JPH06347932A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent deterioration of sensitivity and contrast and increase of black spots occurring on unexposed parts and to enable faithful reproduction of an ultrahigh contrast image by removing soluble salts by flocculation and precipitation with a modified gelatin in the desalting step of the manufacturing process of an emulsion and incorporating a specified hydrazine derivative in an emulsion layer or another hydrophilic colloidal layer. CONSTITUTION:The desalting process is executed by the flocculation precipitation with the modified gelatin to remove the soluble salts in the manufacturing process of the emulsion, and the silver halide photographic sensitive material contains in the emulsion layer or another hydrophilic colloidal layer the hydrazine derivative represented by the formula in which R1 is an aliphatic or aromatic group; G1 is -CO- or the like; G2 is a simple bond or -O- or the like; and one of A1 and A2 is H and the other is H or the like.

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 for printing plate making, and more particularly to a silver halide photographic light-sensitive material capable of obtaining high contrast.

[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.

The lith-type silver halide photographic light-sensitive material (hereinafter, also simply referred to as "lith-type light-sensitive material") used for infectious development has, for example, an average particle diameter of 0.2 μm, a narrow particle distribution and a well-formed particle shape. And a silver chlorobromide emulsion having a high silver chloride content (at least 50 mol% or more). By processing the lith-type light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, that is, 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 air oxidation and have extremely poor preservability, it is difficult to keep the development quality constant during continuous use.

A method is known in which a rapid and high-contrast image is obtained without using the lith developer. For example, as disclosed in JP-A-56-106244, a light-sensitive material containing a hydrazine derivative is processed with an alkali developing solution. According to these methods, it is possible to obtain a high-contrast image even by processing with a developing solution having good preservative property and capable of rapid processing.

[0006] In these techniques, in order to fully exert the high contrast property of the hydrazine derivative, it was necessary to carry out processing with a developer having a pH of pH 11.2 or higher. pH 11.2 or higher
The pH developing solution is more stable than the lith developing solution because the developing agent is easily oxidized when exposed to air, but due to the oxidation of the developing agent, a super-high contrast image may not be often obtained.

In order to compensate for this drawback, JP-A-63-29751
Japanese Patent Laid-Open Nos. 1-179939, 1-179940 and U.S. Pat.
No. 4 and the like disclose a light-sensitive material containing a hydrazine derivative and a nucleation accelerator which bring about a high contrast even in a developer having a relatively low pH of less than 11.2.

However, in the case of an image forming method in which a light-sensitive material containing such a contrast-improving agent is processed with a developer having a pH of less than 11.0, sensitization or softening occurs over time, and unexposed areas after development processing are exposed. The current situation is that there is a problem that the sandy fog that occurs, so-called black spots, deteriorates, and satisfactory performance cannot be obtained. Further, the residual color of the film after processing these photosensitive materials is also a big problem.

[0009]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to prevent deterioration of sensitivity and softening, or increase of black spots generated in an unexposed portion even when processed with a developer having a pH of less than 11.0. It is an object of the present invention to provide a silver halide photographic light-sensitive material capable of faithfully expressing a produced ultra-high contrast image.

A second object of the present invention is to provide a silver halide photographic light-sensitive material having the above-mentioned properties and having less residual color after processing.

[0011]

The above object of the present invention is to eliminate soluble salts in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support during the production process of the emulsion. The desalting treatment is carried out by coagulating and precipitating with modified gelatin, and the emulsion layer or other hydrophilic colloid layer contains a hydrazine derivative represented by the following general formula (1). It is achieved by a silver photographic light-sensitive material.

The present invention will be specifically described below.

The light-sensitive material of the present invention contains a hydrazine derivative represented by the following general formula (1).

