JPH09146241A - Silver halide photosensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the safety of a hydroquinone compound and improve the generation of a Y stain and an M stain in a dark place by incorporating at least one kind of hydroquinone derivative and a specific compound in a nonphotosensitive hydrophilic colloid layer. SOLUTION: Of the silver halide photosensitive material which has at least one photosensitive silver halide emulsion layer and the nonphotosensitive hydrophilic colloid layer adjacent to the emulsion layer on its base, the nonphotosensitive hydrophilic colloid layer contains at least one kind of hydroquinone derivative represented by a formula I and the compound shown by a formula II. In the formula I, R11 is a class-2 alkyl group and R12 is a substituent. In the formula II, R11 -R14 are a hydrogen atom or alkyl group and R15 and R16 are a hydrogen atom or substituent. Consequently, the stability of the hydroquinone compound is improved to the generation of Y and M stains, thereby obtaining the photosensitive material which has superior storage properties of dye in a light place and also has its color reproducibility improved.

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 a method for processing the same, and more specifically, it improves the storage stability of the silver halide photographic light-sensitive material in the bright and dark places, and has a good manufacturing stability. The present invention relates to a silver halide photographic light-sensitive material which is excellent and inexpensive, and a processing method thereof.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material or a light-sensitive material) generally contains a silver halide and a color forming coupler and contains an oxidizing agent of a developing agent in a processing solution during development processing. In order to prevent the silver halide emulsion layers from mixing with each other when there are two or more silver halide emulsion layers which form a coloring dye by the reaction of the body and the color coupler. An intermediate layer of the non-hydrophilic colloid layer is provided. The intermediate layer is a compound having a function of capturing an oxidized product of a developing agent for the purpose of preventing an oxidized product of the developing agent, which is stained from the silver halide emulsion layer during development, from going to another silver halide emulsion layer and reacting. Has been added. As the compound for capturing the oxidized product of the developing agent, a hydroquinone compound has been shown to be effective according to US Pat. No. 2,336,327 and the like, and it is generally practical to use a hydroquinone compound. Is.

One of the advantages of the hydroquinone compound is that it is inexpensive to manufacture and can be supplied inexpensively, but from the point of view of the raw material, a secondary alkyl group is superior to a compound having a primary or tertiary alkyl group as a substituent. It is known that those having as a substituent are advantageous.

On the other hand, in recent years, a demand for improving the fastness of a dye-formed image formed of a silver halide photographic light-sensitive material has been increasing day by day. Particularly, the fastness of the dye image at the time of storing the album has become very high performance by using QAA6 paper (commonly known as 100 years print) manufactured by Konica Corporation. On the other hand, the uncolored part turns yellow (hereinafter, Y
Stain) or magenta discoloration (hereinafter M
As a result of intensive studies, the cause of these Y stains and M stains is mainly due to the secondary alkyl part of the hydroquinone compound contained in the photosensitive material. It was discovered that there are some due to deterioration during storage, some due to hydroquinone becoming quinone, and some due to decomposition of magenta coupler. Among these, regarding the improvement of Y stain or M stain due to the decomposition of the magenta coupler, it was found that when a pyrazoloazole type magenta coupler was used, the generation of Y stain or M stain was greatly improved. Therefore, when a pyrazoloazole type compound is used for the magenta coupler, the demand for improvement of the Y stain or M stain due to the hydroquinone compound has become more and more important.

A method for increasing the stability of hydroquinone compounds is disclosed in JP-A-51-6024, in which an oxidizing agent diffusible in an alkaline treatment liquid or an aromatic hydrocarbon compound having one or more hydroxyl groups is oxidized. Methods of using inhibitors have been proposed. However, JP-A-51-6
The storage stability described in JP-A No. 024/1994 is JP-A-51-60.
As described in No. 24, page 163, upper left line 4 to line 12, the storage stability in a dispersion state is indicated, and in the silver halide photographic light-sensitive material after coating which is the scope of claims of the present invention. It is a substance that has a different meaning from the stability of the hadroquinone compound. Also, JP-A-54-700
36, JP-A-54-25823, and JP-A-53-10.
No. 430, etc., a phenol or tocopherol derivative is used to improve the storage stability of the hydroquinone derivative and improve the white background.
Like No. 6024, it is a product in which the white background and the like are improved as a result of enhancing the stability of the dispersion liquid, and does not describe the stability over time of the hydroquinone compound contained in the photosensitive material.

[0006]

SUMMARY OF THE INVENTION A first object of the present invention is to improve the stability of hydroquinone compounds in a silver halide light-sensitive material, thereby improving the production of Y stain and M stain in the dark. To provide silver photographic light-sensitive material. The second object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in the storage stability of the dye formed in a bright place. A third object of the present invention is to provide a silver halide photographic light-sensitive material having no secondary absorption and improved color reproducibility. A fourth object of the present invention is to provide an inexpensive silver halide photographic light-sensitive material which is excellent in production stability. A fifth object of the present invention is to provide a silver halide photographic light-sensitive material and a processing method therefor, which does not cause a problem in an image to be formed even if the development processing time is greatly shortened.

