JPH07333775A - Silver halide photographic material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic material with very high contrast which, even when processed with a developer with a pH of less than 11, prevents sensitivity fluctuation and softening resulting from successive processes and prevents increase in the number of black dots generated in an unexposed part. CONSTITUTION:This silver halide photographic material contains a hydrazine derivative of the formula I and a silver salt of a methine compound of the formula II. In the formula I, R1 represents an aliphatic group or an aromatic group, and either contains a partial structure of -(CH2CH2O)n-,-(CH2CH (CH3) O)n-, or -(CH2CH (OH) CH2O)n- ((n) is an integer of 1 or greater) as a part of its substituent, or contains a quaternary ammonium cation as a part of its substituent. In the formula II, 'Dye' represents an atom group having a methine dye structure; L represents a divalent bond consisting of carbon atom, nitrogen atom, oxygen atom and sulfur atom; 'Sal' represents a group forming a refractory salt with silver ion; m1 represents 1 or 2; m2 represents 0 or 1; and m3 represents 1, 2, 3 or 4.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a high contrast silver halide photographic light-sensitive material.

[0002]

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

As a lithographic silver halide photographic light-sensitive material used for infectious development, for example, the average particle size is about 0.2 μm or less, the particle distribution is narrow and well-shaped, and the content of silver chloride is high (at least). 50 mol% or more) consisting of silver chlorobromide emulsion. By processing the lith-type silver halide photographic light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lith-type developer, an image with high contrast, high sharpness and high resolution can be obtained.

However, since these lith-type developers are susceptible to aerial oxidation, their preservative properties are extremely poor.
It is difficult to keep the development quality constant during continuous use.

There is known a method of rapidly obtaining a high-contrast image without using the lith developer. For example, as disclosed in JP-A-56-106244, a silver halide photographic light-sensitive material containing a hydrazine derivative is treated with an ordinary alkaline developing solution. According to these methods, the stability of the developer is good,
A high contrast image can also be obtained by processing with a developer capable of rapid processing.

However, in these techniques, in order to fully exert the high contrast of the hydrazine derivative, the pH of 11.2 or higher is used.
Had to be processed with a developer solution containing H 2. pH
A high pH developer of 11.2 or more is more stable than the lith developer although the developing agent is easily oxidized when exposed to air.
Due to the oxidation of the developing agent, an ultrahigh contrast image cannot often be obtained.

In order to compensate for such drawbacks, Japanese Patent Laid-Open No. 63-297
51 gazette, JP-A 1-179939 JP, 1-179940 JP,
US Pat. No. 4,975,354 has a relatively low pH of less than 11.2.
There is disclosed a silver halide photographic light-sensitive material containing a hydrazine derivative capable of increasing the tone even with a H developing solution and accelerating nucleation.

In the case of an image forming method in which a silver halide photographic light-sensitive material containing such a contrast-increasing agent is processed with a developer having a pH of less than 11.0, sensitization or softening is caused by continuous processing, and unprocessed after development processing. At present, there is a problem that sandy fog, which is a so-called black spot, that occurs in the exposed portion is deteriorated, and satisfactory performance cannot be obtained.

Further, when a silver halide photographic light-sensitive material containing these hardening agents is subjected to low replenishment and ultra-rapid processing by using an automatic processor, the sensitivity is lowered and the softening is remarkable.

[0010]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide a method of forming a super-high contrast image in which sensitivity fluctuations and softening due to continuous processing and increase of black spots generated in an unexposed area are prevented. To provide.

A second object of the present invention is to provide a super-high contrast image in which fluctuations in sensitivity and softening due to continuous processing and an increase in black spots generated in an unexposed area are prevented even when processed with a developer having a pH of less than 11. To do.

A third object of the present invention is to provide a silver halide photographic light-sensitive material which does not cause sensitivity deterioration and softening when low replenishment and ultra-rapid processing is carried out using an automatic processor.

[0013]

The above problems have been solved by the present invention described below. That is, at least one silver halide emulsion layer is provided on a support, the emulsion layer or another hydrophilic colloid layer contains a hydrazine derivative represented by the general formula (I), and A silver halide photographic light-sensitive material comprising at least one silver salt of a methine compound represented by (II).