[0014]

[Chemical 2]

In the formula, R ₁ represents an aliphatic group or an aromatic group, and-(CH ₂ CH ₂ O) n-,-(C
Contains a partial structure of H ₂ CH (CH ₃ ) O) n−, — (CH ₂ CH (OH) CH ₂ O) n− (where n is an integer of 1 or more) or contains a quaternary ammonium cation To do. G ₁ is a -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 is a single bond, -O- group, -S- group, or -N (R ₂₎ - represents a group, R ₂ represents an aliphatic group, an aromatic group or a hydrogen atom. When multiple R _2's are present in the molecule, 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.

The general formula (1) 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 typical examples of the substituent include 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, carbonamide, sulfonamide, carboxyl,
Examples of the substituents include phosphoric acid amide and the like. Preferred substituents are linear, branched or cyclic alkyl groups (preferably having 1 to 20 carbon atoms) and aralkyl groups (preferably having 7 carbon atoms).
~ 30), alkoxy groups (preferably 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 having 2 to 40 carbon atoms), a sulfonamide group (preferably 1 to 1 carbon atoms) 40 groups), ureido groups (preferably having 1 to 40 carbon atoms), phosphoric acid amide groups (preferably having 1 to 40 carbon atoms) and the like.

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 (II), general formula (III), general formula (IV) or general formula (V).

[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 (II), (III), R 7 as defined in (IV)) in combination It is a divalent group created. More preferably, R ₃ is an alkylene group having 1 to 10 carbon atoms or those and --S
-, - SO -, - SO 2 - is a bivalent group produced by combining, R ₄ and R ₅ 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 preferable substituents are those listed as the substituents for R ₁ .

In the general formulas (II) and (III), 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 (II), (III) and (IV), X ^- represents a counter anion or a counter anion moiety when forming an inner salt.

In the general formulas (III), (IV) and (V), 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 (IV) may be the same or different, and may combine with each other to form a ring. Z ₁ and R ₆ may be substituted, and as the preferable substituents, those enumerated as the substituents of R ₁ are applicable.

In the general formula (V), 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 is as in formula (1) synonymous.

As G ₁ in the general formula (1), --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 (1) 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), aralkyl (eg o-hydroxybenzyl), aryl group (eg phenyl, 3,5-dichlorophenyl) , O-methanesulfonamidophenyl, etc., 4-methanesulfonylphenyl, 2-hydroxymethylphenyl, etc.), and a hydrogen atom is particularly preferable. R ₂ may be substituted, and as the substituent,
The substituents listed for R ₁ are applicable. Also, R ₂ is G ₁
Portions of -R ₂ disrupts the residual molecule, -G ₁ -R ₂ moiety of atoms may be such as to rise to cyclization reaction to form a cyclic structure containing, as an example, for example, JP 63 -29751
And the like.

R ₁ or R _{2 in} the general formula (1) may have a ballast group or a 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 (1) of the present invention is, for example, disclosed in JP-A-61-213847, JP-A-62-260153 and US Pat. No. 4,684,60.
4, Japanese Patent Application No. 63-98803, U.S. Patents 3,379,529, 3,62
0,746, 4,377,634, 4,332,878, JP-A-49-12
9536, 56-153336, 56-153342, U.S. Pat.
It can be synthesized by utilizing the method described in No. 8,604, No. 4,994,365 and the like.

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 (1) 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 compound of the general formula (1) is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluoroalcohol, etc.), ketones (acetone, methylethylketone, etc.), dimethylformamide, dimethylsulfoxide. , 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 desalting method used in the present invention will be described. The silver halide emulsion is generally desalted after physical ripening in order to remove unnecessary salts. As a desalting method, there are a gelation method, a dialysis method, and a salting-out method using water-soluble sulfuric acid. In the present invention, the object was achieved by a method using a modified gelatin agent.

The theory of desalting using a modified gelatin agent is considered as follows. That is, when dibasic acid anhydride is reacted with gelatin, it reacts with the amino group of gelatin and Ge
l-NH-CO-R-COOH is formed, the amino group disappears, and the acid group becomes 1
Add more. When the pH of such gelatin is lowered below the pK value of the acid group, the acid group becomes a non-dissociative type, the amino group reacts with most of it, water solubility is reduced, and gelatin can be aggregated. The modified gelatin used in the present invention is a modified gelatin in which at least 50% or more of amino groups of gelatin molecules are substituted with acyl, carbamoyl, sulfonyl, thiocarbamoyl, alkyl and / or aryl groups.