[0007]

The above object of the present invention has been achieved by the following constitution.

(1). A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and a non-light-sensitive hydrophilic colloid layer adjacent to the emulsion layer, wherein the non-light-sensitive hydrophilic colloid layer has the following general formula: (HQ
-1) at least one of hydroquinone derivatives represented by
A silver halide photographic light-sensitive material comprising a seed and a compound represented by the following general formula (I).

[0009]

[Chemical 6]

(In the formula, R ₁₁ represents a secondary alkyl group,
R ₁₂ represents a substituent. )

[0011]

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(In the formula, R _I1 , R _I2 , R _I3 and R _I4 each represent a hydrogen atom or an alkyl group, and R _I5 and R _I5
Each _I6 represents a hydrogen atom or a substituent. (2). A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and a non-light-sensitive hydrophilic colloid layer adjacent to the emulsion layer, wherein the non-light-sensitive hydrophilic colloid layer has the above general formula A silver halide photographic light-sensitive material containing at least one hydroquinone derivative represented by (HQ-1) and a compound represented by the following general formula (II).

[0013]

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(In the formula, R _{II1 to} R _II4 each represent a hydrogen atom or a substituent.) (3). The silver halide photographic light-sensitive material described in (1) or (2), wherein the light-sensitive silver halide emulsion layer contains a compound represented by the following general formula (M-1).

[0015]

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(In the formula, Z represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X is a hydrogen atom or a color developing group. (Represents a group capable of splitting off upon reaction with an oxidized product of a developing agent, and R represents a hydrogen atom or a substituent.) (4). The halogen according to (1), (2) or (3), wherein the non-photosensitive hydrophilic colloid layer contains at least one compound represented by the following general formula (HQ-2). Silver halide photographic light-sensitive material.

[0017]

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(In the formula, R ₂₁ represents a tertiary alkyl group, and R _21
22 represents a substituent. ) (5). In the non-photosensitive hydrophilic colloid layer, the general formula (H
(1), (2), (3) characterized by containing at least two hydroquinone derivatives represented by Q-1)
Alternatively, the silver halide photographic light-sensitive material according to (4).

(6). Any one of (1) to (5) above
5. A method for processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material according to the item 1 above in a color development processing time of 30 seconds or less.

The present invention will be described in detail below.

The hydroquinone derivative represented by the general formula (HQ-1) will be described.

In the above general formula (HQ-1), the secondary alkyl group represented by R ₁₁ is represented by the following general formula (HQ
-A).

[0023]

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(In the formula, R _A1 and R _A2 each represent a substituent.) In the general formula (HQ-A), R _A1 and R _A2 may be any substituents, and R _A1 and R _A2 Examples of the substituents represented are the same as those of the substituents represented by R _I5 and R _I6 described below.

The number of carbon atoms contained in the general formula (HQ-A) is preferably 8 or more because it does not flow out during the development processing. Further, more preferably, the carbon number is 10 or more and 20.
Less than. Those having 20 or more carbon atoms are not preferable because they are difficult to purify in production, the production cost of the hydroquinone derivative is high, and the production stability and performance stability of the silver halide photographic light-sensitive material are greatly impaired.

The hydroquinone derivative represented by the general formula (HQ-1) used in the present invention is, for example, JP-B-46-4289.
0, 51-12250, JP-A-4-103550.
No. and the like.

In the general formula (HQ-1), the substituent represented by R ₁₂ is R _I5 and R _I6 described later, respectively.
Examples thereof include those having the same meaning as the substituent represented by.

The compound represented by formula (HQ-2) will be described.

In the present invention, the compound represented by the general formula (HQ-2) is a compound in which a tertiary alkyl group is substituted as a substituent, and the tertiary alkyl group is specifically the following general formula ( HQ-B). That is, in the general formula (HQ-2), the tertiary alkyl group represented by R ₂₁ is represented by the following general formula (HQ-B).

[0030]

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(In the formula, R _B1 , R _B2 and R _B3 each represent a substituent.) In the general formula (HQ-B), R _B1 , R _B2 and R _B3 may be any substituents, and R _{Examples of} the substituents represented by _B1 , R _B2 , and R _B3 include those having the same _meanings as the substituents represented by R _I5 and R _I6 described later, and the like.

In the general formula (HQ-2), the substituent represented by R ₂₂ may be any substituent as long as it is the same as the substituent represented by R _I5 and R _I6 described later. To be

In the present invention, the hydroquinone derivative represented by the general formula (HQ-1) is a compound represented by the general formula (HQ-2) or the general formula (HQ) from the viewpoint of manufacturability of a silver halide photographic light-sensitive material. It is preferable to use two or more kinds of the compounds represented by the hydroquinone derivative represented by -1) in combination.

