JPH06347931A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent fluctuation of sensitivity, deterioration of contrast, and increase of black spots against time lapse and to enable faithful reproduction of a highly precise image in the silver halide photographic sensitive material containing a specified hydrazine derivative by forming a region specified or higher in the transmission absorption degree of the total constituent layers including emulsion layers on one side of a support. CONSTITUTION:The silver halide photographic sensitive material has at least one silver halide emulsion layer on a support and contains the hydrazine derivative represented by the formula and the region having the transmission absorption degree of >=3.1 in the wavelength range of 400-450nm in the constituent layers including the emulsion layer on one side of the support. In the formula, R1 is an aliphatic or aromatic group; G1 is -COor the like; G2 is a simple bond or -O- or the like: and each of A1 and A2 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 used in a process called "return" in a plate making process.

[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.

On the other hand, the quality of scanners has been improved in the plate making industry, and high-definition image output of 600 lines / inch or more is becoming popular. However, in the plate making process, plate making is rarely done directly from the output scanner film, and multiple patterns, character images, etc. are printed and composited on the return film in the plate making process to form the final image for the printing plate. Is normal. At this time, if the scanner photosensitive material that is output with high precision using the conventional return photosensitive material is returned, the problem occurs that halftone dots become thick and faithful reproduction cannot be performed. Therefore, it is desired to provide a reversal light-sensitive material capable of faithfully reproducing a high-definition image.

[0010]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a reversal silver halide photographic light-sensitive material which is capable of preventing fluctuations in sensitivity, softening and increase of black spots over time, and capable of faithfully expressing high-definition images. To provide. Still another object is to provide a silver halide photographic light-sensitive material for printing plate making which has the above-mentioned properties and has a processing performance with a developer having a pH of less than 11.0.

[0011]

The above object of the present invention is to have at least one silver halide emulsion layer on a support,
In a silver halide photographic light-sensitive material containing the hydrazine derivative represented by the general formula (I) [Chemical formula 1] in the emulsion layer or other hydrophilic colloid layer, the silver halide emulsion layer is included on a support. The transmission absorbance of all the constituent layers on the
It is achieved by a silver halide photographic light-sensitive material having a region of 3.1 or more at any wavelength in the range of 400 to 450 nm.

In the emulsion layer of the above light-sensitive material,
It is preferable to contain a dye having an absorption at 400 to 450 nm.

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 (I).

[0015]

[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 (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 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.

R₁Aliphatic groups, aromatic groups or their groups
The substituent is-(CH₂CH₂O) n−, − (CH₂CH (CH ₃) O) n− or − (CH₂
CH (OH) CH₂O) n- or contains a quaternary ammonium
It contains a nickel cation. n is preferably an integer from 1 to 15
Good R₁Is preferably the following general formula (II) or general formula
It is represented by (III), general formula (IV) or general formula (V).

[0022]

[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 intramolecular 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 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 -CO
In the case of a — group, preferred among 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 ₁
It may be _{one that} splits the -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, and examples thereof include JP-A-63- And those described in 29751.

R ₁ or R ₂ of the general formula (I) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. 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 is, for example, disclosed in JP-A-61-213847, JP-A-62-260153 and US Pat. No. 3,379,52.
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.

[0035]

[Chemical 4]

[0036]

[Chemical 5]

[0037]

[Chemical 6]

[0038]

[Chemical 7]

[0039]

[Chemical 8]

[0040]

[Chemical 9]

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

The compound of the general formula (I) is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluoroalcohol etc.), ketones (acetone, methyl ethyl ketone 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.

In the present invention, the absorbance between 400 and 450 nm is 3.
In order to have one or more areas, it is preferable to add a dye into the light-sensitive material. The dye may be water-soluble or water-insoluble. The water-insoluble dye is preferably added in the form of solid dispersion of fine particles. When a water-insoluble dye is used, it is desirable that the dye be decolorized or dissolved in the processing solution by pH or redox reaction so that the dye does not remain in the processed light-sensitive material.

