴ and R ⁵ are a hydrogen atom or a halogen atom; ⁶ has 1 to 4 carbon atoms
Represents an alkyl group or an alkoxy group.

Specific examples of the compound represented by the general formula [H '] are shown below.

[0106]

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[0107]

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The hydrazine derivative represented by the general formula (Hc)
Or when the compound of (Hd) is contained,
No. 4203, page 69, line 1 to page 144, line 12, at least one of the nucleation promoting compounds described above was used in combination with a silver halide emulsion layer and / or
Alternatively, it is preferably contained in a non-photosensitive layer on the side of the silver halide emulsion layer on the support.

The typical specific examples of the nucleation promoting compound are shown below.

[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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As still another specific example, Japanese Patent Application No. Hei.
Nos. 1 to 1-26 described on pages 69 to 72, compounds II-1 to II-29 described on pages 73 to 78, pages 80 to 83
Compounds III-1 to III-25 described on page 84, compounds IV-1 to IV-41 described on pages 84 to 90, and compound V-1-1 described on pages 92 to 96 Compounds V-II-1 to V-II-30 described on pages 98 to 103, compounds V-III-1 to V-III described on pages 105 to 111 -35, 113 ~ 1
Compounds IV-1 to IV-I-44 described on page 21, pages 123 to 1
Compounds VI-II-1 to VI-II-68 and 13 described on page 35
Compounds VI-III-1 to VI-III- described on pages 7 to 143
There are other than the representative examples described above in 35.

Specific compounds other than those described above are described in
There are compound examples (1) to (61) and (65) to (75) described on pages 542 (4) to 546 (8) of 2-841.

The hydrazine derivatives represented by the general formulas [H] and [H '] can be synthesized by the method described in JP-A-2-841, pages 546 (8) to 550 (12).

The hydrazine derivative is added at the silver halide emulsion layer and / or the layer adjacent thereto. The amount of addition
It is preferably 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver, and more preferably 1 × 10 ^-5 to 1 × per mol of silver halide.
10 ^-2 moles.

Next, the branched cyclodextrin, the cyclodextrin polymer and the compound represented by the general formula [I] will be described.

The branched cyclodextrin used in the present invention is a known cyclodextrin obtained by branching or binding a water-soluble substance such as a monosaccharide such as glucose, maltose, cellobiose, lactose, sucrose, galactose and glucosamine and a disaccharide to a known cyclodextrin. Preferably, maltosyl cyclodextrin in which maltose is bound to cyclodextrin (the number of binding molecules of maltose may be one, two, or three), or glucosyl in which glucose is bound to cyclodextrin Cyclodextrin (The number of binding molecules of glucose is 1 molecule, 2 molecules,
Or any of three molecules).

Specific methods for synthesizing these branched cyclodextrins are described, for example, in Starch Chemistry, Vol. 33, No. 2, p. 119.
-126 (1986), P.127-132 (1986), Starch Chemistry, No.3
Vol. 0, No. 2, pp. 231 to 239 (1983) can be synthesized by a known synthesis method. For example, maltosyl cyclodextrin is obtained by using cyclodextrin and maltose as raw materials and isoamylase and pullulanase. It can be produced by a method of binding maltose to cyclodextrin using an enzyme. Glucosylcyclodextrin can be produced in a similar manner.

In the present invention, examples of the branched cyclodextrin preferably used include the following specific compounds.

[Exemplary Compounds] D-1 α-cyclodextrin with one molecule bonded to maltose, D-2 β-cyclodextrin with one molecule bonded to maltose, D-3 γ-cyclodextrin with one molecule bonded to maltose, D -4 α-cyclodextrin with two molecules of maltose bonded, D-5 β-cyclodextrin with two molecules of maltose bonded, γ-cyclodextrin with two molecules of maltose bonded, and three molecules of D-7 maltose bonded α-cyclodextrin, D-8 β-cyclodextrin in which three molecules of maltose are bonded, D-9 γ-cyclodextrin in which three molecules of maltose are bonded, D-10 α-cyclodextrin in which one molecule of glucose is bonded, D-11 Β-cyclodextrin with one molecule of glucose bound, D-12 one molecule of glucose bound γ-cyclodextrin, α-cyclodextrin in which two molecules of D-13 glucose are bonded, β-cyclodextrin in which two molecules of D-14 glucose are bonded, γ-cyclodextrin in which two molecules of D-15 glucose are bonded, D-16 Α-cyclodextrin in which three molecules of glucose are bound, β-cyclodextrin in which three molecules of D-17 glucose are bound, γ-cyclodextrin in which three molecules of D-18 glucose are bound, and the structures of these branched cyclodextrins are described in HPL.
C, NMR, TLC (thin layer chromatography), INEPT method (In
sensitive nuclei enhanced by polarization transfe
Although various measurement methods such as r) have been studied, they have not yet been determined even with current science and technology, and are in the stage of estimation structure. However, the fact that each monosaccharide or disaccharide or the like is bound to cyclodextrin is that there is no error in the above measurement method. Therefore, in the present invention,
When multiple molecules of monosaccharides or disaccharides are bonded to cyclodextrin, for example, they are individually bonded to each glucose of cyclodextrin as shown below, or linearly bonded to one glucose. It is intended to include both of the above.

