JPH08297344A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PURPOSE: To obtain an image stable even in processing with a developing soln. of a relatively low pH and having a very high contrast even after storage in a raw state over a long period of time by forming a silver halide emulsion layer and a nonphotosensitive hydrophilic colloidal layer contg. a specified compd. CONSTITUTION: This silver halide photographic sensitive material has a silver halide emulsion layer and a nonphotosensitive hydrophilic colloidal layer on the substrate and the colloidal layer contains a compd. represented by the formula ED-X-[C(R1 )=C(R2 )]n -C(A1 )(A2 )-Y-Z, wherein ED is a group which releases a group represented by the formula -X-[C(R1 )=C(R2 )]n -C(A1 )(A2 )-Y-Z when oxidized, X is -O-, -S- or -N(R3 )-, each of R1 -R3 is H or a monovalent group, (n) is 1 or 2, each of A1 and A2 is H, an alkyl or aryl, Y is -O-, -S-, etc., and Z is a monovalent group having silver halide adsorbing ability in the form of only Z or Y-Z.

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, and particularly to a silver halide photographic light-sensitive material and a method for forming an image containing a compound capable of making a photographically useful group available in a development processing step. It is about.

[0002]

2. Description of the Related Art In the field of silver halide photographic light-sensitive materials for photoengraving, with the diversification and complexity of printed materials, it is strongly desired to improve the reproducibility of the original manuscript in Mincho / Gothic characters, copy dots, and stretching. Has been done. The photoengraving process includes a process of converting a continuous-tone original into a halftone dot image. In this step, a technique capable of reproducing an image with ultrahigh contrast is desired, and for example, a method using a hydrazine derivative as described in JP-A-56-106244 is used. According to this method, although photographic characteristics with high sensitivity and ultra-high contrast can be obtained, since the infectious developability is too strong, it is easy to blacken even a portion of a halftone dot that is a white background in halftone image photography, resulting in halftone dots. The gradation was very short, and the reproducibility of the original document was poor, which was a drawback in terms of image quality.

In order to improve the reproducibility, it is necessary to have a mechanism for selectively suppressing the development only at the large dots or the portions where the thin lines of characters are missing. Examples of such attempts include, for example, JP-A-61-213847 and JP-A-62-260.
153 and hydrazine derivatives disclosed in JP-A-4-136839, or JP-A-4-438,
A known method is to add a redox compound such as a hydroquinone derivative disclosed in JP-A-4-563, JP-A-4-6548 and JP-A-4-6551 to a silver halide emulsion layer to release a development inhibitor in a silver image manner. Has been. However, a silver halide photographic light-sensitive material in which a hydrazine derivative and the above-mentioned redox compound are used in combination in the same emulsion layer has a new problem of insufficient effect on halftone. Further, the redox reactivity of these redox compounds is easily dependent on the pH of the developing solution, and the pH is relatively low (p
(H = 11 or less) When processed with a developer, a super-high contrast image was obtained, but the effect on halftone was still insufficient.

[0004]

The object of the present invention is to obtain a stable image even in the processing with a developer having a relatively low pH (pH = 11 or less) and to obtain an ultrahigh contrast image after long-term raw storage. Another object of the present invention is to provide a silver halide photographic light-sensitive material having a wide halftone reproduction range and an image forming method.

[0005]

The above objects of the present invention can be achieved by the following constitutions.

1. On a support, each has at least one silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer, and at least one of the non-photosensitive hydrophilic colloid layers is represented by the following general formula (1): A silver halide photographic light-sensitive material comprising a compound represented by:

General formula (1) ED-X- [C (R ₁ ) = C (R ₂ )] _n -C (A ₁ ) (A
₂ ) -YZ In the formula, ED is oxidized to give the general formula (2) =-X.
- _{[C (R 1) = C (} R 2) ] _{n -C (A 1) (A} 2) -Y
Represents a group capable of releasing a group represented by -Z, X represents -O-,-
S-, or -N (R ₃₎ - represents a. R _{1 to} R ₃ represent a hydrogen atom or a monovalent group, and R _{1 to} R ₃ may combine with each other to form a ring. n represents 1 or 2, A ₁ and A ₂ represent a hydrogen atom, an alkyl group, or an aryl group,
Y is -O -, - S-, or -N (R ₄₎ - represents a. R ₄ has the same meaning as R ₃ . R ₄ may combine with Z to form a ring. Z represents a monovalent group having a capability of adsorbing silver halide, alone or YZ.

2. The silver halide photographic light-sensitive material as described above, wherein the group represented by ED is represented by the following general formulas [3] to [8].

[0009]

[Chemical 4]

In the formula, R ₁ represents an alkyl group, an aryl group or a heterocyclic group, and R ₂ and R ₃ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group or an oxalyl group. , A heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group, R ₄ represents a hydrogen atom, and R _{5 to} R ₉ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. r ₁ , r ₂ and r ₃ each represent a substituent capable of substituting on the benzene ring, and X ₁ and X ₂ are O or N.
H represents, Z represents an atomic group necessary for constituting a 5- or 6-membered heterocycle, W represents N (R ₁₀ ) (R ₁₁ ), or OH, and R ₁₀ and R ₁₁ are hydrogen atoms. Represents an alkyl group, an aryl group or a heterocyclic group. COUP represents a coupler residue capable of causing a coupling reaction with an oxidized product of an aromatic primary amine developing agent, * represents a coupling site of the coupler, m ₁ and p ₁ represent an integer of 0 to 3, q ₁ represents an integer of 0-4.

3. The silver halide photographic light-sensitive material as described above, wherein the non-photosensitive hydrophilic colloid layer is provided on the side closer to the support than the silver halide emulsion layer.

4. The silver halide photographic light-sensitive material as described above, wherein the silver halide emulsion layer contains 60 mol% or more of silver chloride.

5. The silver halide photographic light-sensitive material as described above, wherein the content of gelatin contained in the non-photosensitive hydrophilic colloid layer is 1.0 g / m ² or less per layer.

6. Halogenation as described above, characterized in that at least one of the layers in which the dye is substantially immobilized is provided between the support and the silver halide emulsion layer closest to the support. Silver photographic light-sensitive material.

7 The content of gelatin contained in the non-photosensitive hydrophilic colloid layer provided on each surface of the support is 4.0 g / m ² or less on each surface, Silver halide photographic light-sensitive material.

8. The above silver halide photographic light-sensitive material, wherein each of at least one silver halide emulsion layer or hydrophilic colloid layer contains at least one hydrazine derivative and a nucleation accelerator.

9. The above halogenation, characterized in that at least one silver halide emulsion layer or hydrophilic colloid layer each contains at least one hardener which acts by activating a carboxyl group. Silver photographic light-sensitive material.

10 The hardener is represented by the following general formula

The above silver halide photographic light-sensitive material represented by [9].

[0019]

Embedded image

In the formula, R ₁₂ and R ₁₃ represent an alkyl group or an aryl group, and R ₁₂ and R ₁₃ may form a ring. R ₁₄
Represents a hydrogen atom or a substituent. L represents a single bond or a divalent group. X ₃ represents a single bond or O, N (R ₁₅ ), R ₁₅
Represents a hydrogen atom, an alkyl group or an aryl group.

11. A method for forming an image of a silver halide photographic light-sensitive material, which comprises exposing the above-mentioned silver halide photographic light-sensitive materials 1 to 10 in an imagewise manner and then treating with a developer having a pH of 11 or less.

12 An image forming method of the above silver halide photographic light-sensitive material, which comprises using a developing agent represented by the following general formula [A].

[0023]

[Chemical 6]

In the formula, R _a represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an amino group, an alkoxy group, a sulfo group, a carboxyl group, an amide group,
Represents a sulfonamide group, Y ₁ represents —O—, —S—, Y ₂ represents —O—, —S— or —N (R _b ) —, and R _b is a substituted or unsubstituted alkyl group, Represents an aryl group.

The present invention adopts a constitution in which the compound represented by the general formula (1) is contained in the non-photosensitive hydrophilic colloid layer, whereby the high activity of the compound represented by the general formula (1) is maintained for a long time. Since it can be maintained even after raw storage, it is stable even when processed with a developer having a relatively low pH (pH = 11 or less), and ultra-high contrast images can be obtained even after long-term raw storage, and halftone reproduction is possible. It has the effect of widening the range.

The present invention will be specifically described below.