[0014]

[Chemical 2]

[In the formula, R ₁ represents an aliphatic group or an aromatic group, and as a part of the substituent,-(CH ₂ CH ₂ 0) n-,
− (CH ₂ CH (CH ₃ ) 0) n−, − (CH ₂ CH (OH) CH ₂ 0) n− (however,
n is an integer of 1 or more) or a group containing a quaternary ammonium cation as a part of the substituent. R ₁ may also contain a silver halide adsorption group. G ₁ is -CO- group, -COCO- group, -CS- group, -C (= NG ₂
R ₂ )-group, -SO- group, -SO ₂ -group or -P (O) (G ₂ R ₂ )-
Represents a group. G ₂ represents a simple bond, —O— group, —S— group or —N (R ₂ ) — group, R ₂ represents an aliphatic group, an aromatic group or a hydrogen atom, and a plurality of R's in the molecule. _{If two} are present they may be the same or different. One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl group, or an arylsulfonyl group. ] General formula (II) (Dye) _m1 [-(L) _m2- Sal] _m3 [In the formula, Dye represents an atomic group having a methine dye structure,
L represents a divalent linking group having a skeleton of an atom or atomic group selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and Sal represents a group which forms a sparingly soluble salt with a silver ion,
m1 is 1 or 2, m2 is 0 or 1, m3 is 1,
Represents 2, 3 or 4. The present invention will be described in detail below.

The general formula (I) will be described in more detail.

The aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. This alkyl group has a substituent.

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 an aryl group to form a condensed heterocyclic group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and an isoquinoline ring. Of these, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group. The aryl group or unsaturated heterocyclic group of R ₁ is substituted.

The aliphatic group or aromatic group of R ₁ is substituted, and a typical substituent is, for example, a halogen atom,
Alkyl, aralkyl, alkenyl, alkynyl, alkoxy, aryl, substituted amino, ureido, urethane,
Aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl,
Hydroxyl, cyano, sulfo, aryloxycarbonyl, acyl, alkoxycarbonyl, acyloxy,
Each group such as carbonamide, sulfonamide, carboxyl, phosphoric acid amide and the like can be mentioned, and a preferable substituent is a linear, branched or cyclic alkyl group (preferably having 1 carbon atom).
~ 20), aralkyl group (preferably having 7 to 30 carbon atoms)
Group), an alkoxy group (preferably having 1 to 30 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 30 carbon atoms), an acylamino group (preferably 2 to 40 carbon atoms) Group), sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms), phosphoric acid amide group (preferably having 1 to 40 carbon atoms), etc. .

The aliphatic group, aromatic group or their substituents for R ₁ is-(CH ₂ CH ₂ O) n-,-(CH ₂ CH (CH ₃ ) O) n- or-(CH ₂
It contains CH (OH) CH ₂ O) n- or contains a quaternary ammonium cation. n is preferably an integer of 1 to 15. R ₁ is preferably represented by the following general formula (6), general formula (7), general formula (8) or general formula (9).

[0021]

[Chemical 3]

In the above general formula, L ₁ and L ₂ are each -CON.
(R ₇ )-group, -N (R ₇ ) CON (R ₈ )-group, -SO ₂ N (R ₇ )-group or-
N (R ₇ ) S0 ₂ N (R ₈ )-represents a group, which may be the same or different. R ₇ and R ₈ are each a hydrogen atom or a carbon number of 1 to 6
Represents an alkyl group having 6 to 10 carbon atoms and is preferably a hydrogen atom. m is 0 or 1. R ₃ , R ₄ and R
₅ is a divalent aliphatic group or aromatic group, preferably an alkylene group, an arylene group or -O-,
-CO -, - S -, - SO -, - SO 2 -, - N (R 9) - (R 9 is the formula (6), (7), (8), the same meaning as R ₇ (9) ) Is a divalent group made by combining. More preferably, R ₃ is an alkylene group having 1 to 10 carbon atoms or a combination thereof with —S—, —SO—, or —SO ₂ —
R ₄ and R ₅ are each a valent group and are each an arylene group having 6 to 20 carbon atoms. Particularly, R ₅ is preferably a phenylene group.
R ₃ , R ₄ and R ₅ may be substituted, and as the preferable substituents, those enumerated as the substituents of R ₁ are applicable.

In the general formulas (6) and (7), Z ₁ represents an atomic group necessary for forming a nitrogen-containing aromatic ring. Preferable examples of the nitrogen-containing aromatic heterocycle formed by Z ₁ and a nitrogen atom include pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, imidazole ring, pyrazole ring, pyrrole ring, oxazole ring, thiazole ring and benzo thereof. In addition to the condensed ring, a pteridine ring, a naphthyridine ring and the like can be mentioned.

In the general formulas (6), (7) and (8), X ^- represents a counter anion or a counter anion moiety when forming an inner salt.

In the general formulas (7), (8) and (9), R ₆ represents an aliphatic group or an aromatic group. Preferably R ₆
Is an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms.

The three R _{6 s} in the general formula (8) may be the same or different, and may combine with each other to form a ring. R ₆ may be substituted, and as the preferable substituents, those enumerated as the substituents of R ₁ are applicable.