[0124]

Embedded image

Since the ring structure of the existing cyclodextrin is kept as it is, it exhibits the same inclusion function as that of the existing cyclodextrin, and the addition of highly water-soluble maltose or glucose increases the solubility in water. The feature is that it has been improved.

The branched cyclodextrin used in the present invention can be obtained as a commercial product. For example, maltosyl cyclodextrin is commercially available as Isoelite (registered trademark) manufactured by Shimizu Minato Seika.

Next, the cyclodextrin polymer used in the present invention will be described.

The cyclodextrin polymer used in the present invention is preferably a polymer represented by the following general formula [II].

[0129]

Embedded image

The cyclodextrin polymer used in the present invention can be produced by polymerizing cyclodextrin with, for example, epichlorohydrin.

The cyclodextrin polymer preferably has a water solubility, that is, a solubility in water of not less than 20 g per 100 ml of water at 25 ° C., and for this purpose, the polymerization degree n ₂ in the following general formula [IV] is 3 to 3. The water solubility of the cyclodextrin polymer itself and the effect of solubilizing the substance are higher as this value is smaller.

These cyclodextrin polymers are described, for example, in JP-A-61-97025 and German Patent 3,544,842.
It can be synthesized by a general method described in the specification and the like.

The cyclodextrin polymer may be used as an inclusion compound of the cyclodextrin polymer as described above.

The amount of the cyclodextrin, cyclodextrin derivative, branched cyclodextrin or cyclodextrin polymer used in the present invention is, for example, preferably in the range of 0.1 to 100 g, more preferably 0.5 to 50 g / l per 1,000 ml of the developing solution.

CD in the general formula [I] is a residue of the cyclodextrin represented by the general formula [III] (part of a plurality of hydroxyl groups of the cyclodextrin molecule has been removed).

[0136]

Embedded image

Among them, those particularly useful in the present invention are n = 4
Α-cyclodextrin, β-cyclodextrin with n = 5 or γ-cyclodextrin with n = 6, respectively.

Specific examples of the compound represented by the formula [I] are shown below, but the present invention is not limited thereto.

[0139] The layer to be added to the silver halide photographic material of the compound represented by the formula [I] is a silver halide emulsion layer and / or a layer adjacent thereto. The amount added more preferably preferably in the range of 1 to 2000 mg / m ² in the range of 5 to 500 mg / m ^2. When the compound represented by the general formula [I] is contained in a processing solution, the processing solution refers to a developing solution or a fixing solution, and the amount of addition is preferably in the range of 0.1 to 100 g / l, more preferably
It is 0.5 to 50 g / l.

When the compound of the general formula [I] of the present invention is contained in the silver halide emulsion layer of the light-sensitive material or an adjacent layer thereof, at least one of the hydrazine derivative and the compound of the general formula [I] is converted to the silver halide emulsion layer. After the chemical ripening of the silver halide emulsion forming the silver emulsion layer is completed, the silver halide emulsion is contained in the above layer or the coating composition for forming the layer.

The cyclofructan used in the present invention is represented by the following general formula [IV].

[0142]

Embedded image

Of these, those particularly useful in the present invention are those wherein n =
5, n = 6 and n = 7.

Furthermore, the cyclofructan moiety according to the present invention performs an inclusion function to form an inclusion compound. In the present invention, the inclusion compound can be used.

The inclusion compound of cyclofructan is
Similar to the inclusion compound of cyclodextrin, for example, F. Cramer, "Einschlus verbindungen" Spri
nger (1954) or by M. Hagen (M. Hagan)
"Clathrate Inclusion Compound" (Cla
As described in “Thrate Inclusion Compound” Reinheld (1962), “a three-dimensional structure formed by bonding atoms or molecules has pores of an appropriate size, in which other atoms or molecules are fixed. A substance that forms a specific crystal structure by entering at a composition ratio. "

The cyclofructan clathrate can be prepared in the same manner as the cyclodextrin clathrate shown below. This is merely a few examples, and is of course not limited to these.