Examples of substituents for the amino group of gelatin are:
U.S. Pat. Nos. 2,691,582, 2,614,928 and 2,525,753 are described.

Examples of useful substituents include (1) alkylacyl, arylacyl, acetyl and acyl groups such as substituted and unsubstituted benzoyl, (2) alkylcarbamoyl,
Carbamoyl groups such as arylcarbamoyl, (3) sulfonyl groups such as alkylsulfonyl, arylsulfonyl, etc., (4) thiocarbamoyl groups such as alkylthiocarbamoyl, arylthiocarbamoyl, etc., (5) C1-C1
18 straight-chain or branched alkyl groups, and (6) substituted or unsubstituted phenyl, naphthyl and aryl groups such as pyridyl and furyl aromatic heterocycles.

Preferred modified gelatin is an acyl group --COR ¹ or a carbamoyl group --CON (R ¹ ) R ²
It is gelatin replaced by.

R ¹ is a substituted or unsubstituted aliphatic group (eg, an alkyl group having 1 to 18 carbon atoms, an allyl group), an aryl group or an aralkyl group (eg, a phenethyl group), and R 1
² is a hydrogen atom, an aliphatic group, an aryl group, or an aralkyl group.

Particularly preferred is when R ¹ is an aryl group,
This is the case where R ² is a hydrogen atom.

Specific examples of the amino group substituent of modified gelatin are shown below, but the present invention is not limited thereto.

[0050]

[Chemical 10]

The modified gelatin can be used before the desalting step in the silver halide emulsion, but is preferably during the desalting step. The amount of modified gelatin added is not particularly limited, but when used for desalting, it is 0.1% of the substance (preferably gelatin) contained as a protective colloid after desalting.
~ 10 times the amount (weight) is suitable, and particularly preferably 0.2 ~
It is 5 times (weight).

The modified gelatin coagulates the silver halide grains together with the protective colloid. After the modified gelatin is added, the pH may be adjusted to coagulate the silver halide emulsion. The pH for coagulation is preferably 5.5 or less, particularly 4.8 to 2. The acid used for pH adjustment is not particularly limited, but organic acids such as acetic acid, citric acid and salicylic acid, and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid are preferably used. Heavy metal ions such as magnesium ions, cadmium ions, lead ions and zirconium ions may be added in combination with the modified gelatin.

The removal of dissolved substances (desalting) may be carried out once, or may be repeated several times. When it is repeated several times, modified gelatin may be added each time it is removed, or modified gelatin may be added first.

In the present invention, since the above-mentioned general formula (1) is contained as a hydrazine derivative, JP-A-4-98239 7
At least one of the nucleation accelerating compounds described on page 26, lower left column, line 1 to page 26, lower left column, line 11 is located on the silver halide emulsion layer and / or the silver halide emulsion layer side of the support and is not exposed to light. It is preferable to include it in the functional layer.

Examples of the nucleation accelerator include those represented by the following general formula (2) or (3).

[0056]

[Chemical 11]

In the general formula (2), R ₂₁ , R ₂₂ , R 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. A ring can be formed by R ₂₁ , R ₂₂ , and R ₂₃ . Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. A compound having a molecular weight of 100 or more is preferable to have diffusion resistance,
More preferably, the molecular weight is 300 or more. Further, preferable adsorption groups include nitrogen-containing heterocycles, mercapto groups, thioether groups, thione groups, thiourea groups and the like.

Specific compounds include those shown below.

[0059]

[Chemical 12]

[0060]

[Chemical 13]

[0061]

[Chemical 14]

In the general formula (3), Ar represents a substituted or unsubstituted aryl group or heteroaromatic ring. R ₃₁ represents an optionally substituted alkyl group, alkenyl group, alkynyl group or aryl group. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have a preferable diffusion resistant group, the molecular weight is preferably 120 or more, particularly preferably 300 or more.