Further, in the present invention, it is particularly preferable that the silver halide emulsion layer substantially contains a dye having an absorption between 400 and 450 nm. To add a dye to the emulsion layer, the dye may be added to the emulsion layer coating solution.
When a non-photosensitive adjacent layer is simultaneously coated in multiple layers on the emulsion layer, the coating liquid for the adjacent layer may contain a water-soluble dye. This is because the water-soluble compound diffuses from each layer immediately after coating, so that the emulsion layer substantially contains the dye.

According to the present invention, the absorbance between 400 and 450 nm is 3.1.
Having the above range means that there is a region having an absorbance of 3.1 or more at any wavelength in the range of 400 to 450 nm, and the absorbance does not need to be 3.1 or more in the entire region of 400 to 450 nm.

Examples of the water-soluble dye having absorption between 400 and 450 nm include compounds represented by the following general formulas (1), (2), (3) and (4).

[0047]

[Chemical 10]

In the formula, R ¹ is an atomic group represented by —OX or —N (X) (Y), and X and Y are each a hydrogen atom, an alkyl group, a cyanoalkyl group, a carboxyalkyl group, A sulfoalkyl group, a hydroxyalkyl group, a halogenated alkyl group or an optionally substituted alkyl group or its sodium or potassium salt, R ² and R ³ are each a hydrogen atom,
Represents a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylthio group or a group similar to the above-OX group, and Q is at least one halogen atom, a carboxyl group, a sulfo group or a sulfoalkyl group or sodium or potassium thereof. It represents a phenyl group or a sulfoalkyl group, a sulfoalkoxyalkyl group or a sulfoalkylthioalkyl group substituted with a salt, and L represents a methine group which may be substituted. R ⁴ represents an alkyl group, a carboxyl group, an alkoxycarbonyl group or an acyl-substituted or unsubstituted amino group. m represents 1 or 2, and n represents 0 or 1.

[0049]

[Chemical 11]

In the formula, R ⁵ , R ⁶ , R ⁸ , R ⁹ and R ¹⁰ are respectively
It represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, a carboxyl group or a sulfo group or a sodium or potassium salt thereof, and R ⁷ represents an alkyl group or a carboxyl group.

[0051]

[Chemical 12]

In the formula, R ¹¹ and R ¹² are each an alkyl group,
Represents a substituted alkyl group, an aryl group, an alkoxycarbonyl group or a carboxyl group, and R ¹³ and R ¹⁴ respectively represent an alkyl group substituted with a sulfo group or a carboxyl group, an aryl group substituted with a sulfo group or a carboxyl group, or its It represents a sodium or potassium salt, and L represents a substituted or unsubstituted methine chain. M represents a sodium, potassium or hydrogen atom, and p represents 0 or 1.

[0053]

[Chemical 13]

In the formula, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each represent an alkyl group, a hydroxyalkyl group, a cyano group, an alkylcyano group, an alkoxy group or a sulfoalkyl group.
R ¹⁹ and R ²⁰ each represent a sulfo group or a sulfoalkyl group.

Specific examples of the compounds represented by the general formulas (1) to (4) are described below in 1-1 to 1-19 described in [Formula 5] to [Formula 12] of Japanese Patent Application No. 5-5990. , 2-1 to 2-3, 3-1 to 3−
7, 4-1 to 4-6 can be mentioned.

As the hydrazine derivative, the above general formula (I)
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.

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

[0058]

[Chemical 14]

In the general formula (VI), R ₁₁ , R ₁₂ and R
Each ₁₃ 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 ₁₁ , R ₁₂ , and R ₁₃ are
They 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 (VII), 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 (VI) and (VII) include those shown below.