In the general formula (9), L ₃ is —CH ₂ CH ₂ O—
Group, a -CH ₂ CH (CH ₃₎ O- group or a _{-CH 2 CH (OH) CH 2} O- radical, n has the same meaning as in formula (I).

As G ₁ in the general formula (I), --CO--
The group, —SO ₂ — group is preferred, and —CO— group is most preferred.
A hydrogen atom is preferable as A ₁ and A ₂ .

The alkyl group represented by R ₂ in the general formula (I) is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, benzene). Including rings). G ₁ is -C
In the case of an O-group, preferred ones of the groups represented by R ₂ are
Hydrogen atom, alkyl group (eg methyl, trifluoromethyl, 3-hydroxypropyl, 3-methanesulfonamidopropyl, phenylsulfonylmethyl etc.), aralkyl (eg o-hydroxybenzyl), aryl group (eg phenyl, 3,5- Dichlorophenyl, o-methanesulfonamidophenyl, etc., 4-methanesulfonylphenyl, 2-hydroxymethylphenyl etc.) and the like, with a hydrogen atom being particularly preferred. R ₂ may be substituted, and as the substituent,
The substituents listed for R ₁ are applicable. Also, R ₂ is G
_It may be _{one that} splits the _1- R ₂ moiety from the residual molecule to cause a cyclization reaction to form a cyclic structure containing atoms of the -G ₁ -R ₂ moiety. -297
Examples include those described in No. 51.

R ₁ or R ₂ of the general formula (I) may have a ballast group or polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and examples thereof include an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
It can be selected from among alkylphenoxy groups and the like.
Further, examples of the polymer include those described in JP-A No. 1-100530.

As the silver halide adsorbing group which R ₁ can have, --S-- group, --S--S-- group, --NHC (= S) NH--
Group, a 5- or 6-membered nitrogen-containing heterocyclic group (benzotriazole,
Triazole, imidazole, thiazole, oxazole, etc.), mercapto group or disulfide bond 5
And a 6-membered nitrogen-containing heterocyclic group (2-mercaptothiadiazole, 5-mercaptotetrazole, 2-mercaptobenzoxazole and the like). In particular, it is preferable to have a 5-S-membered nitrogen-containing heterocyclic group having a -S- group, a mercapto group or a disulfide bond.

The compound of the general formula (I) of the present invention can be obtained, for example, from JP-A-61-213847 and JP-A-62-260153, and US Pat.
No. 9, No. 3,620,746, No. 4,684,604, No. 4,377,634,
4,332,878, JP-A-49-129536, 56-153336,
56-153342, U.S. Pat. Nos. 4,988,604, and 4,994,365.

The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0034]

[Chemical 4]

[0035]

[Chemical 5]

[0036]

[Chemical 6]

[0037]

[Chemical 7]

[0038]

[Chemical 8]

[0039]

[Chemical 9]

The amount of the compound of the general formula (I) added is
It is preferably contained in an amount of 1 × 10 ^{−6 to} 5 × 10 ⁻² mol, and particularly preferably 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol, per mol of silver halide.

The compounds of the general formula (I) are suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluoroalcohol etc.), ketones (acetone, methyl ethyl ketone etc.), dimethylformamide, dimethyl sulfoxide. , Dissolved in methyl cellosolve and the like. Also, by well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, mechanically emulsified dispersion Can also be created and used. Alternatively, the redox compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

Next, the general formula (II) will be described in more detail.

In the general formula (II), the group represented by Dye represents an atomic group having a methine dye structure, and for example, a methine chain such as cyanine, merocyanine, merostyryl, styryl, oxonol, and triarylmethane is a conjugated double bond. A group having a dye structure bonded thereto. Specific examples of these dyes include, for example, JP-A-63-202665.
Cyanine dyes described in Soviet Patent No. 653,257, JP-A Nos. 52-29727, 52-60825 and 52-135335
No. 56, No. 56-27146, No. 56-29226, No. 59-10944, No. 59
-15934, 59-111847, 63-34539, U.S. Pat.Nos. 2,944,896, 3,148,187 and other merocyanine dyes, JP-A-59-211041, 59-211042, 60
-135936, 60-135937, 61-204630, 61-2059
No. 34, No. 62-56958, No. 62-70830, No. 62-92949, No.
No. 62-185758, a merostil dye described in JP-A No. 50-
145125, 55-33103, 55-120660, 55-161233
No. 62-185755, 63-139949, 63-231445,
63-264745, U.S. Patent 4,187,275, British Patent 1,
521,083, Oxonol dyes described in Belgium Patent 869,677, etc., JP 59-55437, 59-228250 JP, U.S. Pat. There are dyes, and further,
TH James “The Theory of Photographic Process” 1
977 Published by Macmillan, FM Harmer, “Heterocycli
c compounds Cyanine dyes and related compounds “Joh
n Wiley & Sons (New York London) 1964, DMSt
urmer, “The Chemistry of Heterocyclic Compounds
"ed.A.Weissbergerand ECTaylor. 1977," The
Chemistry of Synthetic Dyes "Academic Press (NewY
ork London) Vol.II. 1952, Vol.IV. Selected from those listed in publications such as 1971.