The general formula (HQ used in the present invention will be described below.
Specific examples of the hydroquinone derivative represented by -1) and the compound represented by the general formula (HQ-2) are shown below, but the invention is not limited thereto.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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The compound represented by formula (I) will be described.

In the general formula (I), R _I1 , R _I2 ,
Among the hydrogen atoms or alkyl groups represented by R _I3 and R _I4 , examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group. Group, octyl group, dodecyl group, etc., and these alkyl groups may be substituted.

Among the hydrogen atoms or substituents represented by R _I5 and R _I6 , the substituent may be any one that can be substituted, such as an alkyl group, an aryl group, a heterocyclic group, an alkenyl group or a cycloalkyl group. , A cycloalkenyl group, a halogen atom, a cyano group, an amino group, and the like, and the substituents described in pages 1626 to 1628 of the Physical and Chemical Dictionary (published by Iwanami Shoten, 3rd edition).

The compound represented by the general formula (I) used in the present invention can be easily synthesized by a known synthesis method. In the present invention, the compound represented by the general formula (I) may be solid or liquid at room temperature. When it is liquid at room temperature, its dielectric constant has nothing to do with the effect of the present invention.

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

[0047]

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[0048]

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The compound represented by formula (II) will be described.

In the general formula (II), R _{II1 to} R _II4
In the hydrogen atom or the substituent represented by, the substituent may be anything that can be substituted, for example, an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a halogen atom, Examples thereof include a cyano group, an amino group and the like, substituents described in pages 1626 to 1628 of the Physical and Chemical Dictionary (published by Iwanami Shoten, 3rd edition).

The compound represented by the general formula (II) used in the present invention can be easily synthesized by a known synthesis method. In the present invention, the compound represented by the general formula (II) may be solid or liquid at room temperature. When it is liquid at room temperature, its dielectric constant has nothing to do with the effect of the present invention.

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

[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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In the present invention, examples of the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material include the compounds represented by the above-mentioned general formula (M-1), and more specifically, JP-A-4-114154. Of the general formula (M-I) and (M-
Couplers represented by II) can be mentioned. Specific compounds include those described as MC-1 to MC-11 in the same publication, page 4, lower left column to page 5, upper right column. More preferable among the above-mentioned magenta couplers are couplers represented by the general formula (M-I) described in the upper right column of page 4 of the same publication, of which the RM of the general formula (M-I) is A coupler which is a tertiary alkyl group is excellent in light resistance and is particularly preferable. MC-8 to MC-11 described in the upper column on page 5 of the publication are excellent in reproducing colors from blue to purple and red, and are also excellent in detail delineation power, and thus are preferable.

In the present invention, it is preferable that the compound represented by the general formula (I) or (II) is not used in the same layer as the ultraviolet protective agent.

The silver halide photographic light-sensitive material of the present invention can be developed by a general method of developing a silver halide photographic light-sensitive material, but it is processed in order to reduce labor costs and utility costs in recent years. It is desired to shorten the time, and in order to shorten the processing time, it is necessary to activate the development processing solution, but the silver halide photographic light-sensitive material of the present invention does not deteriorate even if it is subjected to such processing. No color image is obtained.
In the present invention, the development processing time is preferably 30 seconds or less, more preferably 20 seconds or less, and further preferably 10 seconds or less. Further, the treatment time is preferably 5 seconds or more in view of the activity of the treatment liquid.

The composition of the silver halide photographic emulsion according to the present invention has any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferable. Quick processing,
From the viewpoint of processing stability, a silver halide emulsion containing preferably 97 mol% or more, and more preferably 98 to 99.9 mol% silver chloride is preferable.

To obtain the silver halide emulsion according to the present invention, a silver halide emulsion having a portion containing silver bromide in a high concentration is particularly preferably used. In this case, the portion containing a high concentration of silver bromide may be epitaxy-bonded to silver halide emulsion grains, a so-called core-shell emulsion, or may be formed only partially without forming a complete layer. May simply have regions with different compositions. Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

In order to obtain the silver halide emulsion according to the present invention, it is advantageous to contain heavy metal ions. Heavy metal ions that can be used for such purposes include iron,
Iridium, platinum, palladium, nickel, rhodium,
Examples include Group 8 to 10 metals such as osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to the silver halide emulsion in the form of salt or complex salt.

When the heavy metal ion forms a complex, its ligand or ion is cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl. , Ammonia, and the like. Among them, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion and the like are preferable.

In order to add a heavy metal ion to the silver halide emulsion according to the present invention, the heavy metal compound is added to the physical layer before the formation of silver halide grains, during the formation of silver halide grains and after the formation of silver halide grains. It may be added at any place during each step during aging. In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, a heavy metal compound can be dissolved together with a halide salt and continuously added during the whole or part of the grain forming process.