The present invention has at least one silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support, and at least one non-photosensitive hydrophilic colloid layer has the following general formula: A silver halide photographic light-sensitive material (hereinafter, referred to as a light-sensitive material) containing the compound represented by (1).

First, the compounds represented by the general formulas (1) and (2) will be described in detail.

General formula (1) ED-X- [C (R ₁ ) = C (R ₂ )] _n -C (A ₁ ) (A
₂ ) -YZ In the formula, ED is oxidized to give the general formula (2) =-X.
- _{[C (R 1) = C (} R 2) ] _{n -C (A 1) (A} 2) -Y
Represents a group capable of releasing a group represented by -Z, X represents -O-,-
S-, or -N (R ₃₎ - represents, R ₁ to R ₃ represents a hydrogen atom or a monovalent group,, R ₁ to R ₃ may bond to each other to form a ring. n represents 1 or 2, A ₁ and A ₂ represent a hydrogen atom, an alkyl group, or an aryl group,
Y is -O -, - S-, or -N (R ₄₎ - represents a. R ₄ has the same meaning as R ₃ , R ₄ may combine with Z to form a ring, and Z may be a monovalent group having a capability of adsorbing silver halide, either alone or in YZ. Represent

In the formula, the group represented by ED is preferably hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines and reductones.

As the monovalent group represented by R _{1 to} R ₃ in the general formula (1), a halogen atom (chlorine atom, bromine atom, etc.),
Alkyl group (eg methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), aralkyl group (eg benzyl Group, 2-phenethyl group etc.), aryl group (eg phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group etc.), alkoxy group (eg methoxy group, ethoxy group, isopropoxy group, butoxy group etc.), An aryloxy group (for example, a phenoxy group, etc.),
Cyano group, acylamino group (for example, acetylamino group,
Propionylamino group etc.), alkylthio group (eg methylthio group, ethylthio group, butylthio group etc.), arylthio group (eg phenylthio group etc.), sulfonylamino group (eg methanesulfonylamino group, benzenesulfonylamino group etc.), ureido group ( For example, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group) Group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg ethylsulfamoyl group, dimethylsulfamoyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg fluorine group). Nonoxycarbonyl group etc.), sulfonyl group (eg methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group etc.), acyl group (eg acetyl group, propanoyl group, butyroyl group etc.), amino group (methylamino group, ethylamino group) , Dimethylamino group, etc.), hydroxy group, nitro group, nitroso group, amine oxide group (eg pyridine-oxide group), imide group (eg phthalimido group etc.), disulfide group (eg benzene disulfide group, benzothiazolyl 2-disulfide group etc.) ), And a heterocyclic group (for example, a pyridyl group, a benzimidazolyl group, a benzthiazolyl group, a benzoxazolyl group, etc.).

R _{1 to} R _{3 in} the general formula (1) may be bonded to each other to form a ring, but in the present invention, it is preferable to form a ring. The ring is preferably an aromatic ring, which may be a monocyclic ring or a condensed ring, and may be a benzene ring or a 5- or 6-membered aromatic heterocycle having at least one of Benzoorg, O, S, and N atoms in the ring ( For example, 6-membered ring azines such as pyridine, pyrazine and pyrimidine rings and their benzerogues: 5-membered ring azoles such as pyrrole, thiophene, furan and benzerogues, imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, thiadiazole and oxadiazole. And its Ben Xerogue). Examples of preferable rings include a benzene ring formed by combining R ₁ and R ₂ and a pyridine ring, and a pyrazole ring formed by combining R ₂ and R ₃ . These rings may have a substituent, and specific examples thereof include the monovalent groups described above.

Preferred examples of the alkyl group and aryl group represented by A ₁ and A ₂ in the general formula (1) include a methyl group, an ethyl group, a normal butyl group and a phenyl group. These groups may be further substituted, and examples of the substituent include the monovalent groups described above.

R ₄ in the general formula (1) has the same meaning as R ₃ and the monovalent group represented by Z has, for example, at least one of O, S and N atoms in the ring. 5- or 6-membered aromatic heterocycle (for example, 6-membered ring azine such as pyridine, pyrazine, pyrimidine ring and its benzerogue, pyrrole, thiophene, furan and its benzerogue, imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, thiadiazole , 5-membered ring azoles such as oxadiazole and its benzerogues).

Examples of the group represented by ED include the groups represented by the following general formulas [3] to [8]. The groups represented by the general formulas [3] to [8] will be described below.

[0036]

[Chemical 7]

In the general formulas [3] to [8], R ₁ represents an alkyl group, an aryl group or a heterocyclic group, R ₂ and R ₃ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, A sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group, R ₄ represents a hydrogen atom, and R _{5 to} R ₉ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Represents In the general formulas [3] to [8], r ₁ , r ₂ and r ₃ each represent a substituent capable of substituting on the benzene ring, X ₁ and X _{2 each} represent O or NH, and Z represents a 5- or 6-membered group. Represents an atomic group necessary to form a heterocycle, W represents N (R ₁₀ ) (R ₁₁ ), or OH;
R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

In the general formulas [3] to [8], COUP represents a coupler residue capable of causing a coupling reaction with an oxidation product of an aromatic primary amine developing agent, and * represents a coupling site of the coupler. m ₁ and p ₁ is an integer of 0 to 3, q ₁ is an integer of 0-4.

In the general formulas [3] to [8], R ₁ and R ₅ to
Preferred examples of the alkyl group, aryl group and heterocyclic group represented by R ₁₁ include a methyl group, a p-methoxyphenyl group and a pyridyl group, and an acyl group represented by R ₂ and R ₃ , a carbamoyl group, Of the cyano group, nitro group, sulfonyl group, aryl group, oxalyl group, heterocyclic group, alkoxycarbonyl group and aryloxycarbonyl group, acyl group, carbamoyl group and cyano group are preferable. The total carbon number of these groups is preferably 1-20.

In the general formulas [3] to [8], R _{1 to} R ₁₁ may further have a substituent, and as the substituent, for example, R _{1 to} R ₃ in the general formula (1) described above can be used. Represented by the monovalent group represented by, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, a cyano group, an acylamino group, an alkylthio group, an arylthio group, a sulfonylamino group, In addition to ureido group, sulfamoylamino group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfonyl group, acyl group, amino group, hydroxyl group, nitro group, imide group, heterocyclic group, nitroso group Group, amine oxide group (eg, pyridinedione-oxide group), disulfide group (eg, benzenesulfide group) Benzoiazoriru 2 disulfide group).

Examples of the coupler residue represented by COUP include the following. Examples of cyan coupler residues include phenol couplers and naphthol couplers. Examples of magenta couplers include 5-pyrazolone couplers, pyrazolone couplers, cyanoacetylcoumarone couplers, open chain acylacetonitrile couplers, and indazolone couplers. Examples of the yellow coupler residue include a benzoylacetanilide coupler, a pivaloylacetanilide coupler, and a malondianilide coupler. As the colorless coupler residue, an open-chain or cyclic active methylene compound (for example, indanone, cyclopentanone, malonic acid diester, imidazolinone, oxazolinone,
Thiazolinone, etc.) Further, among the coupler residues represented by COUP, those which are preferably used can be represented by the following general formula [Coup-1] to general formula [Coup-8].

[0042]

Embedded image

In the formula, R ₁₆ represents an acylamido group, anilino group or ureido group, and R ₁₇ represents a phenyl group which may be substituted with one or more halogen atoms, alkyl groups, alkoxy groups or cyano groups.

[0044]

[Chemical 9]

In the formula, R ₁₈ and R _{19 each} represent a halogen atom, an acylamido group, an alkoxycarbonylamido group, a sulfoulide group, an alkoxy group, an alkylthio group, a hydroxy group or an aliphatic group, and R ₂₀ and R ₂₁ each represent a fatty acid. It represents a group group, an aromatic group or a heterocyclic group.

Further, one of R ₂₀ and R ₂₁ may be a hydrogen atom. a represents an integer of 1 to 4 and b represents an integer of 0 to 5. When a and b are plural, R _{18 and} R ₁₉ may be the same or different.

[0047]

[Chemical 10]

In the formula, R ₂₂ represents a tertiary alkyl group or an aromatic group, and R ₂₃ represents a hydrogen atom, a halogen atom or an alkoxy group. R ₂₄ represents an acylamide group, an aliphatic group, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group,
It represents an alkoxy group, a halogen atom or a sulfonamide group.