L represents a divalent linking group having a skeleton of an atom or atomic group selected from carbon atom, nitrogen atom, oxygen atom and sulfur atom. Preferred groups are alkylene groups (eg,
Methylene group, ethylene group, propylene group, pentylene group etc.), arylene group (eg phenylene group etc.), alkenylene group (eg ethylene group, propenylene group etc.), sulfonyl group, sulfinyl group, ether group, thioether group, carbonyl Group, -N (R)-group (R is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group), -N = group, a heterocyclic divalent group (for example, triazine-2,4 -Diyl group, pyrimidine-2,4-diyl group, thiazole-2,4-diyl group, benzoxazole-2,5-diyl group, etc.) composed of one or more of C20 or less It is a divalent linking group and may have a substituent. Examples of the substituent include common ones such as a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (eg, methyl group, ethyl group, isopropyl group, butyl group, etc.), aralkyl group (eg, Benzyl group, phenethyl group etc.), alkoxy group (eg methoxy group, ethoxy group etc.), alkoxycarbonyl group (eg ethoxycarbonyl group etc.), alkylthio group, hydroxy group, carboxy group, sulfo group, sulfonyl group (eg methanesulfonyl group) , P-toluenesulfonyl group, etc.),
Carbamoyl group (eg N-methylcarbamoyl group, morpholinocarbonylamino group etc.), acyl group (eg acetyl group, benzoyl group etc.), acylamide group (eg acetamide group etc.), sulfonamide group (eg methanesulfonamide group, butane) Any group such as a sulfonamide group), a cyano group, an amino group (for example, an ethylamino group, a dimethylamino group, etc.), an ureido group or the like is selected.

M1 is 1 or 2, m2 is 0 or 1,
m3 represents 1, 2, 3 or 4. Sal represents a group that forms a sparingly soluble salt with silver ions, and includes, for example, a mercapto group, an acetylene group, a thiocarbonyl group, a thioamide group, a thiourethane group, a thioureido group (for example, 3-ethylthioureido group, 3-phenylthio). A ureido group), or a saturated or unsaturated 5 containing at least one nitrogen atom in the ring.
Member to 7-membered heterocyclic residue. Preferred groups include general formulas (VII) and (I
X) or the groups represented by the general formulas (II) to (VI) described in JP-A-2-225476.

Next, specific examples of the methine compound according to the present invention will be shown.

[0047]

[Chemical 10]

[0048]

[Chemical 11]

[0049]

[Chemical 12]

[0050]

[Chemical 13]

[0051]

[Chemical 14]

[0052]

[Chemical 15]

[0053]

[Chemical 16]

[0054]

[Chemical 17]

[0055]

[Chemical 18]

[0056]

[Chemical 19]

[0057]

[Chemical 20]

[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

[0060]

[Chemical formula 23]

[0061]

[Chemical formula 24]

[0062]

[Chemical 25]

The methine compound according to the present invention can be dyed from an intermediate raw material in which a sparingly soluble silver salt-forming group represented by Sal has been substituted in advance, or a method in which a methine dye structural moiety represented by Dye and a Sal moiety are combined. However, it can be selected and synthesized arbitrarily. Various known binding reactions can be used to introduce the Sal group, for example, addition reaction to unsaturated groups such as vinyl group and carbonyl group, active hydrogen substituents such as amino group and hydroxy group and acid derivatives, It is carried out by a substitution reaction with a halogen derivative. In conducting these reactions, "New Experimental Chemistry Course 14" edited by the Japan Society of Chemistry, synthesis and reaction of organic chemistry,
Volumes IV, Maruzen (1962), "Organic Reactions" Vo
l, 1,3,12 John Wiley & Sons (New York London),
“The Chemistry of Functional Groups” John Wiley
& Sons (New York London), LFFiester and M.Fies
er, “Advanced Organic Chemistry” Maruzen (1962), etc.
Many publications can be consulted.

These methine dyes according to the present invention are reacted with an aqueous solution of a soluble silver salt to form a difficult silver salt, which is dispersed and added to a silver halide photographic light-sensitive material.

Regarding the method for producing a silver salt from these dyes and the method for adding it to a light-sensitive material, the above-mentioned British Patent 1,
The methods described in 077,049 and US Pat. No. 3,471,293 can be referred to.