◎ Journal of the American Chemical Society
ical Society, Vol. 71, p. 354, 1949 ◎ Chemishe Berichte, ninth
0, 2572, 1957 ◎ 90, 2561, 1957 When the cyclofructan compound represented by the general formula [IV] of the present invention is added to a light-sensitive material, it is preferably 1 mg / m ² or more.
More preferably at 1000 mg / m ² is ^{10mg / m 2 ~500mg / m 2} . When added to the processing solution, the processing solution is preferably a developing solution or a fixing solution, and more preferably a developing solution. The addition amount is preferably in the range of 0.1 g to 100 g / l, more preferably 0.5 g to 50 g / l.

[0148] The curlex arene used in the present invention is represented by the following general formula [V].

[0149]

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The branched cyclodextrin, the cyclodextrin polymer, the compound represented by the general formula [I], the cyclofructan and the kalex arene form an inclusion compound by including a hydrazine derivative. In the present invention, such an inclusion compound can also be used.

The effects produced by the constitution of the present invention are completely different from those of ordinary polysaccharides or cellulose and cannot be predicted from them.

In the silver halide photographic light-sensitive material according to the present invention, at least one conductive layer can be provided on the support. Typical methods for forming the conductive layer include a method using a water-soluble conductive polymer, a hydrophobic polymer, and a curing agent, and a method using a metal oxide. For these methods, for example, the methods described in JP-A-3-265842, pages 5 to 15 can be used. In the silver halide emulsion used in the silver halide photographic light-sensitive material according to the present invention, silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride are usually used. Any of the silver halide emulsions used for the above silver halide emulsion can be used, but silver chlorobromide, silver bromide or silver iodobromide containing 4 mol% or less of silver iodide is preferred.

The silver halide grains contained in the silver halide emulsion are (standard deviation of particle size) / (average value of particle size).
Monodisperse particles having a coefficient of variation represented by × 100 of 15% or less are preferable.

For the silver halide photographic light-sensitive material according to the present invention, various techniques and additives known in the art can be used.

For example, the silver halide photographic emulsion and the backing layer may contain various chemical sensitizers, color tones, hardeners, surfactants, thickeners, plasticizers, sliding agents, development inhibitors, ultraviolet absorbers. Agents, antiirradiation dyes, heavy metals, matting agents and the like can be further contained by various methods.
Further, a polymer latex can be contained in the silver halide photographic emulsion and the backing layer.

These additives are described in more detail in Research Disclosure, Vol. 176, Item / 7643 (December 1978).
And Vol. 187, Item / 8716 (November 1979), and the relevant locations are summarized below.

Additive Type RD / 7643 RD / 8716 Chemical sensitizer page 23 648 right column 2. Sensitivity increasing agent Same as above 3. 3. Spectral sensitizers, pages 23 to 24, right column, page 648 to supersensitizers, right column, page 649. Brightener page 24 5. 5. Antifoggant and stabilizer page 24 to 25 page 649, right column 6. Light absorbers, filter dyes, pages 25 to 26, right column, page 649 to ultraviolet absorbers, left column, page 650 7. Stain inhibitor 25 pages right column 650 pages left to right column 8. Dye image stabilizer page 25 Hardening agent Page 26 651 Left column 10. Binder page 26 Same as above 11. Plasticizers and lubricants Page 27 Right column on page 650 12. Coating aids, surfactants 26-27 Same as above 13. Examples of the support that can be used in the silver halide photographic light-sensitive material of the present invention include cellulose acetate, cellulose nitrate, and the like.
Examples thereof include polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass, and metal. These supports are subjected to a base treatment as required.

[0158]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples.

Comparative Example 1 (Preparation of silver halide photographic emulsion A) A silver iodobromide emulsion (2 mol% of silver iodide per mol of silver) was prepared by a double jet method. During this mixing, K ₂ IrCl ₆ was added to silver 1
8 × 10 ^-7 mol was added per mol. The obtained emulsion was a cubic monodispersed emulsion having an average particle size of 0.20 μm (the coefficient of variation of the particle size distribution was 9%). Washing and desalting were carried out in a conventional manner. 40 after desalination
The pAg at ℃ was 8.0. Subsequently, 200 mg of the following sensitizing dye D-1 and 10 mg of D-2 per mol of silver were added to this emulsion, and a mixture of the following compounds [A], [B] and [C] was further added. To give Emulsion A.