[0049]

[Chemical 11]

In the formula, R ₂₅ is an aliphatic group, an alkoxy group, an acylamino group, a sulfonamide group, a sulfamoyl group,
The diacylamino group, R ₂₆ represents a hydrogen atom, a halogen atom or a nitro group.

[0051]

[Chemical 12]

R ₂₇ and R ₂₈ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

These rings may have a substituent,
Specifically, 1 represented by R _{1 to} R ₃ in the above general formula (1)
The substituents mentioned for the valent group can be mentioned.

Specific examples of the compounds represented by the general formulas [3] to [8] corresponding to ED * will be listed below, but the present invention is not limited thereto.

[0055]

[Chemical 13]

In the following, ★ -X- [C (R ₁ ) = C
Specific examples of (R ₂ )] _n -C (A ₁ ) (A ₂ )-★★ are listed, but the present invention is not limited thereto.

[0057]

Embedded image

[0058]

[Chemical 15]

Specific examples of ★ -YZ are listed below, but the present invention is not limited thereto.

[0060]

Embedded image

[0061]

[Chemical 17]

[0062]

Embedded image

Specific examples of the compound represented by the general formula (1) are listed below, but the invention is not limited thereto.

[0064]

[Table 1]

[0065]

[Table 2]

The compound represented by the general formula (1) is preferably 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻² mol / m ² , and more preferably 1.0 × 10 ⁻⁷ to 1. 0 × 10 ^-4 mol /
Used in the range of m ² .

The compound represented by the general formula (1) can be used by dissolving it in a suitable water-miscible organic solvent such as alcohols, ketones, dimethyl sulfoxide, dimethylformamide, methyl cellosolve and the like. Also, it can be added as an emulsified dispersion using a known oil. More preferably, fine particles can be dispersed and used by a method known as a solid dispersion method.

A method for producing a solid fine particle dispersion of the compound represented by the general formula (1) is described in JP-A-52-927.
No. 16, No. 55-155350, No. 55-155535
No. 1, No. 63-197943, No. 3-182743
No. WO88 / 04794, and the like. Specifically, it can be produced using a fine disperser such as a ball mill, a planetary mill, a vibration mill, a sand mill, a roller mill, a jet mill and a disc impeller mill.

In order to obtain a dispersion of the compound represented by the general formula (1), when the compound is water-insoluble at a relatively low pH and water-soluble at a relatively high pH, the compound is weakly alkaline. A method of precipitating fine particulate solids by lowering the pH to weak acidity after dissolving in an aqueous solution is also a method of adjusting the pH of a weak alkaline solution of the compound represented by the general formula (1) and an acidic aqueous solution. However, a method of producing a solid in the form of fine particles by mixing them simultaneously is mentioned. The obtained solid fine particle dispersion may be used alone, or two or more kinds may be mixed and used, or may be mixed with another solid fine particle dispersion and used. When two or more kinds are mixed and used, they may be dispersed individually and then mixed, or may be simultaneously dispersed.

When the solid fine particle dispersion of the compound represented by the general formula (1) is produced in the presence of an aqueous dispersion medium, it is preferable that a surfactant be present during or after the dispersion. As such a surfactant, any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used, but preferably, for example, alkyl sulfonates, alkylbenzene sulfonates. , Alkylnaphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, N-acyl-N-alkyl taurines, and other anionic surfactants and saponins, alkylene oxide derivatives , Nonionic surfactants such as alkyl esters of sugars.

Particularly preferred are the above-mentioned anionic surfactants. Specific examples of the surfactant include, but are not limited to, the compounds of 1 to 32 described in Japanese Patent Application No. 5-277011, pages 46 to 32.

The amount of the anionic activator and / or the nonionic activator used is not uniform depending on the kind of the activator or the conditions of the dispersion of the compound represented by the general formula (1).
Usually, it may be 0.1 to 2000 mg, preferably 0.5 to 10 per 1 g of the compound represented by the general formula (1).
The amount is 00 mg, more preferably 1 to 500 mg. The concentration in the dispersion may be usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight. The surfactant may be added at a position before the dispersion of the compound represented by the general formula (1) is started, or if necessary, it may be further added to the dispersion liquid of the compound after the completion of the dispersion. These anionic activators and / or nonionic activators may be used alone, or may be used in combination of two or more kinds, respectively, and both activators may be combined.

The solid fine particle dispersion of the compound represented by the general formula (1) is preferably dispersed so that the average particle size is 0.01 to 5 μm, more preferably 0.01.
To 1 μm, particularly preferably 0.01 to 0.5 μm
Is. The coefficient of variation of the particle size distribution of the solid fine particle dispersion is preferably 50% or less,
It is more preferably 40% or less, and particularly preferably 3
0% or less. Here, the variation coefficient of the particle size distribution is a value represented by the following formula.

(Standard deviation of particle size) / (Average value of particle size) × 100 To the solid fine particle dispersion, a hydrophilic colloid used as a binder of a photographic constituent layer is added before the start of dispersion or after the end of dispersion. You can

As the hydrophilic colloid, it is advantageous to use gelatin, but in addition, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin and phthalated gelatin, and an ethylene group capable of polymerizing with gelatin are also used. Graft polymer with monomer, carboxymethyl cellulose, hydroxymethyl cellulose, cellulose derivative such as cellulose sulfate, polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-N-vinylpyrrolidone, poly Synthetic hydrophilic polymers such as methacrylic acid, agar, gum arabic, alginic acid, albumin and casein can be used. You may use these in combination of 2 or more types.

The amount of the hydrophilic colloid added to the solid fine particle dispersion is 0.1 to 12% by weight.
It is preferable to add it so that it becomes 0.5% to 8%. The amount of the solid fine particle dispersion used is not uniform depending on the type of dye, the characteristics of the light-sensitive material, etc., but is 1 to 1000 mg per 1 m ^{2 of} the photographic light-sensitive material.
And more preferably 5 mg to 800 mg, particularly preferably 10 mg to 500 mg.

As the light-sensitive material, it is preferable that at least one non-photosensitive hydrophilic colloid layer contains the solid fine particle dispersion from the viewpoint of improving the raw storage stability and widening the halftone reproduction range.

As the non-photosensitive hydrophilic colloid layer,
The coating amount of the hydrophilic colloid is preferably 0.05 to 2.0 g / in order to give a high-contrast image with less deterioration in sensitivity.
m ² , more preferably 0.1 g / m ^{2 to} 1.2 g / m ^2.
It is preferable to contain it so that

As the light-sensitive material, the above-mentioned non-photosensitive hydrophilic colloid layer is provided on the side closer to the support than the silver halide emulsion layer so that the released development inhibitor acts effectively and gives a preferable halftone gradation. It is preferably provided.

The content of gelatin contained in the non-photosensitive hydrophilic colloid layer provided on each surface of the support is 4.0 g per one surface so as to give a preferable halftone gradation.
/ M ² or less is preferable.

The term "substantially immobilizing a dye" means that the dye does not diffuse into other emulsion layers or hydrophilic colloid layers before the development processing, or even if the dye diffuses, other emulsion layers or hydrophilic colloid layers. It means a state in which the amount is contained so as not to affect the above.

As the dye used in the layer, for example, compounds of the general formulas (I) to (VI) are preferably used.

[0083]

[Chemical 19]

In the formula, A and A ′ each represent an acidic nucleus, which may be the same or different, B represents a basic nucleus, Q represents an aryl group or a heterocyclic group, and Q ′ represents a heterocyclic group. Represents a group, X ₄ and Y each represent an electron-withdrawing group,
They may be the same or different, and L ₁ , L ₂ and L ₃ each represent a methine group. m ₂ represents 0 or 1, t is 0,
1 or 2, and p ₂ represents 0 or 1. However, the dyes represented by the general formulas (I) to (VI) have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule.

The acidic nuclei represented by A and A'in the general formulas (I), (II) and (III) are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanin, hydantoin and thio. Hydantoin, oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone,
Examples include pyrazolopyridone.

The basic nucleus represented by B in the general formulas (III) and (V) is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole, thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole. , Indole.