[0064]

[Chemical 15]

[0065]

[Chemical 16]

[0066]

[Chemical 17]

[0067]

[Chemical 18]

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

The 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, Japanese Patent Publication No. 62-4702, JP-A-3-51844, and JP-A 4-26838 are used as silver sludge inhibitors.
The compounds described in JP-A 4-362942, JP-A 1-319031 and the like can be mentioned. Particularly preferred are compounds represented by the following general formula (VIII) or (IX).

[0072]

[Chemical 19]

In the formula, R ₃₁ and R ₃₂ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group,
It represents an aralkyl group, a hydroxyl group, a mercapto group, a carboxyl group, a sulfo group, a phosphono group, an amino group, a nitro group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group or a sulfamoyl group. R ₃₁ and R ₃₂ may combine with each other to form a ring.

M ₁ and M ₂ represent a hydrogen atom, an alkali metal atom or an ammonium group, and R ₃₃ represents a hydrogen atom or a halogen atom.

Typical examples of the compounds represented by formula (VIII) or (IX) are shown below.

[0076]

[Chemical 20]

[0077]

[Chemical 21]

[0078]

[Chemical formula 22]

These silver sludge inhibitors are preferably added to the developing solution, but they may be added to the light-sensitive material.

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 developer, 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 9.5-10.5.

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, etc. 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 developing solution may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a viscous liquid with a high viscosity in a semi-kneaded state. 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 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 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 leading edge of the film is inserted into the automatic developing machine to when it exits from 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.

The halogen composition of silver halide in the silver halide emulsion is not particularly limited, but is preferably silver chloride or silver chlorobromide (silver bromide is preferably 5 mol% or less).

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, reduction sensitization and noble metal sensitization methods are known, and any of these may be used alone or in combination. The preferred chemical sensitization method is sulfur sensitization, and as the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanins, etc. may be used in addition to the sulfur compounds contained in gelatin. it can.

The gold sensitization method is a typical one of the noble metal sensitization methods, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, platinum, palladium, rhodium and other complex salts may be contained.

Examples of reduction sensitizers include stannous salts, amines,
Formamidine sulfinic acid, a silane compound, etc. can be used.

The average grain size of silver halide is preferably 0.7 μm or less, and particularly preferably 0.5 to 0.1 μm. The average particle size is a term that is commonly used and easily understood by experts in the field of photographic science. The particle size means a particle diameter when the particles are spherical or particles which can be approximated to a sphere. If the particle is a cube

[0095]

[Equation 1]

Let be the particle size. It is determined by an algebraic average or a geometric average based on the average particle projected area. For details on how to determine the average particle size, see (Mies, James: The Theory of the Photographic Process “CE
Mees & T.H. James: The theory of the photographic
process ”), 3rd edition, pp. 36-43 (1966 (published by McMillan“ Mcmillan ”)).

The shape of the silver halide grains is not limited,
Any shape such as a flat plate shape, a spherical shape, a cubic shape, a 14-sided shape, a regular octahedron shape or the like may be used. Further, the grain size distribution is preferably narrow, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total grain number falls within a grain size range of ± 40% of the average grain size is particularly preferable.

As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Gives a silver halide emulsion having a substantially uniform grain size.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Resear).
ch Disclosure) 176, 17643, 22-23 (December 1978) or cited.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azoles, for example, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-
Phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3, 3a, 7-Tetrazaindenes), pentazaindenes, etc .; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. may be added. it can.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
Methyloldimethylhydantoin etc.), dioxane derivative (2,3-dihydroxydioxane etc.), active vinyl compound (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-
Methylenebis- [β- (vinylsulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, phenoxymucochloric acid etc.) isoxazole , Dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination.

The photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer of the present invention may be used for various purposes such as coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Known surfactants may be used.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid,
A wide variety of synthetic hydrophilic polymeric substances such as polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers can be used.

Examples of gelatin include lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Gelatin oxygen decomposition products can also be used.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (eg vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination,
Alternatively, it is possible to use a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

The silver halide emulsion of the present invention may be spectrally sensitized with a short-wave sensitizing dye, but is preferably not spectrally sensitized.