The amount of the heavy metal ions added to the silver halide emulsion is 1 × 10 ^-9 per mol of silver halide.
Mol or more and 1 × 10 ^-2 mol or less, particularly preferably 1 × 10 ⁻² mol or less.
It is preferably at least 10 ^-8 mol and not more than 5 10 ^-5 mol.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,6
66, JP-A-55-26589, JP-B-55-42
737 and The Journal of Photographic Science (J. Photogr. Sci.) 2
1, 39 (1973) and the like, particles having an octahedral shape, a tetradecahedral shape, a dodecahedron shape, and the like can be prepared and used. Further, particles having a twin plane may be used.

The silver halide grains according to the present invention are preferably grains having a single shape, but it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The grain size of the silver halide grain according to the present invention is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm.
m, and more preferably 0.2 to 1.0 μm.

This particle size can be measured using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains according to the present invention is preferably monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably a coefficient of variation. It is to add two or more kinds of monodisperse emulsion of 0.15 or less to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution, and R is the average grain size.) The grain size referred to here is the diameter of spherical silver halide grains. Further, in the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but the one obtained by the simultaneous mixing method. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Further, JP-A-57-92523 and 57-57.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in DE-A-2,921,164. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
For example, an apparatus described in No. 501776, which takes out the reaction mother liquor from the reactor and concentrates it by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant, may be used.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion according to the present invention can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and the sulfur sensitizer is preferable. Thiosulfates as sulfur sensitizers,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, inorganic sulfur and the like can be mentioned.

The addition amount of the sulfur sensitizer according to the present invention is preferably changed according to the kind of silver halide emulsion to be applied and the magnitude of expected effect, but it is 5 × 10 5 per mol of silver halide. ^{-10 to} 5 × 10 ^-5 mol range,
Preferably, it is in the range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

The gold sensitizer according to the present invention can be added in the form of various gold complexes other than chloroauric acid, gold sulfide and the like. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol of silver halide.
It is preferably molar. More preferably, 1 × 10 ⁻⁵
Mol to 1 × 10 ⁻⁸ mol.

A reduction sensitization method may be used as the chemical sensitization method for the silver halide emulsion according to the present invention.

The silver halide emulsion according to the present invention is intended to prevent fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fog that occurs during development. Antifoggant known in
Stabilizers can be used. As examples of preferred compounds that can be used for such purposes, JP-A-2-14
The compound represented by the general formula (II) described in the lower column of page 7 of JP-A-6036 can be mentioned, and a more preferred specific compound is (IIa-1) described on page 8 of the same publication. )-(IIa-8), (IIb-1)-(II
b-7) or 1- (3-methoxyphenyl)-
Examples thereof include compounds such as 5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole. These compounds have a silver halide emulsion grain preparation step, a chemical sensitization step, and
At the end of the chemical sensitization step, it is added in a step such as a coating liquid preparation step. When chemical sensitization is carried out in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 × per mol of silver halide.
It is preferably used in an amount of about 10 ^-4 mol. When added at the end of chemical sensitization, 1 x per mol of silver halide
An amount of about 10 ⁻⁶ mol to 1 × 10 ⁻² mol is preferable, and 1 ×
The amount is more preferably from 10 ⁻⁵ mol to 5 × 10 ⁻³ mol. In the step of preparing a coating solution, when added to the silver halide emulsion layer, 1 × 10 ⁻⁶ mol to 1 × 10 ⁶ mol per mol of silver halide is used.
An amount of about ^-1 mol is preferred, and 1 × 10 ^-5 mol to 1 × 10
^-2 mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ^-9 mol to 1 × 10 ^-3 mol per 1 m ² .

In the present invention, a dye having absorption in various wavelength regions can be used in the silver halide photographic light-sensitive material for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. Particularly, as the dye having absorption in the visible region, the dyes of AI-1 to 11 and the dyes described in JP-A-3-251840, page 308, can be used. The dyes described in the specification of JP-A-6-3770 are preferably used, and as the infrared-absorbing dye, there can be used general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A No. 1-280750. The compounds represented are preferable because they have preferable spectral characteristics, have no influence on the photographic characteristics of the silver halide photographic emulsion, and have no stain due to residual color. Specific examples of preferred compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column of the same publication.

For the purpose of improving sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is preferable to make the spectral reflection density 0.7 or more, more preferably 0.8 or more.

In the present invention, it is preferable to add a fluorescent whitening agent to the light-sensitive material because the white background can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

In the present invention, when the silver halide photographic light-sensitive material is used as a color photographic light-sensitive material, it is spectrally sensitized to a specific region in the wavelength range of 400 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention.
BS-1 to 8 described on page 28 of JP-A-251840 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. Nos. S-1 to S-17 described on pages 15 to 17
Are preferably used in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like or water, or adding it as a solid dispersion. It may be added.

In the present invention, as the coupler used in the silver halide photographic light-sensitive material, a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm is formed by a coupling reaction with an oxidant of a color developing agent. Any compound that can be used can be used, but as a typical example, a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 5
Typical are magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of 00 to 600 nm, and cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

In the present invention, as the cyan coupler which can be preferably used in the silver halide photographic light-sensitive material, the general formulas (CI) and (C) described in JP-A-4-114154, page 5, lower left column are described. -II) can be mentioned. Specific compounds are described in the same specification on page 5, lower right column to page 6, lower left column, CC-1 to
Mention may be made of those described as CC-9.