Examples of the aryl group represented by Q in the general formulas (I) and (IV) include a phenyl group and a naphthyl group. In addition, Q in the general formulas (I), (IV) and (VI)
Examples of the heterocyclic group represented by and Q'include a pyridyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, an indolyl group, a furyl group and a thienyl group. The aryl group and the heterocyclic group include those having a substituent. As a preferable substituent, an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, t-butyl group, octyl group, 2-hydroxyethyl group, 2-methoxyethyl group, etc.), hydroxy group, cyano group, Halogen atom (eg, fluorine atom, chlorine atom, etc.), C1-C6 alkoxy group (eg, methoxy group, ethoxy group, 2-hydroxyethoxy group, methylenedioxy group, butoxy group, etc.), substituted amino group (eg, Dimethylamino group, diethylamino group, dibutylamino group, N-ethyl-N-hydroxyethylamino group, N-
Ethyl-N-methanesulfonamide ethylamino group, morpholino group, piperidino group, pyrrolidino group etc.), carboxy group, sulfonamide group (eg methanesulfonamide group, benzenesulfonamide group etc.), sulfamoyl group (eg sulfamoyl group, methyl (Sulfamoyl group, phenylsulfamoyl group, etc.), and these substituents may be combined.

The electron withdrawing groups represented by X ₄ and Y in the general formulas (IV) and (V) may be the same or different,
Substituent constant Hammett's σp value (Toshio Fujita, "Chemical Region Special Issue No. 122, Structure-Activity Relationship of Drugs", 96-
Page 103 (1979) Nankodo et al. ) Is 0.3 or more, for example, a cyano group, an alkoxycarbonyl group (eg, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, a phenoxycarbonyl group, 4 -Hydroxyphenoxycarbonyl group), carbamoyl group (eg, carbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group, etc.), acyl group (eg, methylcarbonyl group, ethylcarbonyl group, butylcarbonyl group, phenylcarbonyl group) , 4-
And an ethylsulfonyl group (eg, a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, an octylsulfonyl group, etc.) and an arylsulfonyl group (eg, a phenylsulfonyl group, a 4-chlorosulfonyl group, etc.). .

L ₁ , L ₂ and L _{3 of the} general formulas (I) to (V)
The methine group represented by includes those having a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a hexyl group, etc.), an aryl group (for example, a phenyl group, Tolyl group, 4-hydroxyphenyl group etc.), aralkyl group (eg benzyl group, phenethyl group etc.), heterocyclic group (eg pyridyl group, furyl group, thienyl group etc.), substituted amino group (eg dimethylamino group, diethylamino group) , Anilino groups, etc.) and alkylthio groups (eg, methylthio groups, etc.).

The dyes represented by the general formulas (I) to (IV) are
A dye having at least one carboxy group in the molecule is preferably used. Among the general formulas (I) to (VI), the dye represented by the general formula (I) is preferred, and the dye represented by the general formula (I)
Further preferred are dyes in which Q is a furyl group.

Specific examples of the compounds represented by formulas (I) to (VI) include, for example, Japanese Patent Application No. 5-277011.
No. described on pages 30 to 30. I-1 to No. I-30, II
-1 to II-12, III-1 to III-8, IV-1 to IV-
9, V-1 to V-8, and VI-1 to VI-5, but not limited thereto.

Specific examples of the compounds represented by formulas (I) to (VI) are shown below.

[0093]

Embedded image

[0094]

[Chemical 21]

As a method for obtaining the "layer in which the dye is substantially fixed", the dye is applied in the same manner as in the method for obtaining the solid fine particle dispersion of the compound represented by the general formula (1). It is preferable to apply the composition after the addition.

The method for producing the solid fine particle dispersion of the dye is the same as the method described in the literature mentioned in the section for producing the solid fine particle dispersion of the compound represented by the general formula (1). Good.

When the solid fine particle dispersion of the dye is produced in the presence of an aqueous dispersion medium, it is preferable to allow a surfactant to coexist during or after the dispersion. Examples of such a surfactant include the surfactant used in the solid fine particle dispersion of the compound represented by the general formula (1).

The solid fine particle dispersion of the dye is preferably dispersed so that the average particle diameter is 0.01 to 5 μm, more preferably 0.01 to 1 μm, and particularly preferably 0.01 to 0 μm. It is 0.5 μm. The coefficient of variation of the particle size distribution of the solid fine particle dispersion is 50%.
It is preferably the following, more preferably 40% or less, and particularly preferably 30% or less.

The variation coefficient of the particle size distribution is the same as the equation for obtaining the variation coefficient of the solid fine particle dispersion of the compound represented by the general formula (1).

The kind of the hydrophilic colloid used when dispersing the solid fine particle dispersion of the dye and the addition amount thereof are hydrophilic as used in the solid fine particle dispersion of the compound represented by the general formula (1). Similar to sex colloid.

The preferable amount of the solid fine particle dispersion of the dye is not uniform depending on the kind of the dye, the characteristics of the light-sensitive material and the like, but it is 1-1000 mg / m ^{2 of} the light-sensitive material, more preferably 5-800 mg. Particularly preferably 1
It is 0 to 500 mg.

When the light-sensitive material contains a solid fine particle dispersion of a dye, it may be contained in at least one hydrophilic colloid layer. Gelatin is preferably used for the hydrophilic colloid layer. The hydrophilic colloid layer preferably has a coating amount of the hydrophilic colloid of 0.05 to 2.0 g / m ² , and more preferably 0.1 to 2.0 g / m ^2. It is 1.2 g / m ² .

In order to effectively prevent light scattering and to provide a preferable halftone, at least one layer in which the dye is substantially fixed is supported with the silver halide emulsion layer closest to the support. It is preferably provided between the body and the body.

The solid fine particle dispersion of the compound or dye represented by the general formula (1) is a layer constituting a light-sensitive material, for example, a silver halide emulsion layer, an emulsion layer upper layer, an emulsion layer lower layer, a protective layer or a support layer. You may use it for layers, such as a body subbing layer and a backing layer.

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

[0106]

[Chemical formula 22]

In the formula, E is an aliphatic group which may have a substituent (preferably an aliphatic group having 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms), Aromatic group (preferably monocyclic or condensed ring aryl group), heterocyclic group (preferably monocyclic or condensed ring at least nitrogen,
A heterocycle containing one heteroatom selected from sulfur and oxygen), and particularly preferred are an aryl group and a heterocycle group.

The aryl group and heterocyclic group of E may have a substituent. As a typical substituent, an alkyl group (preferably having a carbon number of 1 to 20), an aralkyl group (preferably a monocyclic or condensed ring having an alkyl portion having a carbon number of 1 to 3), an alkoxy group (preferably Alkyl moiety having 1 to 20 carbon atoms), substituted amino group (preferably amino group substituted with alkyl group having 1 to 20 carbon atoms or alkylidene group), acylamino group (preferably having 1 to 40 carbon atoms) ), Sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms), hydrazinocarbonylamide group (preferably having 1 to 40 carbon atoms), hydroxyl group , A phosphoamide group (preferably having a carbon number of 1 to 40) and the like, among which a sulfonamide group is preferable. These substituents can be further substituted with an aliphatic, aromatic or heterocyclic group. Further, E preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group commonly used in a non-moving photographic additive such as a coupler is preferable, and as the ballast group, an alkyl group or an alkenyl group having 8 or more carbon atoms and relatively inert to photographic properties is preferable. , Alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like. As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group,
A mercapto heterocyclic group, or JP-A-64-90439.
And the adsorbing group described in the above item. E ₃ is an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group. , An oxalyl group or a heterocyclic group, together with E ₂ and the nitrogen atom to which they are attached,

[0109]

[Chemical formula 23]

May be formed.

R ₂₉ represents an alkyl group, an aryl group or a heterocyclic group, and R ₃₀ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. As E ₃ , an acyl group or an oxalyl group is particularly preferable. E ₁ and E ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group (etoxaryl, etc.) Represents

Specific examples of the compound represented by the general formula [H] are described in, for example, Japanese Patent Application No. 6-103982, pages 20 to 27 (H
Examples thereof include, but are not limited to, the compounds described as -1) to (H-44).

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

[0114]

[Chemical formula 24]

[0115]

[Chemical 25]

The synthesis method of the hydrazine derivative represented by the general formula [H] is described in JP-A Nos. 62-180361 and 62-1.
78246, 63-234245, 63-23
No. 4246, No. 64-90439, JP-A-2-37.
No. 2, No. 2-841, No. 2-947, No. 2-1207
No. 36, No. 2-230233, No. 3-125134
U.S. Pat.Nos. 4,686,167, 4,988,604, 4,994,36
The methods described in No. 5, European Patent Nos. 253,665, 333,435, etc. can be referred to.