Various other additives are used in the light-sensitive material used in the present invention. For example, desensitizers, plasticizers, slip agents, development accelerators, oils, dyes, etc.

Regarding these additives and the above-mentioned additives, specifically, those described in Research Disclosure No. 176 (supra), pages 22 to 31 can be used.

In the light-sensitive material used in the present invention, the emulsion layer and the protective layer may be a single layer or a multilayer composed of two or more layers. In the case of multiple layers, an intermediate layer or the like may be provided between them.

In the light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for light-sensitive materials. Useful as the flexible support are films made of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene and polyethylene terephthalate.

[0112]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Latex Lx-A) 1.0 kg of gelatin was added to 60 liters of water.
A mixture of 0.01 kg of sodium dodecylbenzene sulfonate and 0.05 kg of ammonium persulfate and a mixture of styrene 3.0 kg, methyl methacrylate 3.0 kg and ethyl acrylate 3.2 kg under a nitrogen atmosphere while stirring at a liquid temperature of 60 ° C. and 2-
Sodium acrylamido-2-methylpropanesulfonate (0.8 kg) was added over 1 hour, followed by stirring for 1.5 hours, steam distillation for 1 hour to remove residual monomers, and then cooling to room temperature and adjusting the pH with ammonia. Adjusted to 6.0. The obtained latex liquid was made up to 75 kg with water. As described above, a monodisperse latex having an average particle size of 0.1 μm was obtained.

(Emulsion preparation) A silver nitrate solution and an aqueous solution of sodium chloride and potassium bromide were mixed with 8 × rhodium hexachloride complex.
A solution added to 10 ^-5 mol / Agmol was simultaneously added to the gelatin solution while controlling the flow rate, and then desalted according to a conventional method to obtain a cubic crystal having a grain size of 0.13 μm and 1 mol% of silver bromide. ,
A monodisperse silver chlorobromide emulsion was obtained.

This emulsion was sulfur sensitized in the usual way and 6-methyl-4-hydroxy-1,3,3a, 7 tetrazaindene was added as a stabilizer. Furthermore, after adding the following compounds,
The following additives were added to prepare an emulsion coating solution.

Hydrazine derivative (shown in Table 1) 1 × 10^-Fourmol / mol Ag p-Nonylphenol / ethylene oxide 35 mol adduct 100 mg / m² (C_FiveH₁₁N-CH₂CH₂OCH₂CH₂)₂S 1 x 10^-3mol / molAg Silver sludge inhibitor (VIII-1) 1.7mg / m² Emulsion coating liquid Potassium bromide 5mg / m² 2,5-Dimethyl-4-isothiazolin-3-one 1mg / m² 0.5N sodium hydroxide aqueous solution Adjusted to pH 5.6 Compound (Dyes A to E below) Amount shown in Table 1 Saponin (20%) 0.5cc / m² Sodium dodecylbenzene sulfonate 20mg / m² 5-methylbenzotriazole 10mg / m² 1-phenyl-5-mercaptotetrazole 2mg / m² 2,5-di (carboxymethylthio) -1,3,4-thiadiazole 10mg / m² 3,3,3 ', 3'-Tetramethyl-5,6,5', 6'-Tetrahydroxy-1,1'-spirobiindane 6mg / m² Latex Lx-A 0.5g / m² Styrene-maleic acid copolymer (thickener) 90mg / m² When applying the emulsion, the amount of gelatin is 1.2 g / m²Was adjusted so that

Next, an emulsion protective layer coating solution, a backing layer coating solution, and a backing protective layer coating solution were prepared with the following compositions.