[0160]

Embedded image

(Preparation of silver halide photographic light-sensitive material) A photosensitive silver halide emulsion layer of the following formula (1) was coated on one side of an undercoated polyethylene terephthalate support with a gelatin amount of 2.0 g / m ² and silver by coating as the amount is 3.2g / m ^2,
Further, an emulsion protective layer having the following formula (2) was coated thereon so that the amount of gelatin became 1.0 g / m ² , and the surface of the support opposite to the emulsion layer (subbed) was coated with the following. The backing layer of formula (3) is coated so that the amount of gelatin is 2.4 g / m ^2, and the backing protective layer of formula (4) below is further coated so that the amount of gelatin is 1 g / m ^2. Established.

The pH of each layer was adjusted with sodium carbonate and / or citric acid, and the film surface pH of the outermost layer was adjusted.
(1) to (4) were prepared.

Formulation (1) (Composition of photosensitive silver halide emulsion layer) Gelatin 2.0 g / m ² Silver halide emulsion A Silver amount 3.2 g / m ² Stabilizer: 4-methyl-6-hydroxy-1,3, 3a, 7-tetrazaindene 30 mg / m ² Antifoggant: 5-nitroindazole 10 mg / m ² 1-phenyl-5-mercaptotetrazole 5 mg / m ² Surfactant: sodium dodecylbenzenesulfonate 0.1 g / m ²

[0164]

Embedded image

Hydrazine derivatives shown in Table 1 7 × 10 ⁻⁵ mol / m ²

[0166]

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Formulation (3) (backing layer composition)

[0168]

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Gelatin 2.4 g / m ² Surfactant: Sodium dodecylbenzenesulfonate 0.1 g / m ² Surfactant: S-1 6 mg / m ² Colloidal silica 100 mg / m ² Hardener: E 55 mg / m ²

[0170]

Embedded image

[0171] Formulation (4) (Backing protective layer composition) Gelatin 1 g / m ² Matting agent: average particle size 5.0μm monodisperse polymethyl methacrylate A cleat 50 mg / m ² Surfactant: ^S-2 10mg / m 2 dura Agent: Glyoxal 25 mg / m ² Hardener: HA-1 35 mg / m ² Photosensitive materials (1) to (4) were stored at 23 ° C. and 50% RH for 24 hours and then sealed and packaged (Storage I). It was left at 55 ° C. for 3 days as a thermotreatment for the age (preservation II). A step wedge was stuck to the photosensitive material sample under the above two storage conditions,
After exposure to tungsten light of K for 5 seconds, processing was carried out under the following conditions using a rapid processing automatic developing machine GR-26SR manufactured by Konica Corporation into which a developing solution and a fixing solution having the following compositions were charged.

The processing conditions are as follows.

Developer Formulation (1) Sodium bisulfite 40 g N-methyl-p-aminophenol sulfate 350 mg Disodium ethylenediaminetetraacetate 1 g Sodium chloride 5 g Potassium bromide 1.2 g Trisodium phosphate 75 g 5-methylbenztriazole 250 mg 2-Mercaptobenzthiazole 23 mg Benztriazole 83 mg Hydroquinone 29 g Diisopropylaminoethanol 2.3 ml Amine compound Am-1 0.5 ml Potassium hydroxide Amount to adjust the pH of the working solution to 11.6 Water was added at the time of use to make 1 L.

[0174]

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Fixer Formulation (1) Ammonium thiosulfate (59.5% W / V aqueous solution) 830 ml Ethylenediaminetetraacetic acid disodium salt 515 mg Sodium sulfite 63 g Boric acid 22.5 g Acetic acid (90% W / V aqueous solution) 82 g Citric acid (50% W aqueous solution) / V aqueous solution) 15.7 g Gluconic acid (50% W / W aqueous solution) 8.55 g Aluminum sulfate (48% W / W aqueous solution) 13 ml Glutaraldehyde 3 g Sulfuric acid Amount to bring the pH of the working solution to 4.6 Add water at the time of use to 1 L Finished.