The amount of the hydrazine derivative used in the light-sensitive material is 5 × 10 ^{-7 to} 5 × 10 ^-1 per mol of silver halide.
It is preferably molar, and particularly 5 × 10 ^{−6 to} 5 × 10
It is preferably in the range of ^-2 mol. When using a hydrazine derivative, a nucleation accelerator is also used.

Examples of the nucleation accelerator include Japanese Patent Application No.
The compounds described on pages 28 to 29 of No. -103982 are mentioned, and specific examples thereof are, for example, Japanese Patent Application No. 6-1039.
No. 82, pages 30-35 (Na-1)-(Na-22)
Or the compound described as (Nb-1)-(Nb-12) can be mentioned.

Preferred examples of the nucleation accelerator are mentioned here for reference, but the present invention is not limited thereto.

[0120]

[Chemical formula 26]

The amount of the nucleation accelerator used in the light-sensitive material is preferably 5 × 10 ^{−7 to} 5 × 10 ⁻¹ mol, and particularly 5 × 10 ^{−6 to} 5 × 10 5 mol, per mol of silver halide. It is preferably in the range of ^-2 mol.

In order to obtain an ultrahigh contrast image, at least one silver halide emulsion layer or hydrophilic colloid layer preferably contains at least one hydrazine derivative and a nucleation accelerator.

As the silver halide in the silver halide emulsion layer used in the present invention, particularly when the phenomenon time is less than 30 seconds, silver chlorobromide or 60 containing 60 mol% or more of silver chloride is used.
Silver chloroiodobromide containing silver chloride at a mol% or more is particularly preferable,
In particular, a super-high contrast image can be obtained. The average grain size of silver halide is preferably 0.7 μm or less, and particularly preferably 0.5 to 0.1 μm, from the viewpoint of expanding the halftone reproduction range.

The average particle size is a term which 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. When the particle is a cube, it is converted into a sphere, and the diameter of the sphere is taken as the particle size. For more information on how to determine average particle size, see: Themes of the Photographic Process (CEMees)
& TH James: The theory of the photographic proc
ess), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmillan")). There is no limitation on the shape of the silver halide grains used, and any shape such as a tabular shape, a spherical shape, a cubic shape, a tetradecahedral shape, a regular octahedron shape and 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 the grain size range of ± 40% of the average grain size is particularly preferable. As a method for producing silver halide grains, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like 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 form of simultaneous mixing method,
A method in which the pAg in the liquid phase in which silver halide is produced is kept constant, that is, a so-called controlled double jet method can be used. According to this method, the crystal form is regular and the grain size is almost uniform. A silver halide emulsion is obtained. The silver halide grain used in the silver halide emulsion has at least one of a grain forming process and a grain growing process.
In one process, cadmium salt, zinc salt, lead salt, thallium salt,
It is preferable to add a ruthenium salt, an osmium salt, an iridium salt or a rhodium salt, or a complex salt containing these elements. For more information on silver halide emulsions and their preparation methods, see Research Disclosure (hereinafter,
RD No. 176, 17643, pp. 22-23 (1
(December, 1978 issue)) or cited.

The silver halide emulsion may or may not be chemically sensitized, but sulfur sensitization, reduction sensitization and noble metal sensitization methods are known as chemical sensitization methods when they are carried out.
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 other than the sulfur compound contained in gelatin, such as thiosulfates, thioureas, rhodanins, and polysulfide compounds, are used. Can be used.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, 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 the reduction sensitizer include stannous salt, amines,
Formamidine sulfinic acid, a silane compound, etc. can be used.

The silver halide emulsion can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon ring fused to the nuclei of indolenin, benzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole , Quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-
A 5- or 6-membered heterocyclic ring such as a 2,4-dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus can be applied. Specifically, RD176 No. 17643, pages 2-3 (1978).
Dec.), U.S. Pat. Nos. 4,425,425 and 4,425,426, and compounds represented by the general formula [1] described in Japanese Patent Application No. 5-129157, page 3 (specific examples include 1-1 to 1-5 described on pages 17 to 22
7), the compound represented by the general formula [2] on page 4 (specific examples thereof include, for example, 2-
1-2-48), and the compounds represented by the general formula [3] on pages 4-5 (specific examples thereof are pages 35-48).
3-1 to 3-48), Japanese Patent Application No. 5-12915.
No. 8 page 3 compound represented by the general formula [1] (specific examples are, for example, 1-1 to 1-1 described on pages 14 to 16 thereof).
-14), a compound represented by the general formula [2] described on page 4 (specific examples thereof include 2 described on pages 17 to 18).
-1 to 2-6), a compound represented by the general formula [3] on page 5 (specific examples include 3-
1 to 3-4), the compound represented by the general formula [4] on page 6 (specifically, for example, 4-1 to 4-14 on pages 20 to 22), Japanese Patent Application No. Compounds represented by the general formula [I] described on pages 4 to 5 of No. 5-207984 (specific examples include, for example, [I] -1 to pages 12 to 24)
[I] -37), a compound represented by the general formula [1] described in Japanese Patent Application No. 5-261265, p.
Compounds 1-1 to 1-26 described on pages 3 to 16) and compounds represented by the general formula [2] described on page 5 (specific examples include 2-described on pages 20 to 22). 1-2-14), 5
The compound represented by the general formula [3] described on pages 7 to 6 (specific examples include 3- (1) described on pages 27 to 29).
To 3- (14)), and the compounds represented by the general formula [4] on pages 6 to 7 (specific examples thereof are pages 41 to 42).
4-1 to 4-6) described on page can be used.
The sensitizing dye may also be dissolved using ultrasonic vibration as described in US Pat. No. 3,485,634. In addition, as a method of dissolving or dispersing the sensitizing dye of the present invention in an emulsion, U.S. Patent Nos. 3,482,981 and 3,585,195, and
The methods described in 3,469,987, 3,425,835, 3,342,605, British Patents 1,271,329, 1,038,029, 1,121,174, and U.S. Patents 3,660,101, 3,658,546 can be used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in RD 176, 17643, page 23, IV, item J (December 1978).

Various compounds may be incorporated 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, such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines, mercaptotriazines; for example of oxazoline thione Thioketo compounds such as; azaindenes such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3
a, 7-Tetrazaindenes), pentazaindenes, etc .; benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers, such as benzene sulfonic acid amide, can be added.

The silver halide emulsion and the non-photosensitive hydrophilic colloid 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, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (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.) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin. Etc. alone Can be used in combination, but the compounds represented by the general formulas (1) to (7) described in JP-A-5-289219, pages 3 to 5 are preferable, and specific examples thereof include the same specification. H-1 to H-39 described on pages 6 to 14 of the book.

In the silver halide emulsion layer and the non-photosensitive hydrophilic colloid of the light-sensitive material, a hardener which acts by activating a carboxyl group, that is, a free carboxyl group of a protein-like binder (eg gelatin) is added. Preferred are those containing hardeners that are capable of reacting, thereby reacting with free amino groups to form peptide bonds, and thus form crosslinks in the binder.

As the hardener, the following general formula can be used.

[9]
The compound represented by is particularly preferably used.

[0133]

[Chemical 27]

General formula

In the compound represented by [9],
R ₁₂ and R ₁₃ have a linear, branched or cyclic carbon number of 1 to
Examples thereof include 20 alkyl groups (eg, methyl group, ethyl group, butyl group, cyclohexyl group, 2-ethylhexyl group, dodecyl group) and aryl groups having 6 to 20 carbon atoms (eg, phenyl group, naphthyl group). Also, R ₁₂ and R
₁₃ may have a substituent, and as an example of the substituent, a substituent for substituting the aryl group represented by Q in the general formulas (I) and (IV) described above, or the general formula (I), ( IV) and (VI)
Examples of the substituents for substituting the heterocycle represented by Q and Q'of

It is also preferable that R ₁₂ and R ₁₃ are combined to form a ring together with a nitrogen atom, and particularly preferable examples are cases where a morpholine ring and a pyrrolidine ring are formed. R ₁₄ represents a hydrogen atom or a substituent, and examples of the substituent include those enumerated above as the substituents for substituting the aryl group and the heterocycle, and a hydrogen atom is particularly preferable.