Specific compounds include those shown below.

[0064]

[Chemical 15]

The compound represented by formula (2) or (3) of the present invention is preferably contained in the photographic light-sensitive material. When incorporated in a photographic light-sensitive material, it is incorporated in a silver halide emulsion layer or an adjacent hydrophilic colloid layer. Particularly preferably, it is contained in the layer containing the hydrazine derivative of the present invention.

The light-sensitive material of the present invention preferably has at least one conductive layer 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, see, for example, JP-A-3-265842, page 5, lower right column, line 1 to line 15.
The method described in the upper left column of the page and the sixth line can be used. The silver halide emulsion used in the present invention (hereinafter referred to as a silver halide emulsion or simply an emulsion) includes, for example, silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, And any of those used for ordinary silver halide emulsions such as silver chloride can be used, but silver chlorobromide, silver bromide or iodobromide containing 4 mol% or less of silver iodide is preferable. It is silver or silver chloroiodobromide.

[(Standard deviation of particle size)] / (average value of particle size)
Monodisperse particles represented by × 100 and having a coefficient of variation of 15% or less are preferable.

The light-sensitive material of the present invention is characterized in that 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. Other layers include, for example, emulsion protective layer, antihalation layer, U
Examples thereof include a V absorption layer, an intermediate layer and a conductive layer. Silver halide emulsion layers, although the total amount of gelatin contained in the hydrophilic colloid layer and other layers containing a redox compound is 3.5 g / m ² or less, preferably 0.5~3.3g / 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. , An anti-irradiation dye, a heavy metal, a matting agent and the like can be further contained by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion of the present invention 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). It is summarized below.

Additive Type RD / 7643 RD / 8716 1. Chemical sensitizer Page 23 Page 648 Right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggants and stabilizers 24 to 25 pages 649 right column 6. Light absorbers, filter dyes 25 to 26 pages 649 right column ~ ultraviolet absorbers 650 page left column 7. Anti-stain agent page 25 right column page 650 left-right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binder page 26 Same as above 11. Plasticizer, lubricant Page 27 Page 650 Right column 12. Coating aid, surface active agent, pages 26 to 27, same as above 13. Antistatic Agent Page 27 As above As a support which 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 a surface treatment if necessary.

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

The developing agents that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone, etc.), 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 (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline , 1- (p-aminophenyl)
-3-aminopyrazoline, 1- (p-amino-N-methylphenyl)
-3-aminopyrazoline etc.) can be used alone or in combination, but it is preferable to use them in combination with 3-pyrazolidones and dihydroxybenzenes or with aminophenols and dihydroxybenzenes. preferable. The developing agent is usually preferably used in an amount of 0.01 to 1.4 mol / liter.

In the present invention, as a silver sludge-preventing agent, JP-B-62-4702, JP-A-3-51844, JP-A-4-26838,
4-362942 and 1-319031, more preferably compounds represented by the following general formula (VI) or (VII) can be used.

[0075]

[Chemical 16]

In the formula, R ₁₁ and R ₁₂ are hydrogen atom, alkyl group, aryl group, aralkyl group, hydroxy group, mercapto group, carboxy group, sulfo group, phosphono group, amino group, nitro group, cyano group, halogen atom. , An alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, and an alkoxy group. Also R
₁₁ and R ₁₂ may combine to form a ring structure.

In the general formula (VII), M ₁ and M ₂ are hydrogen atoms and N
represents a, K, NH ₄ , and X ₁ represents a hydrogen atom or a halogen atom.

Typical examples of the compounds represented by formulas (VI) and (VII) are shown below.