[0176]

The density of the obtained sample was measured with an optical densitometer Konica PDA-65, and the relative sensitivity was defined as 100 when the sensitivity at a density of 2.5 of sample No. 1 was set to 100. Further, the gamma was indicated by the tangent of the density of 0.1 and 2.5. did. A gamma value of less than 6 cannot be used, and a gamma value of 6.0 or more and less than 10.0 still has insufficient high contrast performance. When the gamma value is 10.0 or more, the image becomes a super-high contrast image, and is sufficiently practical.

The black spots in the unexposed areas were also evaluated using a magnifier of 40 times. When no black spots were generated, the highest rank was set to "5", and ranks "4", "3", "2", and "1" were sequentially reduced according to the degree of black spots and evaluated. . Note that 3.5 means the middle between 3 and 4, and 4.5 means the middle between 4 and 5. Ranks "1" and "2" are levels that are not practically desirable.

Table 1 shows the results.

[0180]

[Table 1]

Comparative Example 2 In place of sensitizing dyes D-1 and D-2, the following sensitizing dye D-3 was added in an amount of 15 mg per mol of silver. A hydrazine derivative shown in Table 2 was used in place of "the inclusion compound obtained in 1", and 3 × 10 ^-5 mol / m ² of the nucleation promoting compound N-10 was added to the formula (1). Prepared photosensitive materials (5) to (8) in the same manner as photosensitive materials (1) to (4). The photosensitive materials (5) to (8) were treated in the same manner as in Comparative Example 1 except that the developer formulation was changed to the following developer formulation (2) (Experiment Nos. 2-1 to 2-4). Table 2 shows the results.

[0182]

Embedded image

Developer formulation (2) (Composition A) Pure water (ion-exchanged water) 150 ml Disodium ethylenediaminetetraacetate 2 g Diethylene glycol 50 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-methylbenzo Triazole 200ml 1-Phenyl-5-methylcaptotetrazole 30mg Potassium hydroxide Amount to adjust pH of working solution to 10.5 Potassium bromide 4.5g (Composition B) Pure water (ion-exchanged water) 3ml Diethylene glycol 50g Disodium ethylenediaminetetraacetate 25g Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg When using a developing solution, the above composition A and composition B were dissolved in 500 ml of water in this order in order and finished to 1 liter.

[0184]

[Table 2]

Comparative Example 3 The photosensitive materials of Comparative Examples 1 and 2 (1) were used as photosensitive materials.
To (8), and as the developer, the developer formulation (1) and
Using the developer according to (2), the combination of the two is shown in Table 3 below.
The same experiment as in Comparative Example 1 was performed except that the formulation of the fixing solution and the processing conditions were as shown below. The results are shown in Tables 3 and 4 below.

[0186]

[Table 3]

[0187]

[Table 4]

Example 1 (Preparation of silver halide photographic emulsion B) A silver iodobromide emulsion (2 mol% of silver iodide per mol of silver) was prepared by a double jet method. During this mixing, K ₂ IrCl ₆ was added to silver 1
8 × 10 ^-7 mol was added per mol. The resulting emulsion is cubic monodispersity particles having an average particle size of 0.20 μm (coefficient of variation 9%).
The emulsion was composed of Washing and desalting were carried out in a conventional manner. The pAg at 40 ° C. after desalting was 8.0. Subsequently, a 0.1 mol% aqueous solution of potassium iodide per mol of silver was added to the emulsion to convert the surface of the grains, and then 200 mg of the sensitizing dye D-1 and 10 mg of D-2 were added per mol of silver. Further, a mixture of the compounds [A], [B] and [C] was added to obtain an emulsion B.

(Preparation of a silver halide photographic light-sensitive material) A photosensitive silver halide emulsion layer having the following formulation (5) was coated on one side of a polyethylene terephthalate support as an undercoating agent with a gelatin amount of 2.0 g / m ² and silver by coating as the amount is 3.2g / m ^2,
Further, an emulsion protective layer of the above formula (2) was coated thereon so that the amount of gelatin became 1.0 g / m ^2, and a backing layer was formed on the other undercoat layer on the opposite side according to the above formula (3). The layer was coated so that the amount of gelatin was 2.4 g / m ^2, and the backing protective layer of the above formula (4) was further coated thereon with the amount of gelatin of 1 g / m ^2.
It was applied so as to become.

The pH of each layer was adjusted with sodium carbonate and / or citric acid, and the pH of the outermost layer was adjusted to prepare photosensitive materials (14) to (18) as shown in Table 5. .