In the light-sensitive material of the present invention, the silver salt of the dye represented by the general formula (II) can be contained in the silver halide emulsion layer and used as an anti-irradiation dye. It can also be used as a filter dye or an antihalation dye by incorporating it in a photosensitive hydrophilic colloid layer. Further, two or more kinds of silver salts of the dye of the present invention may be used in combination depending on the purpose of use, or may be used in combination with other dyes as long as the effects of the present invention are not impaired.

In the present invention, the coating amount of the silver salt of the dye in the filter layer or the antihalation layer is from 0.05 to
Preferably 2.0 g / m ^2, in particular 0.1 to 1.0 g / m ² is preferred.

Further, in the present invention, the condensation product of substituted or unsubstituted polyhydroxybenzene and formaldehyde has the effect of preventing the deterioration of the contrast and the regression of the latent image with the passage of time. Specific examples of polyhydroxybenzene compounds which are condensation components of these aldehyde condensates are shown below.

Β-resorcinic acid γ-resorcinic acid 4-hydroxybenzoic acid hydrazide 3,5-hydroxybenzoic acid hydrazide p-chlorophenol sodium hydroxybenzenesulfonate p-hydroxybenzoic acid o-hydroxybenzoic acid m-hydroxybenzoic acid p -Dioxybenzene gallic acid p-hydroxybenzoic acid methyl o-hydroxybenzenesulfonic acid amide N-ethyl-o-hydroxybenzoic acid amide N-diethyl-o-hydroxybenzoic acid amide o-hydroxybenzoic acid-2-methylhydrazide Specifically, it can be selected from the derivatives of the compounds represented by the general formulas (IIa), (IIb) and (IIc) described in JP-B-49-49504.

As the hydrazine derivative, the above-mentioned general formula (I) is used.
In the case of containing halogen, at least one of the nucleation promoting compounds (nucleation promoting agents) described in JP-A-4-98239, page (7), lower left column, line 1 to page (26), lower left column, line 11 is halogen. It is preferably contained in the non-photosensitive layer on the silver halide emulsion layer and / or silver halide emulsion layer side.

In the present invention, examples of the nucleation accelerator preferably used include those represented by the following general formula (10) or (11).

[0072]

[Chemical formula 26]

In the general formula (10), R ₂₁ , R ₂₂ and R
Each of ₂₃ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group or a substituted aryl group. R ₂₁ , R ₂₂ and R
₂₃ can combine with each other to form a ring. Particularly preferred are aliphatic tertiary amine compounds.

These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and more preferably 300 or more. Examples of preferable adsorption groups include nitrogen-containing heterocyclic groups, mercapto groups, thioether groups, thione groups and thiourea groups.

In the general formula (11), R ₂₁ and R ₂₂ each represent a substituted or unsubstituted aryl group, aromatic heterocyclic group or hydrogen atom.

These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. The molecular weight is preferably 120 or more, and particularly preferably 300 or more, in order to have preferable diffusion resistance.

Specific compounds represented by the general formulas (10) and (11) include those shown below.

[0078]

[Chemical 27]

[0079]

[Chemical 28]

[0080]

[Chemical 29]

[0081]

[Chemical 30]

When these are contained in the light-sensitive material, they are contained in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer. It is particularly preferably contained in the silver halide emulsion layer.

In the light-sensitive material of the present invention, at least one conductive layer is preferably provided on the support. As a typical method for forming the conductive layer, a water-soluble conductive polymer,
There are a method of forming using a hydrophobic polymer and a curing agent and a method of forming using a metal oxide. For these methods, for example, the methods described in JP-A-3-265842, page (5) to page (15) can be used. The silver halide emulsion used in the present invention may be a conventional silver halide emulsion such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. However, it is preferable to use silver chlorobromide, silver bromide or 4 mol%.
The following are silver iodobromide or silver chloroiodobromide containing the following silver iodides.

Further, (standard deviation of particle size) / (average value of particle size) × 1
Monodisperse particles having a coefficient of variation represented by 00 of 15% or less are preferable.

In the light-sensitive material of the present invention, the total amount of gelatin on the emulsion layer side is 3.5 g / m ² or less. The emulsion layer side means the side of the layer having a silver halide emulsion with respect to the support, the silver halide emulsion layer, the hydrophilic colloid layer containing a redox compound capable of releasing a development inhibitor compound when oxidized, and Including other layers. Examples of other layers include an emulsion protective layer, an intermediate layer, and a conductive layer. The total amount of gelatin contained in the silver halide emulsion layer, the hydrophilic colloid layer containing the redox compound, and other layers is 3.5 g / m.
^{It is 2} or less, but preferably 0.5 to 3.3 g / m ² .