A yellow coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention is represented by the general formula (YI) described in JP-A-4-114154, page 3, upper right column. A coupler can be mentioned. Specific compounds include those described as YC-1 to YC-9 in the lower left column of page 3 of the same publication. Above all, a coupler in which RY1 of the general formula [Y-1] of the same publication is an alkoxy group or a coupler represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone. preferable. Of these, particularly preferred examples of the compounds include YC-8 and YC-9 described in the lower left column of page 4 of JP-A-4-114154, and
-67388, N described on page 13 to 14 of the specification
o (1) to (47). The most preferred compound is described in JP-A-4-8184.
It is a compound represented by the general formula [Y-1] described in JP-A-7-page 1 and JP-A-11-page 11-17.

In the present invention, when the oil-in-water emulsion dispersion method is used to add a coupler or other organic compound used in a silver halide photographic light-sensitive material, it is usually used.
If necessary, a low-boiling and / or water-soluble organic solvent is dissolved in a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher, and the resulting mixture is dissolved and emulsified by using a surfactant in a hydrophilic binder such as a gelatin aqueous solution. To do. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or at the same time as the dispersion, a step of removing the low boiling organic solvent may be added. As the high-boiling organic solvent that can be used to dissolve and disperse the coupler, dioctyl phthalate, diisodecyl phthalate, phthalates such as dibutyl phthalate, tricresyl phosphate, phosphates such as trioctyl phosphate, Is preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

Further, instead of the method using a high-boiling point organic solvent or in combination with a high-boiling point organic solvent, a water-insoluble and organic-solvent-soluble polymer compound is added, if necessary, to a low-boiling point and / or water-soluble organic solvent. It is also possible to employ a method in which the surfactant is dissolved in a hydrophilic binder such as an aqueous gelatin solution and the resulting mixture is emulsified by various dispersing means using a surfactant.
Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

Preferred compounds as the surfactant used for dispersing the photographic additives and adjusting the surface tension during coating include a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. The thing contained is mentioned. Specifically, A-described in the specification of JP-A No. 64-26854.
1-A-11 are mentioned. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is preferable that the time from dispersion to addition to the coating solution and the time from addition to the coating solution and coating are short and 10 hours each. It is preferably within 3 hours, more preferably within 3 hours and within 20 minutes.

An anti-fading agent is preferably used in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541 and general formula IIIB described in JP-A-3-174150.
Phenolic compound represented by JP-A-64-90445
The amine compounds represented by the general formula A described in JP-A No. 62-182741 and the general formulas XII, XIII and X described in JP-A No. 62-182741.
The metal complexes represented by IV and XV are particularly preferable for the magenta dye. Further, a compound represented by the general formula I 'described in JP-A-1-19649 and JP-A-5-11417
The compound represented by the general formula II described in JP-A No. 2-2,056 is particularly preferred for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in JP-A-4-114154, page 9, lower left column, the compound described in the same publication, page 10, lower left column. Compounds such as (A'-1) can be used. In addition to this, US Pat.
The fluorescent dye-releasing compounds described in No. 74,187 can also be used.

In the present invention, it is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog and improve the light resistance of the dye image. Benzotriazoles are mentioned as preferable ultraviolet absorbers, and particularly preferable compounds are compounds represented by the general formula III-3 described in JP-A-1-250944, and JP-A 64-66.
Compounds represented by the general formula III described in JP-A No. 646, UV-1L to UV-described in JP-A-63-187240.
27L, the compound represented by the general formula I described in JP-A-4-1633, and the compound represented by the general formulas (I) and (II) described in JP-A-5-165144.

In the present invention, it is advantageous to use gelatin as a binder in the silver halide photographic light-sensitive material, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

As the hardener for these binders, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination. JP-A-61-24
It is preferable to use the compounds described in JP-A Nos. 9054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the photosensitive material or the processed sample.

As the support used in the silver halide photographic light-sensitive material of the present invention, any material may be used. Paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, A vinyl chloride sheet, polypropylene which may contain a white pigment, a polyethylene terephthalate support, baryta paper or the like can be used. Of these, a support having a waterproof resin coating layer on both sides of the base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the support was 13% by weight for improving sharpness.
The above is preferred, and more preferably 15% by weight.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the coefficient of variation described in the above publication.