[0079]

[Chemical 17]

[0080]

[Chemical 18]

[0081]

[Chemical 19]

[0082]

[Chemical 20]

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

In the developing solution, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg, carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) , Solubilizers (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds etc.),
Surfactants, antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), development accelerator (for example, US Pat. No. 2,304,025)
Nos. 5,047,456 and Japanese Patent Publication No. 47-45541), a hardener (eg glutaraldehyde or its bisulfite adduct), an antifoaming agent and the like can be added. The pH of the developer is preferably adjusted to 9.5-12.0.

The compounds of the present invention, as a special form of development processing, include a developing agent in a light-sensitive material, for example, an emulsion layer,
You may use it for the activator processing liquid which makes a photosensitive material process in alkaline aqueous solution and develops. Such a developing treatment is often used as one of the rapid processing methods for a light-sensitive material in combination with a silver salt stabilizing treatment with a thiocyanate, and can be applied to such a processing solution.
In the case of such rapid processing, the effect of the present invention is particularly great.

As the fixing solution, those having a generally used composition can be used. The fixer is generally an aqueous solution containing a fixer 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 capable of forming a soluble stable silver complex salt. A compound known as a 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 contain preservatives (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), and pH.
A compound such as a modifier (for example, sulfuric acid), a chelating agent having the ability to soften water, or the like can be included.

The developer may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a semi-kneaded viscous liquid having a high viscosity. Further, it may be diluted before 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 light-sensitive material according to the present invention is preferably processed 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 1 in order to reduce the amount of waste liquid.
250cc or less per m ² . Preferably 75 to ² per m ²
It is 00cc. If the developer replenishment rate is less than 75 cc per m ^2, desensitization, softening, etc. will not be possible to obtain satisfactory photographic performance.

According to the present invention, the total processing time (Dry to Dry) from when the film front end is inserted into the automatic developing machine to when it comes out of the drying zone is 20 when the processing is performed by using the automatic developing machine in order to shorten the developing time. It is preferably -60 seconds. The total processing time referred to here includes all process times required for processing the black-and-white light-sensitive material, and specifically, for processing, for example, developing, fixing, bleaching, washing, stabilizing, drying, etc. It is the time that includes all the process time, that is, the time to Dry to Dry. 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 (Dr
y to Dry) is 30 to 60 seconds.

[0093]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example 1 (Preparation of silver halide emulsion A) Silver chloroiodobromide (70 mol% of silver chloride and 0.2 mol% of silver iodide per 1 mol of silver) was prepared by the simultaneous mixing method. At the time of this mixing, K ₃ RhBr ₆ was added in an amount of 8.1 × 10 ^-8 mol per mol of silver. The obtained emulsion was an emulsion composed of cubic grains having an average grain size of 0.2 μm and a coefficient of variation of 9%.

(Desalting) The obtained emulsion was treated with caustic soda.
After adjusting to pH 5.5, the mixture was divided and desalted under the following conditions.

A) Comparative To 1.0 Kg of the divided emulsion (content: 44 g, 4 g of ossein gelatin), 80 ml of 10% ossein gelatin solution was added at 40 ° C., and after stirring for 10 minutes, 5% polynaphthalene sulfone was added. 90 ml of acid solution and 90 ml of 20% magnesium sulphate were added. 5
After stirring for 1 minute, let stand and allow the emulsion to settle, and then clear the supernatant.
800 ml was removed.

Then, 800 ml of pure water at 40 ° C. was added and stirred for 5 minutes, then 30 ml of 20% magnesium sulfate solution was added,
After stirring for 5 minutes, the mixture was left standing and 800 ml of the supernatant was removed. 20%
The same desalting operation was carried out once again using 30 ml of magnesium sulfate.

The liquid temperature during the operation was kept at 40 ° C.

The following compound [A] was added to the obtained emulsion.
80 ml of a 10% ossein gelatin solution containing the mixture of [B] and [C] was added and redispersed at 55 ° C. to obtain a target emulsion.

[0100]

[Chemical 21]

B) 1.0 kg of the divided emulsion (content: 44 g,
80 ml of a 10% modified gelatin solution was added to ossein gelatin (4 g) at 40 ° C., and the mixture was stirred for 10 minutes. After that, adjust the pH to 4.4 with a 5% sulfuric acid solution, stir for 5 minutes, then let stand,
After allowing the emulsion to settle, 800 ml of the supernatant was removed.