Emulsion protective layer coating solution Gelatin 1.1 g / m ² compound (dye shown in Table 1) Amount shown in Table 1 compound (b) 40 mg / m ² compound (d) 100 mg / m ² spherical monodisperse silica (8 μm) 20 mg / m ² 〃 (3 μm) 10 mg / m ² gallic acid allyl ester 100 mg / m ² compound (a) 1 mg / m ² oxalic acid adjusted to pH 5.8 Latex Lx-A 0.5 g / m ² Styrene-maleic acid co- Polymerized polymer (thickener) 50 mg / m ² Formaldehyde (hardener) 10 mg / m ² Backing layer coating liquid Gelatin 1.0 g / m ² compound (c) 80 mg / m ² compound (d) 15 mg / m ² compound (e) 150 mg / m ² of calcium chloride 0.3 mg / m ² saponin (20% aqueous solution) 0.6 cc / m ² citric acid pH5.5 adjustment latex (m) 300mg / m ² 5- methyl benzotriazole 10 mg / m ² 5-nitro indazole 20 mg / m ² of polyethylene glycol (molecular weight 1540) 10mg / m ² styrene - maleic acid copolymer ( Nebazai) 45 mg / m ² glyoxal (curing agent) 4 mg / m ² Compound (n) 80mg / m ² Backing protective layer coating liquid Gelatin 1.18 g / m ² Compound (a) (1% aqueous solution) 2 ml / m ² Compound ( c) 20 mg / m ² compound (d) 4 mg / m ² compound (e) 50 mg / m ² spherical polymethylmethacrylate (4 μm) 25 mg / m ² sodium chloride 70 mg / m ² compound (a) 1 mg / m ² glyoxal 22 mg / m ² Bisvinylsulfonylmethyl ether (hardener) 5 mg / m ²

[0119]

[Chemical formula 23]

[0120]

[Chemical formula 24]

[0121]

[Chemical 25]

[0122]

[Chemical formula 26]

Each of the coating solutions prepared as described above was applied to the emulsion side by undercoating shown in JP-A-59-19941 to obtain a thickness of 10
After applying corona discharge at 10 W / m ² · min to the backing surface side of 0 μm polyethylene terephthalate base, use the roll-fit coating pan and air knife with the following composition so that the coating amount will be 10 cc / m ^2. Applied and dried.

Drying is performed at 90 ° C., overall heat transfer coefficient is 25 kcal (m ²
・ Hr ・ ° C) parallel flow drying condition for 30 seconds, then 140 ° C ・
It took 90 seconds. The thickness of the layer after drying was 1 μm, and the surface specific resistance of this layer was 1 × 10 ⁸ Ω at 23 ° C. and 55%.

[0125]

[Chemical 27]

Ammonium sulfate 0.5 g / liter Polyethylene oxide compound (average molecular weight 600) 6 g / liter Curing agent 12 g / liter

[0127]

[Chemical 28]

On this base, the emulsion layer and the emulsion protective layer were first coated in order from the side closer to the support as the emulsion surface side, while the temperature was kept at 35 ° C., while the hardener solution was added by the slide hopper system, and then cold air was applied. After passing through the set zone (5 ° C.), a backing layer and a backing protective layer were coated on the side opposite to the emulsion surface while similarly adding a hardening agent with a slide hopper, and set with cold air (5 ° C.). The coating liquid exhibited sufficient setting properties when it passed through each setting zone. Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the backing surface side, it was conveyed in a state in which there was no contact with the roller or the like until winding up. The coating speed at this time was 120 m / min.

(Drying conditions) After setting, the product was dried with a drying air at 30 ° C. until the weight ratio of water / gelatin reached 800%, and the mixture was dried at 800-20
Dry 0% with 35 ° C (30%) dry air, apply the air as it is, and 30 seconds after the surface temperature reaches 34 ° C (it is considered that the drying is completed), use 48 ° C / 2% air. It was dried for 1 minute. At this time, the drying time is from start of drying to water / gelatin ratio of 800%.
0 second, 35% from 800% to 200%, 5 seconds from 200% to the end of drying.

This sensitive material was wound at 23 ° C. and 40%, then cut under the same environment, and placed in a barrier bag which was conditioned for 3 hours at 40 ° C.
After humidity was adjusted to 10% for 8 hours, it was sealed together with cardboard which had been adjusted to humidity at 23 ° C. and 40% for 2 hours.