It is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, more preferably 0.12 μm or less, since the effect of improving the gloss is obtained. In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

In the present invention, the silver halide photographic light-sensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or undercoat layer (adhesiveness of the surface of the support, Applied through one or more undercoat layers for improving antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In the present invention, in order to form a photographic image using the silver halide photographic light-sensitive material, the image recorded on the negative is optically combined with the silver halide photographic light-sensitive material to be printed. It may be imaged and printed, or the image may be converted to digital information and then the image may be displayed on a CRT.
An image may be formed on a (cathode ray tube), and this image may be formed on a silver halide photographic light-sensitive material to be printed and printed, or scanning is performed by changing the intensity of laser light based on digital information. You may bake it.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and is particularly preferably applied to a light-sensitive material for forming an image for direct viewing. For example, color paper, color reversal paper, a photosensitive material for forming a positive image, a photosensitive material for a display, and a photosensitive material for a color proof can be used. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds may be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-methyl-4- (N-ethyl-N-
(Β-Hydroxyethyl) amino) aniline CD-6) 4-amino-3-methyl- (N-ethyl-N- (β-methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino- 5-diethylaminophenylethyl) methanesulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9) 4-amino-3-methyl-N-ethyl-
N-methoxyethylaniline CD-10) 4-amino-3-methyl-N-ethyl-N- (β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-N- (γ. -Hydroxypropyl) aniline In the present invention, the color developer can be used in any pH range, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 1.
It is used in the range of 2.0.

The processing temperature for color development according to the present invention is 35
The temperature is preferably from 70 ° C to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.

To the color developing solution, a known developing solution component compound can be added in addition to the above color developing agent. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

Further, generally, in order to obtain a color image by processing an imagewise exposed silver halide color photographic light-sensitive material,
A metallic silver produced after the color development step is desilvered, and then a treatment step such as washing with water and stabilization is provided. Desilvering consists of a bleaching and fixing process, or a one-bath bleach-fixing process in which these are integrated. In the bleach-fixing process solution, the silver halide photographic light-sensitive material that has been color-developed is generally directly introduced, and as a result, the bleach-fixing solution contains the developing agent brought in from the silver halide photographic light-sensitive material. Be done. recent years,
Shortening the processing time of silver halide color photographic light-sensitive materials has been eagerly desired to improve the productivity of developing laboratories, but in order to shorten the processing time, it is essential to increase the concentration of the developing agent during color development processing. Therefore, the concentration of the developing agent in the bleach-fixing solution tends to increase. Therefore, the concentration of the color developing agent in the bleach-fixing solution is preferably in the range of 2 to 5 g / l, more preferably 4 to 5 g / l.

As a substitute for the washing treatment, a stabilizing treatment may be performed. As a development processing device used for the development processing of the silver halide photographic light-sensitive material of the present invention, even if it is a roller transport type that conveys the light-sensitive material sandwiched between the rollers arranged in the processing tank, It may be an endless belt method in which it is fixed and conveyed, but a processing tank is formed in a slit shape, the processing solution is supplied to this processing tank and the photosensitive material is conveyed, or a spray for spraying the processing solution. A method, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can also be used. When processing in large quantities,
Usually, running processing is carried out using an automatic processor, but at this time, the smaller the replenishing amount of the replenisher is, the more preferable it is, and the most preferable processing form in view of environmental suitability is to add the processing agent in the form of tablets as a replenishing method. That is the open technical report 94-
Most preferred is the method described in 16935.

[0118]

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 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further applied to prepare a silver halide photographic material. The coating liquid was prepared as follows.

First Layer Coating Liquid Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34.
g, (ST-5) 3.34 g, a stain inhibitor (HQ-
1) 0.34 g, 5.0 g of image stabilizer A, 3.33 g of high boiling organic solvent (DBP) and high boiling organic solvent (DN)
P) Ethyl acetate (60 ml) was added and dissolved in 1.67 g, and this solution was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to disperse the yellow coupler. A liquid was prepared. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

Each of the coating liquids for the second to seventh layers was prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 1 and 2.

Further, (H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² .

[0123]

[Table 1]

[0124]

[Table 2]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: Disulfosulfosuccinate (2,2,3,3,4) , 4,
5,5-octafluoropentyl) -sodium salt DBP: dibutylphthalate DNP: dinonylphthalate DOP: dioctylphthalate DIDP: di-i-decylphthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyl (Oxycarbonyl) butyl] hydroquinone Image stabilizer A: pt-octylphenol

[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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(Preparation of blue-sensitive silver halide emulsion) 40 ° C.
In 1 liter of a 2% gelatin aqueous solution kept at
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Hexachloroiridium (IV) acid potassium salt 4 × 10 ^-8 mol Potassium hexacyanoferrate (II) 2 × 10 ^-5 mol Potassium bromide 1.0 g Water added 600 ml (D liquid) Silver nitrate 300 g Water added 600 ml After the addition is complete, Kao Atlas Demol Desalination was performed using a 5% aqueous solution of N and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained. Next, the addition time of (solution A) and (solution B) and (C solution) and (D
The average particle size is 0.64 μm and the variation coefficient of the particle size distribution is 0.0, as in EMP-1 except that the addition time of the solution is changed.
7. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-1B was obtained.

The above EMP-1 was optimally chemically sensitized at 60 ° C. using the following compounds. Also EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (green-sensitive silver halide emulsion) Preparation) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%. Next, an average particle size of 0.50
A monodisperse cubic emulsion EMP-2B having a particle size of .mu.m, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed in a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole In the red photosensitive emulsion, SS-1 was added per mol of silver halide. 2.0 × 10 ^{−3 was} added.