Next, 800 ml of pure water at 40 ° C. was added, the pH was adjusted to 5.7 with 5% caustic soda, and the mixture was stirred for 5 minutes for dispersion.

Further, the desalting operation similar to the above was carried out twice using a sulfuric acid solution and a caustic soda solution.

The liquid temperature during the operation was kept at 40 ° C.

To the resulting emulsion was added 80 ml of a 10% ossein gelatin solution containing a mixture of the same compounds [A], [B] and [C] as in a), and redispersed at 55 ° C. An emulsion of was obtained. pA of the emulsions obtained in both a) and b) at 40 ° C
g was 7.6.

Subsequently, the temperature of the emulsion was adjusted to 60 ° C. and the pH was adjusted.
Was adjusted to 5.58 and EAg was adjusted to 123 mV. Furthermore, HAuC
The chemical sensitization was carried out by adding l ₄ of 2.2 × 10 ^-5 mol per mol of silver and stirring for 2 minutes, and then adding S ₈ of 2.9 × 10 ^-6 mol per mol of silver and further stirring for 78 minutes. At the end of the chemical sensitization, the following compounds were added and then the temperature was lowered to 40 ° C. to complete the chemical sensitization. The number shown indicates the amount added per mol of silver.

4-Methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 7.5 × 10 ^-3 mol 1-phenyl-5-mercaptotetrazole 3.5 × 10 ^-4 mol Gelatin 28.5 g (silver halide photograph Preparation of Photosensitive Material) On one undercoat layer of 100 μm-thick polyethylene terephthalate film having a backing surface described in Example 1 of JP-A-3-92175 and antistatically processed undercoat, one of the following formulations (1) Is coated so that the amount of gelatin is 2.6 g / m ² and the amount of silver is 3.3 g / m ^2, and an emulsion protective layer of the following formulation (2) is applied on it with a gelatin amount of 1.0 g / m ^2. g / m ² and the backing layer on the other side on the other side according to the following prescription (3) so that the amount of gelatin is 2.7 g / m ² . Further, a backing protective layer having the following formulation (4) was applied thereon so that the amount of gelatin would be 1 g / m ² to obtain sample Nos. 1 to 18.

Formulation (1) (Silver halide emulsion layer composition) Gelatin 2.6 g / m ² Silver halide emulsion A Silver amount 3.3 g / m ² Sensitizing dye: A 6.0 mg / m ² Antifoggant 1.7 mg / m ² surfactant ^{100mg / m 2: S-1} 0.64mg / m 2 latex polymer: 0.5 g / m (shown in Table 1) a hydrazine derivative according to ² hardener H-1 60 mg / m ² present invention 2 × 10 ^-4 mol / Ag1mol Nucleation enhancer (2-9) 1 × 10 ^-3 mol / Ag1mol Amount shown in Table 1

[0109]

[Chemical formula 22]

Formulation (2) [emulsion protective layer composition] Gelatin 1.0 g / m ² Surfactant: S-1 12 mg / m ² Surfactant: p-perfluorononyloxy-sodium benzenesulfonate 0.6 mg / m ² Matting agent: Monodisperse silica with an average particle size of 3.5 μm 22 mg / m ² Hardener: 1,3-divinylsulfonyl-2-propanol 40 mg / m ² Formulation (3) [Backing layer composition]

[0111]

[Chemical formula 23]

[0112] Gelatin 2.7 g / m ² Surfactant: Saponin ^{133mg / m 2: S-1} 6mg / m 2 Colloidal silica 100 mg / m ² Hardener: ^H-2 100mg / m 2

[0113]

[Chemical formula 24]

Formulation (4) [Composition of backing protective layer] Gelatin 1 g / m ² Matting agent: Monodisperse with an average particle size of 5.0 μm Polymethyl methacrylate 50 mg / m ² Surfactant: Di- (2-ethylhexyl) -sulfo Succinate-monosodium salt 10 mg / m ² Hardener: Glyoxal 5 mg / m ^{2 The} obtained sample was adhered to a step wedge and He-Ne
As a substitute for a laser, a high-intensity exposure for 10 ^-6 seconds was performed through an interference filter of 633 nm, and then a developing solution and a fixing solution having the compositions shown below were added, and an automatic developing machine GR for rapid processing manufactured by Konica Corporation A development process was carried out at -26SR under the following conditions.