Formulation (5) (Composition of photosensitive silver halide emulsion layer) Gelatin 2.0 g / m ² Silver halide photographic emulsion B Silver amount 3.2 g / m ² Stabilizer: 4-methyl-6-hydroxy-1,3 , 3a, 7- tetrazaindene 30 mg / m ² antifoggant: adenine 10 mg / m ² 1-phenyl-5-mercaptotetrazole 5 mg / m ² surfactant: sodium dodecylbenzenesulfonate 0.1 g / m ² surfactant : S-1 8 mg / m ² A hydrazine derivative shown in Table 5 converted into an inclusion compound with Isoelite P (trademark, branched cyclodextrin, manufactured by Shimizu Port Refining Co., Ltd.) of the hydrazine derivative in the inclusion compound Content 7 × 10 ⁻⁵ mol / m ² Amount of isoelite P 7 × 10 ⁻³ mol / m ² Latex polymer Poly-1 (described above) 1 g / m ² Polyethylene glycol molecular weight 4000 0.1 g / m ² Hardener HA -1 (the) 60 mg / m ² Comparative example 4 formulation (5) hydrazine derivatives in Soerito P well which contains not inclusion in to prepare a light-sensitive material in the same manner as the photosensitive material (14) to (18) (9) to (13).

These photosensitive materials were processed and evaluated in the same manner as in Comparative Example 1 using the developing solution of the developing solution formulation (1). Table 5 shows the results.

[0193]

[Table 5]

Example 2 A photosensitive silver halide emulsion of the formula (5) was prepared by adding 150 mg of the above-mentioned D-3 per mol of silver instead of the sensitizing dyes D-1 and D-2 of the silver halide photographic emulsion B. Nucleation accelerator N-10 in the layer
Was added in the same manner as in Comparative Example 1 except that 3 × 10 ⁻⁵ mol / m ^{2 was} added.

However, the exposure was performed for ^10-5 seconds through an optical wedge and an interference filter of 633 nm, and the developer formulation used was the aforementioned developer formulation (2). Table 6 shows the results.

[0196]

[Table 6]

Example 3 The same experiment as in Example 1 was performed using the photosensitive materials (9) to (30). However, as the developing solution, the developing solution formulations (1) and (2) and the developing solutions of the following (3) and (4) are used. And The results are shown in Tables 7 and 8.

Developer formulation (3) Ethylenediaminetetraacetic acid sodium salt 1 g Sodium sulfite 60 g Boric acid 40 g Hydroquinone 35 g Sodium hydroxide 3 g Sodium bromide 3 g 5-methylbenzotriazole 0.2 g 2-mercaptobenzothiazole 0.1 g 2-mercaptobenzothiazole -5-sulfonic acid 0.2g 1-phenyl-4,4-dimethyl-3-pyrazolidone 0.2g Isoelite P 7g Add water and adjust pH with 1L sodium hydroxide 10.8 Developer formulation (4) Sodium bisulfite 40g N -Methyl-P-aminophenol sulfate 350mg Disodium ethylenediaminetetraacetate 1g Sodium chloride 5g Potassium bromide 1.2g Potassium phosphate 27g Potassium phosphate 20g 5-Methylbenztriazole 250mg 2-Mercaptobenzthiazole 23mg Benztriazole 83mg Hydroquinone 29g 2.3 ml of diisopropylaminoethanol Finished with 1l in water was added and the pH of the elite P 7 g amine compound Am-1 (the) 0.5 ml potassium hydroxide solution used when the amount used to 11.6.

[0199]

[Table 7]

[0200]

[Table 8]

Example 4 A photosensitive silver halide emulsion layer having the following formulation (6) was coated on one side of a polyethylene terephthalate support as an undercoating agent with a gelatin content of 2.0 g / m ² and a silver content of 3.2 g / m ² . ² and an emulsion protective layer of the above formula (2) is further coated thereon so that the amount of gelatin becomes 1.0 g / m ² , and the surface of the support opposite to the emulsion layer is coated. In (undercoating finished), the backing layer of the above formula (3) is applied so that the gelatin amount becomes 2.4 g / m ² ,
Further, a backing protective layer of the above formula (4) was applied thereon so that the amount of gelatin became 1 g / m ² .

The pH of each layer was adjusted with sodium carbonate and / or citric acid, and the pH of the outermost layer was adjusted to prepare photosensitive materials (31) to (36) shown in Table 9.