Various techniques and additives known in the art can be used in the silver halide emulsion of the present invention. For example,
The silver halide photographic emulsion and backing layer used in the present invention include various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents, development inhibitors, and ultraviolet absorbers. , Heavy metals, matting agents and the like can be contained by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion and the backing layer of the present invention.

More specifically, these additives are described in Research Disclosure (RD) Vol. 176, Item / 7643 (1978).
December) and Vol. 187, Item / 8716 (November 1979), and the relevant parts are summarized below.

Additive type RD / 7643 RD / 8716 Chemical sensitizer page 23, page 648, right column Sensitivity enhancer, same as above, whitening agent, page 24 Antifoggants and stabilizers, pages 24 to 25, page 649, right column Light absorbers, filters Dyes 25-26 pages 649 right column-UV absorbers 650 left column Stain inhibitors 25 pages right column 650 left-right columns Dye image stabilizers 25 pages Hardeners 26 pages 651 left columns Binders 26 pages Same as above Plastics Agents, lubricants, page 27, page 650, right column, coating aids, surfactants, pages 26 to 27, same as above, static inhibitor, page 27, same as above, as a support that can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, Cellulose nitrate,
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 an undercoating process if necessary.

The silver halide photographic light-sensitive material according to the present invention can be subjected to development processing after exposure by various methods, for example, a commonly used method.

Examples of the developing agent that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3- Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc., aminophenols (eg o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2 , 4-diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (tato) If 1
-(p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-
Methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.) alone or Although they can be used in combination, it is preferable to use them in a combination of 3-pyrazolidones and dihydroxybenzenes or a combination of aminophenols and dihydroxybenzenes. The developing agent is usually preferably used in an amount of 0.01 to 1.4 mol / l.

In the present invention, examples of sulfites and metabisulfites used as preservatives include sodium sulfite, potassium sulfite, ammonium sulfite and sodium metabisulfite. The sulfite is preferably 0.25 mol / l or more. It is particularly preferably 0.4 mol / l or more.

In the present invention, as a silver sludge inhibitor, Japanese Patent Publication No. 62702/1987, JP-A-3-51844, and JP-A-4-26838,
The compounds described in Nos. 4-362942 and 1-319031 can be used. More preferably, the compound represented by the following general formula (12) or (13) can be used.

When it is contained in a photographic light-sensitive material, it is contained in a silver halide emulsion layer or a hydrophilic colloid layer adjacent to the silver halide emulsion layer. It is preferably contained in the photographic light-sensitive material, and particularly preferably contained in the silver halide emulsion layer.

In the developer, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffer (for example, carbonate, phosphate, borate, boric acid,
Acetic acid, citric acid, alkanolamines, etc., solubilizing agents (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.) ), Surfactants, defoamers, antifoggants (for example, halogens such as potassium bromide, sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole,
Tetrazole, thiazole, etc.), chelating agent (eg ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate etc.), development accelerator (eg US Pat. No. 2,304,025, JP-B-47-45)
Compounds described in JP-A No. 541), a hardener (for example, glutaraldehyde or a bisulfite adduct thereof, etc.), or an antifoaming agent can be added. The pH of the developer is preferably adjusted to 9.5-11.0.

In the present invention, as a special form of development processing, an activator processing solution containing a developing agent in a light-sensitive material, for example, an emulsion layer, and processing the light-sensitive material in an alkaline aqueous solution to perform development may be used. . Such a development process, in combination with a thiocyanate silver salt stabilization treatment,
It is often used as one of the methods for rapid processing of a light-sensitive material, and the effects of the present invention can be obtained even when rapid processing is performed with such a processing solution.

As the fixing liquid, those having a generally used composition can be used. The fixing solution is generally an aqueous solution containing a fixing agent and others, and the pH is usually 3.8 to 5.8.
Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur compounds capable of forming a soluble stable silver complex salt. A known fixing agent can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum and the like can be added to the fixing solution.

If desired, the fixer may include a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), and a chelating agent having a water softening ability. And the like.

The developing solution may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a viscous liquid having a high viscosity and in a semi-kneaded state. Further, it may be diluted at the time of use, or may be used as it is.

In the development processing of the present invention, the development temperature is
It can be set to a normal temperature range of 20-30 ° C,
It can also be set to a high temperature treatment range of 30 to 40 ° C.