Developer Formulation Sodium sulfite 55g Potassium carbonate 40g Hydroquinone 24g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 0.9g Sodium bromide 5g 5-Methylbenzotriazole 0.13g 1-Phenyl-5-mercapto Tetrazole 0.02g Boric acid 2.2g Diethylene glycol 40g VI-5 100mg VII-2 300mg Add water and potassium hydroxide to make 1l / pH 10.5.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6.0g Sodium citrate dihydrate 2.0g (Composition B) Pure water (Ion-exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% W / V aqueous solution) 26.5 g When using the fixer, the above composition A in 500 ml of water is used. , Composition B were melted in this order and finished to 1 l for use. The pH of this fixer was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development 38 ° C 12 seconds Fixing 35 ° C 10 seconds Washing with water 10 seconds Normal temperature 10 seconds Drying 50 ° C 13 seconds Total 45 seconds Densitometer PD
Measured with A-65, the sensitivity of sample No. 1 at a concentration of 2.5 is 100.
The relative sensitivity is shown, and gamma is displayed with the tangent of the densities of 0.1 and 2.5. A gamma value of less than 6 cannot be used, and a gamma value of 6 or more and less than 10 still has insufficient hardness. With a gamma value of 10 or more, it becomes an ultra-high contrast image,
It is fully practical.

The black spots in the unexposed area were also evaluated with a magnifying glass of 40 times. The highest rank is "5" when black spots are not generated at all, and the rank is gradually lowered to "4", "3", "2", "1" according to the degree of occurrence of black spots. It shall be evaluated. Rank "1" and "2"
However, black spots are also levels that are not practically desirable.

Regarding the residual color, four sheets of the sample processed without exposure were piled up and the residual color of the film was visually evaluated. In the 5-level evaluation, "5" was colorless and "1" was a strong residual color. The residual color of less than "3" for general platemaking is a level that is not practically preferable. The results are shown in Table 1.

[0120]

[Table 1]

From the results shown in Table 1, it can be seen that the samples of the present invention have high sensitivity, high gamma, good black spots, and little residual color.

[0122]

According to the present invention, even if a developer having a pH of less than 11.0 is used, a high-contrast photographic characteristic can be obtained without deteriorating the sensitivity, and black spots generated in a halftone dot image can be controlled to obtain a high contrast. It was possible to provide a silver halide photographic light-sensitive material having excellent photographic characteristics and less residual color.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
During the production process of the emulsion, desalting treatment for removing soluble salts is performed by coagulating and precipitating with modified gelatin, and the hydrazine represented by the following general formula (1) is added to the emulsion layer or other hydrophilic colloid layers. A silver halide photographic light-sensitive material containing a derivative. [Chemical 1] In the formula, R ₁ represents an aliphatic group or an aromatic group, and-(CH ₂ CH ₂ O) n-,-(CH ₂ CH (CH ₃ ) O) n is used as a part of the substituent.
_{-, - (CH 2 CH (} OH) CH 2 O) n- ( where, n is an integer of 1 or more) or containing a partial structure of, containing quaternary ammonium cation. R ₁ may also 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 a _{-P (= O) (G 2} R
₂ ) -represents a group. G ₂ is a single bond, -O- group, -S- group, or -N (R ₂₎ - represents a group, R ₂ represents an aliphatic group, an aromatic group or a hydrogen atom. When multiple R _2's are present in the molecule,
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.