The silver coating amount of the light-sensitive material produced as described above was 3.5 g / m ² .

The sample prepared as described above was output with a scanner SG-747 (manufactured by Dainippon Screen Co., Ltd.) and a high-definition (600 lines / inch) halftone dot image was used as an original for the printer P-627GM (Dainippon Contact-exposure using a screen (manufactured by K.K.), rapid processing automatic processor GR-26S manufactured by Konica.
R was developed according to the following processing conditions. (45 sec processing) (developing condition) Step Temperature Time Replenishment rate development 38 ° C. 12 sec 160 cc / m ² fixing 35 ° C. 10 sec 190 cc / m ² washing room temperature 10 seconds Drying 50 ° C. 13 seconds developer formulation Sodium sulfite 55g potassium carbonate 40g Hydroquinone 24g 4-Methyl-4-hydroxymethyl-1-phenyl-3-0.9g Pyrazolidone (Dimeson S) Potassium bromide 5g 5-Methylbenzotriazole 0.13g 1-Phenyl-5-mercaptotetrazole 0.02g Boric acid 2.2g Compound VIII-5 100 mg Compound IX-2 300 mg Diethylene glycol 40 g Water was added to make 1 liter, and pH was adjusted to 1 liter with sodium hydroxide.
Adjust to 10.5.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5 W / V% aqueous solution) 240 cc Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium oxalate dihydrate 2.0 g (Composition B) Pure Water (ion-exchanged water) 17cc Sulfuric acid (50W / v% aqueous solution) 4.7g Aluminum sulphate (Al2o3 equivalent content is 8.1W / V% aqueous solution) 26.5g When used, 500cc water dissolves composition A and composition B in this order. 1
Finished to liters. The pH was adjusted to 4.8 with acetic acid. At this time, the appropriate exposure amount was the exposure amount at which the density of the inverted (blackened) image portion with respect to the non-image portion of the document was 4.6, and the blackened area of the halftone dot image at this exposure amount was measured. Concentration is PDA-65
Density meter (manufactured by Konica Corp.), halftone dot area was measured with ortho light using X-Rite 361T. The halftone dot area of the manuscript was 43.8%.

The developed sample thus obtained was measured with a Konica Digital Densitometer PDA-65, and gamma was represented by the tangent of densities of 0.1 and 2.5. A gamma value of less than 6 is unusable, and a gamma value of 6 or more and less than 10 still has insufficient hardness. Only when the gamma value is 10 or more, a super-high contrast image will be obtained, and it will be practically usable.

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"
The black spots are also levels that are not practically preferable.

The results are also shown in Table 1.

[0137]

[Table 1]

[0138]

[Chemical 29]

The addition amount of the dye in Table 1 is the total of the emulsion layer and the emulsion protection layer, and the addition amount of the dye per unit amount of gelatin was uniform in each layer. In addition, the absorbance was measured with a spectrophotometer UV-260 (Shimadzu Corporation) for the sample without the backing layer and the backing protective layer applied.
Manufactured) to measure the undercoated support.

[0140]

According to the present invention, a return film having good halftone dot performance (precision reproduction of the original), high gamma, and no increase in black spots was obtained.

Claims (2)

[Claims] 1. A halogenated product having at least one silver halide emulsion layer on a support, and the emulsion layer or another hydrophilic colloid layer containing a hydrazine derivative represented by the following general formula (I). In the silver photographic light-sensitive material, the transmission absorbance of all the constituent layers on the side including the silver halide emulsion layer with respect to the support is 3.1 at any wavelength in the range of 400 to 450 nm.
A silver halide photographic light-sensitive material having the above areas. [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. ] 2. A silver halide emulsion layer containing substantially 400
2. The silver halide photographic light-sensitive material according to claim 1, which contains a dye having an absorption at ˜450 nm.