Formula (6) (Composition of photosensitive silver halide emulsion layer) Gelatin 2.0 g / m ² Silver halide emulsion A (described above) Silver amount 3.2 g / m ² Stabilizer: 4-methyl-6-hydroxy-1 , 3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: 5-nitroindazole 10 mg / m ² 1-phenyl-5-mercaptotetrazole 5 mg / m ² Surfactant: sodium dodecylbenzenesulfonate 0.1 g / m ² surfactant: S-1 (described above) 8 mg / m ² hydrazine derivative (described in Table 9) 7 × 10 ⁻⁵ mol / m ² Compound of general formula [I] (described in Table 9) 1 × 10 ^{− 4} mol / m ²

[0204]

Embedded image

Comparative Example 1 using photosensitive materials (31) to (36)
The same experiment was performed. However, as the developing solution, the developing solution of the developing solution formulation (1) was used. Table 9 shows the results.

[0206]

[Table 9]

From Table 9, it can be seen that the coexistence of the hydrazine derivative and the compound of the formula [I] in the silver halide emulsion layer of the silver halide photographic light-sensitive material significantly suppresses the softening over time and the occurrence of black spots. We can see that we can do it.

Example 5 Six kinds of silver halide photographic light-sensitive materials (37) to (42) were prepared in the same manner as the light-sensitive materials (31) to (36) of Example 1 except that the compound of the formula [I] was not added. ) Was prepared.

Comparative Example 1 using photosensitive materials (37) to (42)
The same experiment was performed. However, a developer having the following developer formulation (5) was used as the developer. Table 10 shows the results.

Developer Formulation (5) Sodium bisulfite 40 g N-methyl-p-aminophenol sulfate 350 mg Ethylenediaminetetraacetic acid disodium salt 1 g Sodium chloride 5 g Potassium bromide 1.2 g Potassium phosphate 27 g Potassium phosphate 20 g 5-methyl Benzotriazole 250mg 2-Mercaptobenzothiazole 23mg Benzotriazole 83mg Hydroquinone 29g Diisopropylaminoethanol 2.3ml Amino compound Am-1 (as described above) 0.5ml Compound of general formula [I] (described in Table 10) 7g Potassium hydroxide pH of working solution The amount was adjusted to 11.6. Water was added at the time of use to make 1 liter.

[0211]

[Table 10]

From Table 10, it can be seen that, by treating a silver halide photographic light-sensitive material containing a hydrazine derivative with a processing solution containing a cyclodextrin compound, softening over time and the occurrence of black spots can be significantly suppressed. Recognize.

Example 6 Comparative Example 2 was repeated except that the hydrazine derivative in the above-mentioned formulation (1) was replaced with the inclusion compound in which the hydrazine derivative shown in Table 11 was included in cyclofructan CF-2 or Karexarene K. Light-sensitive materials (5) to (8) of Comparative Example 2
In the same manner as in Comparative Example 2, photosensitive materials (43) to (50) were prepared. Table 11 shows the results.

[0214]

[Table 11]

[0215]

According to the present invention, the disadvantage that the silver halide photographic light-sensitive material containing a hydrazine derivative is softened with the passage of time and black spots are formed in unexposed portions is improved.

Further, the effects of the present invention will be described below.

Many hydrazine derivatives are hardly soluble in water, and are used as additives after being dissolved in water as a hydrochloride or dissolved in an appropriate solvent. However, the hydrazine derivative can be sufficiently dissolved in an aqueous solution of the compound represented by the general formula [I] of the present invention at a concentration of 10 ^-2 mol / l. This facilitates the means for adding the hydrazine derivative.

The hydrazine derivative is decomposed in an aqueous solution or is very unstable in the surrounding atmosphere. However, the presence of the compound of the present invention represented by the general formula [I]
The stability of the hydrazine derivative is increased, and stable image formation is possible even with aging or left at high temperatures.

A silver halide photographic material (containing no compound represented by the general formula [I]) containing a hydrazine derivative in a silver halide emulsion layer and / or a layer adjacent thereto is prepared according to the general formula [I] of the present invention. When processed with a developer containing a compound represented by the formula (I), the stability of the silver halide photographic light-sensitive material is increased in the same manner as in the case where the compound represented by the general formula (I) is contained in the light-sensitive material. Even at high temperatures, stable image formation with high contrast and little black spots can be achieved.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-107680 (JP, A) JP-A-53-48735 (JP, A) JP-A-53-276050 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) G03C 1/06 501 G03C 1/06 502 G03C 1/04 G03C 5/29 501 G03C 5/305

Claims (7)