The black and white silver halide photographic light-sensitive material according to the present invention is preferably processed by using an automatic processor.
At that time, the processing is performed while replenishing a fixed amount of developing solution proportional to the area of the photosensitive material. The development replenishment amount is 250 ml or less per 1 m ² in order to reduce the amount of waste liquid. It is preferably 75 ml or more and 200 ml or less per 1 m ² . Particularly preferably, it is 75 ml or more and 150 ml or less per 1 m ² . 75 ml per 1 m ²
If the replenishment amount of the developing solution is less than the above, satisfactory photographic performance cannot be obtained due to desensitization, softening, and the like.

In order to shorten the developing time, the present invention provides a total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone when processing using the automatic developing machine. It is preferably 20 to 60 seconds. The total processing time referred to here includes all process times required for processing a black and white silver halide photographic light-sensitive material, and specifically includes, for example, development, fixing, bleaching, washing with water, stabilization processing and drying necessary for processing. The time including all process times, that is, Dr
It's y to Dry time. If the total processing time is less than 20 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 30 to 60 seconds.

[0103]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 (Preparation of Silver Halide Emulsion A) A silver chloroiodobromide emulsion containing 70 mol% of silver chloride, 0.2 mol% of silver iodide and the rest of silver bromide was prepared by the simultaneous mixing method. . At the time of simultaneous mixing, K ₃ RhBr ₆ was added at 8.1 × 10 ⁻⁸ mol per mol of silver. The resulting emulsion was a cubic, monodisperse grain with a mean grain size of 0.20 μm (variation coefficient 9
%) Emulsion. Then, the emulsion was desalted with a modified gelatin described in JP-A-2-280139 (a gelatin in which an amino group was substituted with phenylcarbamyl, for example, G-8 in JP-A-2-280139). The EAg after desalting was 190 mv at 50 ° C.

The emulsion thus obtained was adjusted to pH 5.58 and EAg123mv, and the temperature was adjusted to 60 ° C., and chloroauric acid was added to 2.2 mol per mol of silver.
× 10 ^-5 mol was added and stirred for 2 minutes, then S ₈ was added per 1 mol of silver
2.9 × 10 ^-6 mol was added, and the mixture was further stirred for 78 minutes for chemical ripening. At the end of ripening, the following amount was added per mol of silver.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 7.5 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole 3.5 × 10 ^-4 mol and gelatin 28.4 g An emulsion liquid was added.

(Preparation of silver halide photographic light-sensitive material) On one undercoat layer of a polyethylene terephthalate film having a thickness of 100 μm and subjected to the antistatic treatment described in Example 1 of JP-A-3-92175, the following formulation ( A) Further, a silver halide emulsion having the following formulation (B) was coated on the upper layer so that the silver amount was 3.3 g / m ² and the gelatin amount was 2.3 g / m ² .

Further, a coating solution having the following formulation (C) was applied as a protective layer on the upper layer so that the amount of gelatin was 1 g / m ² . On the undercoat layer on the opposite side, a backing layer having the following formulation (D) was applied so that the amount of gelatin would be 2.7 g / m ² .
Further, a protective layer having the following formulation (E) was coated on the upper layer so that the amount of gelatin was 1 g / m ² , and 14 kinds of samples shown in Table 1 were prepared.

Formulation (A) Silver salt of methine compound of the present invention (shown in Table 1) 0.2 g / m ² (ball mill solid fine particle dispersed) Saponin 6 mg / m ² Styrene-maleic acid polymer 15 mg / m ² Gelatin 0.6 mg / m ² Recipe B (silver halide emulsion layer composition)

[0110]

[Chemical 31]

S-1 (sodium-iso-amyl-n-decylsulfosuccinate) 0.64 mg / m ² compound represented by general formula (I) (shown in Table 1) 2.0 × 10 ⁻⁴ mol / mol Ag Nucleation Accelerator Exemplified Compound 10-9 1.0 × 10 ⁻³ mol / mol Ag Formulation C (Emulsion Protective Layer Composition) S-1 12 mg / m ² Matting Agent: Monodispersed Silica with Average Particle Diameter 3.5 μm 22 mg / m ² Hard Membrane agent: 1,3-vinylsulfonyl-2-propanol 40mg / m ²

[0112]

[Chemical 32]

[0113] Formulation D (backing layer composition) saponin ^{133mg / m 2 S-1 6mg} / m 2 Colloidal silica 100 mg / ^{m 2}

[0114]

[Chemical 33]

Formulation E (Backing protective layer composition) Matting agent: Monodisperse polymethylmethacrylate having an average particle size of 5.0 μm 50 mg / m
² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10mg / m ² Hardener: Glyoxal 5mg / m ^{2 The} obtained sample was adhered to a step wedge, and interference of wavelength 633nm was used as a substitute characteristic of He-Ne laser light. After performing high-intensity exposure for 10 ^-6 seconds through a filter, use the developing solution and fixing solution of the following composition and use the automatic processor for rapid processing (GR-26
SR Konica Co., Ltd.) was processed under the following conditions.