L represents a single bond, an alkylene group having 1 to 20 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group), an arylene group having 6 to 20 carbon atoms (eg, phenylene group), and It represents a divalent group such as a divalent group (for example, a baraxylene group), an acylamino group (for example, —NHCOCH ₂ — group), a sulfonamide group (for example, —NHSO ₂ CH ₂ — group) and the like obtained in combination. Of these, preferred are a single bond, an alkylene group such as a methylene group and an ethylene group, and an acylamino group. X ₃ represents a single bond or —O—, —N (R ₁₅ ) —, and R ₁₅ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, benzyl group), carbon number It is an aryl group having 6 to 20 (for example, a phenyl group or the like) or an alkoxy group having 1 to 20 carbon atoms (for example, a methoxy group or the like), and a hydrogen atom is particularly preferable.

General formula

Specific examples of the compound represented by [9] include, but are not limited to, the compounds (1) to (17) described in Japanese Patent Application No. 6-144823, pages 11 to 13.

General formula

Specific examples of the compound represented by [9] include the following.

[0139]

[Chemical 28]

[0140]

[Chemical 29]

The silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer are variously known for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. You may use the surfactant of. As the binder or protective colloid or other hydrophilic colloid layer of the silver halide emulsion, it is advantageous to use gelatin as described above. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzymatic decomposition product can also be used.

The non-photosensitive hydrophilic colloid layer, particularly a layer containing a photographically useful compound, that is, a compound which releases a group represented by the general formula (2) when oxidized, is included in the hydrophilic layer. When the functional colloid is gelatin, setting the content of gelatin in the layer to 1.0 g / m ² or less makes it possible to oxidize the compound sufficiently, and to oxidize the developing agent that should act like an image. The diffusion of the body in the layers in the direction parallel to the support is preferred because it is not unnecessarily large. More preferably, the gelatin in the layer is 0.5 g / m ² or less.

The silver halide emulsion 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, 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, etc. may be used. it can.

The silver halide emulsion used is preferably spectrally sensitized with various sensitizing dyes. Preferred sensitizing dyes are RD176 No. 17643, No. 23.
Pp.-24 (issued in 1978) and 346 No. 3468
5, (issued in 1993) can be used.

Various other additives are used in the light-sensitive material used. Examples thereof include desensitizers, plasticizers, slip agents, development accelerators, oils and dyes. Regarding these additives and the above-mentioned additives, specifically, R
What was described in D176 number, pages 22-31 etc. can be used. The protective layer of the light-sensitive material may be a single layer or a multi-layer composed of two or more layers.

The silver halide emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for a light-sensitive material. What is useful as the flexible support is a film made of a synthetic polymer of cellulose acetate, cellulose acetate butyrate, polystyrene, or polyethylene terephthalate (hereinafter referred to as PET).

The photosensitive material is imagewise exposed and then treated with a developing solution to form an image. The light source used for exposure is not particularly limited, and examples thereof include laser, light emitting diode, xenon flash lamp, halogen lamp, carbon arc lamp, metal halide lamp, and tungsten lamp.

The development processing step includes a developing solution processing step of developing the exposed silver halide and a fixing solution processing step of removing undeveloped silver halide.

As the developing agent or auxiliary developing agent used in the developing solution in the developing solution processing step, 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, erythorbic acid, 1-aryl-3-pyrazolines (for example, 1-
(P-hydroxyphenyl) -3-aminopyrazoline,
1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-
Aminopyrazoline, etc.), transition metal complex salts (Ti, V, C)
It is a complex salt of a transition metal such as r, Mn, Fe, Co, Ni, Cu, etc., and these may be in a form having a reducing power for use as a developing solution, for example, Ti ³⁺ , V ²⁺ , Cr ^2+. , Fe ^2+, etc. in the form of complex salts, and as ligands, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (D
Examples thereof include aminopolycarboxylic acids such as TPA) and salts thereof, phosphoric acids such as hexametapolyphosphoric acid and tetrapolyphosphoric acid, and salts thereof, and the like. ) Or the like can be used alone or in combination, but a combination of 3-pyrazolidones and dihydroxybenzenes, a combination of aminophenols and dihydroxybenzenes, or 3-
It is preferable to use a combination of pyrazolidones and ascorbic acid, a combination of aminophenols and ascorbic acid, a combination of 3-pyrazolidones and transition metal complex salts, a combination of aminophenols and transition metal complex salts, A compound represented by the following general formula [A] is particularly preferable.

[0150]

Embedded image

In the general formula [A], R _a is a hydrogen atom,
Represents a substituted or unsubstituted alkyl group, aryl group, amino group, or alkoxy group, or represents a sulfo group, a carboxyl group, an amido group, or a sulfonamide group, and Y ₁ is -O.
-, - represent S-, Y ₂ is -O -, - S- or -N
(R _b ) —, where R _b represents a substituted or unsubstituted alkyl group or aryl group.

The alkyl group is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms,
The amino group is preferably an unsubstituted amino group or an amino group substituted with a lower alkyl group, the alkoxy group is preferably a lower alkoxy group, the aryl group is preferably a phenyl group or a naphthyl group, and these groups are substituents. A substituent which may have an atom and can be substituted,
Examples of the atom include a hydroxy group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group and a sulfonamide group.

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

[0154]

[Chemical 31]

The developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / l.

Further, it is preferable to perform development processing with a developing solution containing a silver sludge inhibitor. As a silver sludge inhibitor, Japanese Examined Patent Publication No. 62702/1987, JP-A-3-51844,
No. 4-26838, No. 4-362942, No. 1-3
Examples thereof include compounds described in No. 19031.

The developing waste liquid can be regenerated by energizing it. Specifically, an anion exchange is performed by putting a cathode (for example, an electric conductor or semiconductor such as stainless steel wool) in the developing waste liquid and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) in the electrolyte solution. The waste developer tank and the electrolyte solution tank are in contact with each other through the film, and both electrodes are energized for regeneration. It is also possible to process the light-sensitive material while energizing. At that time, various additives added to the developer, for example, preservatives, alkali agents, pH buffers, sensitizers, antifoggants, silver sludge inhibitors, etc., which can be added to the developer, are additionally added. You can do it. Further, there is a method of processing the light-sensitive material while energizing the developing solution, and at that time, an additive which can be added to the developing solution as described above can be additionally added. A transition metal complex salt is preferable as a developing agent for the developing solution used when the developing waste solution is regenerated and used. Examples of sulfites and metabisulfites used as preservatives include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. Sulfite is 0.25 mol /
It is preferably 1 or more. It is particularly preferably 0.4 mol / l 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 (Eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), development accelerator (eg, US Pat. No. 2,304,025)
No. 1, 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 to be processed is 11 or less, but it is preferably adjusted to pH 9.5 to 11, particularly pH 10.2 to 10.8.

As a special form of development processing, an activator processing solution may be used in which a developing agent is contained in a light-sensitive material, for example, an emulsion layer, and the light-sensitive material is processed in an alkaline aqueous solution to carry out development. 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 liquid, those having a generally used composition can be used. The fixing solution is generally an aqueous solution containing a fixing agent and others, and the pH thereof is usually 3.8-5.
8 As the fixing agent, sodium thiosulfate,
Thiosulfates such as potassium thiosulfate and ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, it is possible to use an organic sulfur compound capable of forming a soluble stable silver complex salt, which is known as a fixing agent.

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 contains a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid),
A compound such as a pH adjuster (for example, sulfuric acid) and a chelating agent having the ability to soften water 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, the development temperature is set to 20 to 3
It can be set to a normal temperature range of 0 ° C or 30
It can also be set in the range of high temperature treatment of -40 ° C.

The light-sensitive material 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 rate is usually 3 per 1 m ² in order to reduce the amount of waste liquid.
00 ml or less, preferably 75 to 200 m per 1 m ² .
It is l.

In order to shorten the developing time, the total processing time (Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone when processing using the automatic developing machine
to Dry) is preferably 10 to 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. Time including all process time, that is, Dry to
It's Dry time. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 15 to 5
0 seconds.

In the automatic processor, a heat transfer material having a temperature of 90 ° C. or higher (for example, a heat roller at 90 to 130 ° C.) or 1
A radiant body of 50 ° C. or higher (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc., is used to directly generate an electric current and generate heat, and heat energy is radiated from a resistance heating element to copper, stainless steel, nickel, Those that emit infrared rays by transmitting heat to radiators such as various ceramics) that include those that have a drying zone.