(57) [Claims] 1. A method for processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein a hydrazine derivative is used as a high contrast agent in the silver halide emulsion layer and / or an adjacent layer thereof. A method for processing a silver halide photographic light-sensitive material, comprising processing in the presence of a branched cyclodextrin, a cyclodextrin polymer or a compound represented by the following general formula [I]. In the general formula (I) CD- (O-R) _l [wherein, CD represents a cyclodextrin residue, R represents an alkyl ^{group, -R 1 COOH, -R 1 SO} 3 H, -R 1 NH 2 or - N
(R ¹ ) ₂ , wherein R ¹ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and 1 represents an integer of 1 to 5. ] 2. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The silver halide emulsion layer and / or the layer adjacent thereto contain a hydrazine derivative as a high contrast agent, and contain a branched cyclodextrin, a cyclodextrin polymer or a compound represented by the following general formula [I]. Silver halide photographic material. In the general formula (I) CD- (O-R) _l [wherein, CD represents a cyclodextrin residue, R represents an alkyl ^{group, -R 1 COOH, -R 1 SO} 3 H, -R 1 NH 2 or - N
(R ¹ ) ₂ , wherein R ¹ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and 1 represents an integer of 1 to 5. ] 3. A silver halide photographic material having at least one silver halide emulsion layer on a support,
Include the silver halide emulsion layer and / or its adjacent layer with a hydrazine derivative as a toning agent and with a branched cyclodextrin, a cyclodextrin polymer, a compound represented by the following general formula [I], cyclofructan or curexarene A silver halide photographic light-sensitive material characterized by containing as a clathrate compound. In the general formula (I) CD- (O-R) ₁ [wherein, CD represents a cyclodextrin residue, R represents an alkyl ^{group, -R 1 COOH, -R 1 SO} 3 H, -R 1 NH 2 or - N
(R ¹ ) ₂ , wherein R ₁ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and 1 represents an integer of 1 to 5. ] 4. A silver halide emulsion layer of a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and / or a layer adjacent to the silver halide emulsion layer containing a hydrazine derivative as a high contrast agent. A processing agent for processing a silver photographic light-sensitive material, wherein the processing agent contains a branched cyclodextrin, a cyclodextrin polymer or a compound represented by the following general formula [I]. Agent. In the general formula (I) CD- (O-R) _l [wherein, CD represents a cyclodextrin residue, R represents an alkyl ^{group, -R 1 COOH, -R 1 SO} 3 H, -R 1 NH 2 or - N
(R ¹ ) ₂ , wherein R ¹ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and 1 represents an integer of 1 to 5. ] 5. A silver halide emulsion for forming a silver halide emulsion layer, comprising a hydrazine derivative or an inclusion compound of a hydrazine derivative and a branched cyclodextrin, a cyclodextrin polymer or a compound represented by the following general formula [I]. 2. The processing method according to claim 1, wherein the silver halide emulsion is contained in the silver halide emulsion after the completion of chemical ripening. In the general formula (I) CD- (O-R) _l [wherein, CD represents a cyclodextrin residue, R represents an alkyl ^{group, -R 1 COOH, -R 1 SO} 3 H, -R 1 NH 2 or - N
(R ¹ ) ₂ , wherein R ¹ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and 1 represents an integer of 1 to 5. ] 6. A hydrazine derivative or an inclusion compound of a hydrazine derivative and a branched cyclodextrin, a cyclodextrin polymer or a compound represented by the following general formula [I], 4. A silver halide photographic material according to claim 3, wherein said photographic material is incorporated into a silver halide emulsion after completion of chemical ripening. In the general formula (I) CD- (O-R) _l [wherein, CD represents a cyclodextrin residue, R represents an alkyl ^{group, -R 1 COOH, -R 1 SO} 3 H, -R 1 NH 2 or - N
(R ¹ ) ₂ , wherein R ¹ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and 1 represents an integer of 1 to 5. ] 7. A hydrazine derivative and a branched cyclodextrin, a cyclodextrin polymer, represented by the following general formula [I]
Wherein the compound represented by the formula (I), a cyclofructan or an inclusion compound with calexarene is contained in the silver halide emulsion after completion of chemical ripening of the silver halide emulsion forming the silver halide emulsion layer. Item 6. A silver halide photographic material according to item 3. In the general formula (I) CD- (O-R) _l [wherein, CD represents a cyclodextrin residue, R represents an alkyl ^{group, -R 1 COOH, -R 1 SO} 3 H, -R 1 NH 2 or - N
(R ¹ ) ₂ , wherein R ¹ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and 1 represents an integer of 1 to 5. ]