(Developer Formulation) Sodium sulfite 55 g / liter Potassium carbonate 40 g / liter Hydroquinone 24 g / liter 4-Methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (Dimeson S) 0.9 g / liter Potassium bromide 5 g / L 5-Methyl-benzotriazole 0.13 g / L Boric acid 2.2 g / L Diethylene glycol 40 g / L Silver anti-sludge agent 12-5 100 mg / L 13-2 300 mg / L Water / potassium hydroxide 1 L / pH 10. Set to 5.

(Fixing Solution Formulation) (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate ・ trihydrate 6.5 g Boric acid 6.0 g Sodium citrate ・ dihydrate 2.0 g (Composition B) Pure water (ion-exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ converted content is 8.1% W / V aqueous solution) 26.5 g The composition A and the composition B were melted in this order and finished to 1 liter before use. Of this fixer
The pH was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 33 ° C. 20 seconds Washing with water 20 ° C. normal temperature 20 seconds Drying 40 ° C. 40 seconds The developed sample obtained was subjected to PDA-65 (Konica Digital Density). (Total). The sensitivities in the table are relative sensitivities when the sensitivity of Sample No. 1 at a concentration of 3.0 is 100. Further, gamma is represented by tangents of densities of 0.1 and 3.0. When the gamma value in the table is less than 6, it is a photosensitive material that cannot be used, and even if it is 6 or more and less than 10, the contrast is still insufficient. A gamma value of 10 or more means that a super-high contrast image can be obtained for the first time, indicating that the material is a sufficiently practical photosensitive material.

The black spots in the unexposed area were evaluated with a magnifying glass of 40 times. The highest rank is 5 when no black spots occur, and it is 4, 3, 2, 1 according to the degree of black spots.
And lowered the rank. Ranks 1 and 2 are practically unfavorable levels.

The results obtained are shown in Table 1.

[0121]

[Table 1]

As can be seen from the table, the sample according to the present invention exhibits high sensitivity and gamma, prevents generation of black spots, and exhibits an excellent improving effect.

Example 2 Continuous processing was performed using the sample prepared in Example 1 and the same processing solution.

The replenishment is 150 ml / m ^{2 for} the developing solution and 190 ml for the fixing solution.
/ M ² used the same as the new solution.

The film exposed by the same method as in Example 1 was developed for 30 m ² and the photographic performance in a fatigue developing solution obtained was evaluated.

The sensitivity was expressed as a relative sensitivity when the sensitivity of Sample No. 1 of Example 1 was 100. The obtained results are shown in Table 2.

[0127]

[Table 2]

As is apparent from Table 2, according to the present invention,
It can be seen that even when the developer is fatigued due to running, the sensitivity is not lowered so much that the tone does not become soft and black spots are good.

[0129]

INDUSTRIAL APPLICABILITY According to the present invention, a super-high contrast image having high sensitivity and free from black spots can be obtained even when processed with a developer having a pH of 11.0 or less.

Claims (1)

[Claims] 1. A support having at least one silver halide emulsion layer, wherein the emulsion layer or another hydrophilic colloid layer contains a hydrazine derivative represented by the general formula (I), and And a silver halide photographic light-sensitive material containing at least one silver salt of a methine compound represented by the general formula (II). [Chemical 1] [In the formula, R ₁ represents an aliphatic group or an aromatic group, and as a part of the substituent,-(CH ₂ CH ₂₀ ) n-,-(CH ₂ CH (C
_{H 3) 0) n -,} - (CH 2 CH (OH) CH 2 0) n- ( where either n contains a partial structure of an integer of 1 or more), a quaternary ammonium cation as part of a substituent group Is a group containing Also R
₁ may contain a silver halide adsorbing group. G ₁ is -CO
- group, -COCO- group, -CS- _{group, -C (= NG 2 R 2} ) - group, -SO
- group, -SO ₂ - group, _{or, -P (O) (G 2} R 2) - represents a group. G ₂
Single bond, -O- group, -S- group, or -N (R ₂₎ is - group, R ₂ is an aliphatic group, an aromatic group or a hydrogen atom, a plurality of R ₂ in the molecule If present, they may be the same or different. One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl group, or an arylsulfonyl group. ] General formula (II) (Dye) _m1 [-(L) _m2- Sal] _m3 [In the formula, Dye represents an atomic group having a methine dye structure,
L represents a divalent linking group having a skeleton of an atom or atomic group selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and Sal represents a group which forms a sparingly soluble salt with a silver ion,
m1 is 1 or 2, m2 is 0 or 1, m3 is 1,
Represents 2, 3 or 4. ]