[0168]

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

Example 1 (Preparation of Solid Fine Particle Dispersion) As the compound and dye represented by the general formula (1), a solid fine particle dispersion prepared by the following method was used.

In a 60 ml screw cap container, 21.7 ml of water and Triton X-200 (Ro
hm & Haas) 0.18 g, and a compound of the general formula (1) powdered in a mortar or 1.0 g of the dye is placed in this container, and zirconium oxide beads (2 m
m diameter) 40 ml was added. Then put the cap on the ball mill and disperse at room temperature for 4 days, then 12.5%
A gelatin aqueous solution (8.0 g) was added and mixed well, and the zirconium oxide beads were removed by filtration to obtain a solid fine particle dispersion.

(Preparation of Silver Halide Emulsion) << Emulsion A >> A silver chlorobromide emulsion (70 mol% of silver chloride per mol of silver) was prepared by the simultaneous mixing method. K ₂ Ir when mixed
Cl ₆ was added at 8 × 10 ^-7 mol per mol of silver. The obtained emulsion was an emulsion composed of cubic monodisperse grains (coefficient of variation 12%) having an average grain size of 0.20 μm. Sensitizing dye SD-1 was added to this emulsion in an amount of 7 × 10 ^-4 mol per mol of silver, and sensitizing dye SD-2 was added in an amount of 4 × 10 ^-4 mol per mol of silver. . Thereafter, a mixture of A, B and C was added, and then sodium thiosulfate and potassium chloroaurate were added to carry out chemical sensitization to obtain Emulsion A.

(Preparation of silver halide photographic light-sensitive material) A coating solution having the following formulation was prepared, and an undercoat layer having a thickness of 0.1 μm (see Example 1 of JP-A-59-19941) was applied. 7
On a polyethylene terephthalate (hereinafter referred to as PET) support having a thickness of 5 μm, a backing layer and a backing protective layer (Japanese Patent Application No. 6-105) from the antistatic surface of the support.
No. 670, Example 1), and on the other side, from the support side, an antihalation layer, the emulsion A layer, and a protective layer are coated simultaneously in this order and dried to prepare Samples 1-1 to 23 shown in Tables 3 and 4. I prepared. Also, Samples 1-24 to 26 prepared in the same manner except that the comparative compounds of Samples 1-1 to 3 were added to the emulsion A layer instead of the antihalation layer.

—Antihalation Layer— Gelatin 0.6 g / m ² Amount Represented by Formula (1) or Comparative Compound Tables 3 and 4 Surfactant (S-1) 2 mg / m ² Dye Described in Tables 3 and 4-Emulsion A layer-Amount of gelatin which becomes 1.5 g / m ² as emulsion layer Halogenated emulsion A silver amount, 3.0 g / m ² 4-Methyl-6-hydroxy-1,3,3a , 7-Tetrazaindene 30 mg / m ² adenine 10 mg / m ² sodium 5-sulfonate- ² -mercaptobenzimidazole 5 mg / m ² saponin 0.1 g / m ² colloidal silica (average particle size 0.015 μm) 10 mg / M ² Surfactant (S-1) 2 mg / m ² hydrazine derivative Described in Tables 3 and 4 Nucleation accelerator Described in Tables 3 and 4 Compound A 1.0 g / m ² polyethylene glycol (molecular weight 4000) 0.1 g / m ² -Protective layer- Gelatin 0.5 g / m ² amount Amount of surfactant (S-2) 10 mg / m ² Surfactant (S-3) 5 mg / m ² Matting agent (average particle size 3.5 μm monodisperse silica) 15 mg / m ² Hardener As described in Tables 3 and 4 Compound A: methyl acrylate-2-acrylamide-
2-Methylpropanesulfonic acid-2-acetoxyethyl methyl acrylate copolymer

[0174]

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[0175]

[Chemical 33]

[0176]

Embedded image

(Evaluation of Photographic Performance) The obtained sample was set to 25
After leaving it for 4 hours at 50 ℃ and 50% RH, seal it with a moisture-proof bag and keep it at 55 ℃.
Left for 5 days. After that, the sample was exposed with a tungsten light of 3200 ° K for 5 seconds through an optical wedge or an optical wedge and a contact screen, and then a developing solution and a fixing solution having the composition shown below was added to the automatic developing machine GR-26SR for rapid processing manufactured by Konica Corporation. Was processed under the following conditions.

-Gradation (γ) -The density of the obtained sample was measured with an optical densitometer, Konica PDA-65, and the gradation (γ) was displayed with the tangent of 0.1 and 2.5.

-Halftone-The halftone is expressed by the following equation.

Halftone = LogE (95%) − LogE (5%) LogE (95%): Exposure amount giving 95% halftone dot area LogE (5%): Gives 5% halftone dot area ratio Therefore, the larger the halftone value, the better the halftone.

The compositions of the developing solution and the fixing solution are as follows.

(Developer composition) Potassium sulfite 35.0 g Hydroquinone 20.0 g Compound B 2.0 g Potassium carbonate 12.0 g Potassium bromide 5.0 g Boric acid 8.0 g Disulfoxyethylhydroxylamine disodium salt 5.0 g 5-Methylbenzotriazole 0.3 g 5-Mercaptopurine 0.6 g Diethylene glycol 25.0 g Water was added to make 1 L, and the pH was adjusted to 10.4 with potassium hydroxide.

Compound B: 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, 1.0 g ethylenediaminetetraacetic acid disodium salt (fixing solution composition) ammonium thiosulfate (72.5% W / V aqueous solution) 200 ml Sodium sulfite 17g Sodium acetate / trihydrate 6.5g Boric acid 6.0g Sodium citrate / dihydrate 2.0g Pure water (ion exchange water) 17ml Sulfuric acid (50% W / V aqueous solution) 2.0g Aluminum sulfate ( Aqueous solution having an Al ₂ O ₃ conversion content of 8.1% W / V) 8.5 g The fixing solution was finished to 1 l and used. The pH of this fixer was adjusted to 4.8 with acetic acid.

(Development processing conditions) The time includes the time for wading.

Process Temperature Time Development 38 ° C. for 12 seconds Fixing 35 ° C. for 9 seconds Washing with water 30 ° C. for 9 seconds Drying 50 ° C. for 10 seconds (drying roller was 55 ° C.) Total 40 seconds Material and sample No. The relationship and the results are shown in Tables 3 and 4 below.

[0186]

[Table 3]

[0187]

[Table 4]

As is clear from Tables 3 and 4, Samples 1-6 to 23 of the present invention have higher gradation (γ) after raw storage and improved halftone gradation as compared with Comparative Examples. I understand.

Example 2 (Preparation of silver halide emulsion) << Emulsion B >> A silver chlorobromide emulsion (70 mol% of silver chloride per 1 mol of silver) was prepared by the simultaneous mixing method. K ₂ Ir when mixed
Cl ₆ was added at 8 × 10 ^-7 mol per mol of silver. The obtained emulsion was an emulsion composed of cubic monodisperse grains (coefficient of variation 12%) having an average grain size of 0.20 μm. The sensitizing dye SD-3 was added to this emulsion in an amount of 8 × 10 ^-7 mol per mol of silver, followed by washing with water and desalting by a conventional method. Then, the above A,
After the mixture of B and C was added, sodium thiosulfate and potassium chloroaurate were added for chemical sensitization to obtain Emulsion B.

(Preparation of silver halide photographic light-sensitive material) A coating solution having the following formulation was prepared and placed on a 100 μm-thick PET support on which an undercoat layer similar to that in Example 1 was applied, in the same manner as in Example 1. Samples 2-1 to 10 shown in Table 5 were prepared by coating a backing layer and a backing protective layer on the other side of the support in the order of an antihalation layer, an emulsion B layer and a protective layer from the support side, followed by drying. Also, Samples 2-11 and 2-12 were prepared in the same manner except that the comparative compound of Samples 2-1 and 2-2 was added to the emulsion B layer instead of the antihalation layer.