[0139]

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[0140]

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In the second layer of the silver halide photographic light-sensitive material (Sample No. 101) prepared as described above, the anti-staining agent (represented by the general formulas (HQ-1) and (HQ-2) of the present invention) was used. Compound) to be added in a ratio as shown in Table 3 so that the total amount becomes 0.60 mmol / m ² . Further, 0.10 mmol / m ^{2 of the} additives shown in Table 3 (the compounds represented by the general formulas (I) and (II) of the present invention) was added, and the following evaluations were performed.

(Evaluation of Color Mixing) The prepared samples were exposed to blue and green single colors by a conventional method and then developed in the following development processing steps to prepare yellow and magenta single color developed samples.

The magenta reflection density at a reflection density of 1.8 and the yellow reflection density at a reflection density of 1.8 of the prepared monochromatic color sample of yellow were measured.

(Evaluation of white background after aging with heat (Y stain,
M stain)) The unprepared sample was subjected to development processing in the following development processing step to prepare a white background sample.
The white background sample thus prepared was allowed to stand at 85 ° C. and 60% RH for 21 days to evaluate the white background color (difference).

(Stability of Dye Image in Bright Place) The prepared sample was exposed to a single color of green and developed in the following development process to prepare a magenta single color sample. The magenta monochromatic sample thus prepared was irradiated with light using xenon weather meta (100,000 lux), and the time until the density at the reflection density of 1.0 decreased by 30% was evaluated.

(Development Processing Step) Processing Step Processing Temperature Time Replenishment Amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleach-fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 Second 150 ml Dry 60-80 ° C. 30 seconds The composition of the developing solution is shown below.

(Color developer tank solution and replenisher) Tank solution replenisher Pure water 800 ml 800 ml Triethylenediamine 2 g 3 g Diethylene glycol 10 g 10 g Potassium bromide 0.01 g-Potassium chloride 3.5 g-Potassium sulfite 0.25 g 0.5 g N -Ethyl-N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10. 0g Diethylenetriaminepentaacetic acid sodium salt 2.0g 2.0g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to make the total volume 1 liter, and tank liquid PH = 10.10, replenisher Adjust the pH to 10.60.

(Bleaching Fixing Solution Tank Solution and Replenishing Solution) Diethylenetriamine pentaacetate ammonium ferric acid dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-Amino-5-mercapto-1,3,4- Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust to pH = 5.0 with potassium carbonate or glacial acetic acid.

(Stabilizing Solution Tank Solution and Replenishing Solution) o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP (polyvinylpyrrolidone) 1.0 g Ammonia water (ammonium hydroxide 25% aqueous solution) 2.5 g Nitrilotriacetic acid trisodium salt 1.5 g Water was added to make the total volume 1 liter, and pH was adjusted to 7 with sulfuric acid or ammonia water. Adjust to 5.

The above results are shown in Table 3.

[0151]

[Table 3]

As is apparent from Table 3, when the stain inhibitor of the present invention is used, it is advantageous not only in color mixing but also in shelf stability in the light. Further, addition of the additive of the present invention was found to improve the discoloration of white background (especially M stain) in the dark, which is a major drawback of the stain inhibitor of the present invention. Also, when a stain inhibitor with a substituted secondary alkyl group and a stain inhibitor with a substituted tertiary alkyl group are used in combination, a stain inhibitor with a substituted secondary alkyl group and a stain inhibitor with a substituted tertiary alkyl group are used alone. It was found that the discoloration (stain) was obviously less than the expected discoloration degree than the discoloration of the white background in the dark place.

Example 2 In Example 1, processing was carried out by shortening the developing time and highly activating the processing solution as follows.

Treatment Process Treatment Temperature Time Replenishment Amount Color development 38.0 ± 0.3 ° C. 22 seconds 81 ml Bleach fixing 35.0 ± 0.5 ° C. 22 seconds 54 ml Stabilization 30-34 ° C. 25 seconds 150 ml Dry 60 The composition of the developing treatment solution is shown below.

(Color developer tank solution and replenisher) Tank solution replenisher Pure water 800 ml 800 ml Diethylene glycol 10 g 10 g Potassium bromide 0.01 g-Potassium chloride 3.5 g-Potassium sulfite 0.25 g 0.5 g N-ethyl-N -(Β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 8.0 g 12.5 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxylamine 3.5 g 6.0 g Triethanolamine 10.0 g 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30g 30g Add water to bring the total volume to 1 liter Adjust the pH of the tank solution to 10.10 and the replenisher solution to 10.60.

(Bleaching Fixing Solution Tank Solution and Replenishing Solution) Tank Solution Replenishing Solution Diethylenetriaminepentaacetic acid Ammonium dihydrate 100 g 50 g Diethylenetriaminepentaacetic acid 3 g 3 g Ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml 2-amino-5- Mercapto-1,3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml Water was added to bring the total volume to 1 liter, and potassium carbonate or glacial acetic acid was added to the tank solution at pH = 7. Adjust the pH to 0 and the replenisher to pH = 6.5.