-Antihalation Layer-Amount of gelatin 0.6 g / m ² Compound represented by general formula (1) or comparative compound 40 mg / m ² Surfactant (S-1) 2 mg / m ² AD-8 80 mg / m ² -Emulsion B layer- Gelatin 1.5 g / m ² as emulsion layer Silver halide emulsion B Silver amount 3.0 g / m ² 4-Methyl-6-hydroxy-1,3,3a, 7 -Tetrazaindene 30 mg / m ² adenine 10 mg / m ² sodium 5-sulfonate-2-mercaptobenzimidazole 5 mg / m ² saponin 0.1 g / m ² colloidal silica (average particle diameter 0.015 μm) 10 mg / m ² Surfactant (S-1) 2 mg / m ² hydrazine derivative H-3 25 mg / m ² Nucleation accelerator N-3 10 mg / m ² Polyethylene glycol (molecular weight 4000) 0.1 g / M ² Compound A (same as in Example 1) 1.0 g / m ² -protective layer-gelatin 0.5 g / m ² amount Surfactant (S-2) 10 mg / m ² Surfactant (S- 3) 5 mg / m ² matting agent (monodisperse silica having an average particle diameter of 3.5 μm) 15 mg / m ² hardener (K-2) 20 mg / m ²

[0192]

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(Evaluation of Photographic Performance) The obtained sample was set to 25
After leaving it for 4 hours at 50 ℃ and 50% RH, seal it with a moisture-proof bag and keep it at 55 ℃.
Left for 5 days. Then, after exposure for 10 ^-5 seconds through a light passing through an interference filter having a wavelength of 633 nm through an optical wedge and a contact screen, a rapid treatment by Konica Corporation in which a developing solution having the composition shown below and the fixing solution shown in Example 1 were added. A pair of conveying rollers in the drying zone of the automatic developing machine GR-26SR for processing was processed under the following conditions with an automatic developing machine improved to be heatable (hereinafter referred to as a heating roller). The gradation (γ) was measured as in Example 1.

-Exposure latitude-Exposure latitude is ± 1 from the exposure amount that gives 50% halftone dot.
The percentage of halftone dots at an exposure amount of 2.5% was obtained, and the difference between the two was used as the exposure latitude value. The smaller this value is, the wider the exposure latitude is.

The composition of the developing solution and the developing treatment conditions are as follows.

(Developer composition) Potassium sulfite 35.0 g Developer (listed in Table 5) 20.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 1.0 g Ethylenediaminetetraacetic acid disodium salt 2 0.0 g Potassium carbonate 12.0 g Potassium bromide 5.0 g Boric acid 8.0 g Disulfoxyethylhydroxylamine disodium salt 5.0 g 5-Methylbenzotriazole 0.3 g 5-Mercaptopurine 0.6 g Diethylene glycol 25.0 g Compound (8-9) 0.12 g Water was added to make 1 liter, and the pH was adjusted to 10.4 with potassium hydroxide.

(Development processing conditions) The time includes the time for wading.

Process Temperature Time Development 38 ° C. for 12 seconds Fixing 35 ° C. for 9 seconds Washing with water 30 ° C. for 9 seconds Drying 50 ° C. for 10 seconds (drying roller was 55 ° C.) Total 40 seconds Used materials and sample No. The relationship and the results are shown in Table 5 below.

[0199]

[Table 5]

* Exposure latitude As is clear from the results in Table 5, the sample No. 2 of the present invention was used.
It can be seen that in Nos. 3 to 10, an image with a high gradation (γ) after raw storage and a wide exposure latitude can be obtained.

[0201]

According to the present invention, the pH is relatively low (p
(H11.0 or less) A silver halide photographic light-sensitive material and an image thereof which are stable even when processed with a developing solution, obtain an ultrahigh contrast image even after long-term raw storage, and have a wide halftone reproduction range (exposure latitude). A forming method can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 1/30 G03C 1/30 1/83 1/83 1/91 1/91 5/29 501 5 / 29 501 5/30 5/30

Claims (12)

[Claims] 1. A support having at least one silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer, wherein at least one of the non-photosensitive hydrophilic colloid layers is represented by the following general formula (1): ) A silver halide photographic light-sensitive material comprising a compound represented by Formula (1) ED-X- _{[C (R 1) = C (} R 2) ] _n -C (A ₁₎ (A
₂ ) -Y-Z (In the formula, ED is oxidized to give the general formula (2) =-
X- _{[C (R 1) = C (} R 2) ] _{n -C (A 1) (A} 2) -
Represents a group which releases a group represented by YZ, X is -O-,
-S-, or -N (R ₃₎ - represents a. R _{1 to} R ₃ represent a hydrogen atom or a monovalent group, and R _{1 to} R ₃ may combine with each other to form a ring. n represents 1 or 2, A ₁ and A ₂ represent a hydrogen atom, an alkyl group, or an aryl group,
Y is -O -, - S-, or -N (R ₄₎ - represents a. R ₄ has the same meaning as R ₃ . R ₄ may combine with Z to form a ring. Z represents a monovalent group having a capability of adsorbing silver halide, alone or YZ. ) 2. The group represented by the ED is represented by the following general formulas [3] to [8].
The silver halide photographic light-sensitive material described in. Embedded image (In the formula, R ₁ represents an alkyl group, an aryl group or a heterocyclic group, R ₂ and R ₃ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group,
It represents an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group, R ₄ represents a hydrogen atom, and R _{5 to} R ₉ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. r ₁ , r ₂ and r ₃ represent a substituent capable of substituting on the benzene ring, X ₁ , X ₂ represent O or NH,
Z represents an atomic group necessary for constituting a 5- or 6-membered heterocycle, W represents N (R ₁₀ ) (R ₁₁ ), or OH, and R ₁₀ and R ₁₁ are hydrogen atoms, alkyl groups, It represents an aryl group or a heterocyclic group. COUP represents a coupler residue capable of causing a coupling reaction with an oxidized product of an aromatic primary amine developing agent, * represents a coupling site of the coupler, m ₁ and p ₁ represent an integer of 0 to 3, q ₁ represents an integer of 0-4. ) 3. The silver halide photographic light-sensitive material according to claim 1, wherein the non-photosensitive hydrophilic colloid layer is provided on the side closer to the support than the silver halide emulsion layer. material. 4. The silver halide emulsion layer comprises 60 mol%
4. The silver halide photographic light-sensitive material according to claim 1, containing the above silver chloride. 5. The gelatin content in the non-photosensitive hydrophilic colloid layer is 1.0 g / m ² or less per layer, according to any one of claims 1 to 4. The described silver halide photographic light-sensitive material. 6. A dye-substantially immobilized layer, wherein at least one layer is provided between the support and the silver halide emulsion layer closest to the support.
6. A silver halide photographic light-sensitive material according to any one of items 1 to 5. 7. The content of gelatin contained in the non-photosensitive hydrophilic colloid layer provided on each surface of the support is
7. The silver halide photographic light-sensitive material according to any one of claims 1 to 6, characterized in that both sides have an amount of 4.0 g / m < ² > or less per side. 8. At least one silver halide emulsion layer or at least one hydrophilic colloid layer, respectively.
The silver halide photographic light-sensitive material according to any one of claims 1 to 7, which contains one kind of hydrazine derivative and a nucleation accelerator. 9. A silver halide emulsion layer or hydrophilic colloid layer of at least one layer each containing at least one hardener which acts by activating a carboxyl group. 9. A silver halide photographic light-sensitive material according to any one of items 1 to 8. 10. The silver halide photographic light-sensitive material according to claim 9, wherein the hardener is represented by the following general formula [9]. Embedded image (In the formula, R ₁₂ and R ₁₃ represent an alkyl group or an aryl group, and R ₁₂ and R ₁₃ may form a ring. R ₁₄ represents a hydrogen atom or a substituent. L represents a single bond or a divalent group. Represents the group of.
X ₃ represents a single bond or O or N (R ₁₅ ), and R ₁₅ represents a hydrogen atom, an alkyl group or an aryl group. ) 11. An image of a silver halide photographic light-sensitive material, which comprises exposing the silver halide photographic light-sensitive material according to any one of claims 1 to 10 imagewise and then treating it with a developer having a pH of 11 or less. Forming method. 12. The method of forming an image of a silver halide photographic light-sensitive material according to claim 11, wherein a developing agent represented by the following general formula [A] is used. Embedded image (In the formula, R _a represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an amino group, an alkoxy group, a sulfo group, a carboxyl group, an amide group, and a sulfonamide group, and Y ₁ represents-. O-, -S-, Y ₂ is -O-,
It represents —S— or —N (R _b ) —, and R _b represents a substituted or unsubstituted alkyl group or aryl group, respectively. )