(Stabilizing Solution Tank Solution and Replenishing Solution) o-Phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g PVP 1.0 g Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g Ethylene diamine tetra Acetic acid 1.0 g Ammonium sulfite (40% aqueous solution) 10 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

The same evaluation as in Example 1 was performed, and the results shown in Table 4 below were obtained.

[0159]

[Table 4]

As can be seen from Table 4, the occurrence of color mixing increases when the processing time is shortened and the developing solution is activated. However, it can be seen that the color mixing is improved by using the color mixing inhibitor of the present invention. Even more surprisingly, the use of the additives of the invention also improved the color mixing that occurs in such highly active treatments. Further, as in the case of Example 1, the storability in the dark and the storability in the light were improved.

Example 3 In Example 2, as an automatic developing machine, N manufactured by Konica Corporation was used.
PS-868J, ECOJET-P as processing chemical
Was used according to the process name CPK-2-J1. Evaluation was performed in the same manner as in Example 1, and it was confirmed that the effects of the present invention were obtained.

Example 4 An anti-staining agent (HQ-1) (268.5 g) and a high boiling point solvent (DIDP) (48.0 g) were dissolved in 200 ml of ethyl acetate, and the resulting solution was dissolved in 20% surfactant (SU-).
1) An 8% gelatin aqueous solution containing 55 ml was added and emulsified and dispersed using an ultrasonic homogenizer to prepare a dispersion liquid 1. The prepared dispersion was stored at 40 ° C. for 24 hours and then filtered with a filter to evaluate the filterability.

Further, the color mixing inhibitor and the additive were changed as shown in Table 5, and the filterability was evaluated.

[0164]

[Table 5]

[0165]

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As is clear from Table 5, the antistaining agent substituted with a secondary alkyl group is superior in filterability to the antistaining agent substituted with a primary or tertiary alkyl group and is advantageous in the production of a light-sensitive material. I found out. Furthermore, when two or more types of anti-staining agents substituted with a secondary alkyl group are used in combination,
It was found that the filterability was further improved. Furthermore, when a stain inhibitor substituted with a tertiary alkyl group is also used,
It was found that the filterability was improved.

[0167]

According to the present invention, firstly, a silver halide photographic light-sensitive material in which the generation of Y stain and M stain in a dark place is improved by enhancing the stability of the hydroquinone compound in the silver halide light-sensitive material. To provide. Secondly, to provide a silver halide photographic light-sensitive material excellent in the storage stability of the formed dye in the light. Third, there is no side absorption,
To provide a silver halide photographic light-sensitive material having improved color reproducibility. Fourthly, to provide an inexpensive silver halide photographic light-sensitive material having excellent production stability. Fifthly, it was possible to provide a silver halide photographic light-sensitive material and a processing method therefor, which does not cause a problem in an image formed even if the processing time for which the development processing time is greatly shortened.

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material having on a support at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer adjacent to the emulsion layer,
The non-photosensitive hydrophilic colloid layer has the following general formula (HQ-1)
A silver halide photographic light-sensitive material comprising at least one kind of hydroquinone derivative represented by the following formula and a compound represented by the following general formula (I). Embedded image (In the formula, R ₁₁ represents a secondary alkyl group, and R ₁₂ represents a substituent.) (In the formula, R _I1 , R _I2 , R _I3 and R _I4 each represent a hydrogen atom or an alkyl group, and R _I5 and R _I6 each represent a hydrogen atom or a substituent.) 2. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and a non-light-sensitive hydrophilic colloid layer adjacent to the emulsion layer,
The non-photosensitive hydrophilic colloid layer has the above general formula (HQ-1).
A silver halide photographic light-sensitive material comprising at least one kind of hydroquinone derivative represented by and a compound represented by the following general formula (II). Embedded image (In the formula, R _{II1 to} R _II4 each represent a hydrogen atom or a substituent.) 3. The silver halide photographic light-sensitive material according to claim 1, wherein the light-sensitive silver halide emulsion layer contains a compound represented by the following general formula (M-1). . Embedded image (In the formula, Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a color developing agent. (R represents a group capable of splitting off upon reaction with an oxidant, and R represents a hydrogen atom or a substituent.) 4. The non-photosensitive hydrophilic colloidal layer contains at least one compound represented by the following general formula (HQ-2), wherein: Silver halide photographic light-sensitive material. Embedded image (In the formula, R ₂₁ represents a tertiary alkyl group, and R ₂₂ represents a substituent.) 5. The non-photosensitive hydrophilic colloid layer contains at least two hydroquinone derivatives represented by the general formula (HQ-1), wherein
Alternatively, the silver halide photographic light-sensitive material described in 4 above. 6. A method of processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material according to claim 1 for a color development processing time of 30 seconds or less. .