JPH09166842A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sensitive material less liable to variation in performance due to a humidity charge at the time of exposure and ensuring a stable finish by forming a photosensitive silver halide emulsion layer on a substrate and incorporating a specified compd. SOLUTION: This sensitive material has at least one photosensitive silver halide emulsion layer on the substrate and contains at least one kind of compd. represented by the formula, or contains silver halide particles having >=90mol%, preferably &i95mol% silver chloride content in at least one silver halide emulsion layer and contains at least one kind of compd. represented by the formula in the emulsion layer or other hydrophilic colloidal layer through which water permeates into the emulsion layer. In the formula, each of R1 and R2 is alkyl, aryl or a heterocyclic group. X is O or S and each of (m) and (n) is 0 or 1 bur both of them are not 0.

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 capable of producing a stable finish with little change in performance due to changes in humidity during exposure.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials, particularly silver halide color photographic light-sensitive materials, are widely used today because of their high sensitivity, excellent gradation and sharpness.

However, the development processing of the silver halide color photographic light-sensitive material is a so-called wet processing, and it takes time to prepare the processing solution, it becomes dirty, a waste solution containing various chemicals is discharged, and a dark room is required. There are drawbacks such as a long time from the start of the operation until the first print is obtained. To compensate for these disadvantages and take advantage of the advantages of the silver halide color photographic light-sensitive material described above, until now, skilled engineers have concentrated on developing color negatives to producing color prints in only a few large developing laboratories. The scheme has been taken.

However, although the essence of wet processing has not changed in recent years, improvements in equipment such as printers and automatic processors, improvements in developing solutions, improvements in silver halide color photographic light-sensitive materials and their packaging forms have been accumulated. Therefore, so-called minilabs, which are capable of consistently performing from the development of color negatives to the production of color prints in a small space such as at a photo shop, are rapidly becoming popular.

In recent years, the development processing time has been remarkably shortened by employing a silver halide emulsion containing a high concentration of silver chloride. However, it was not found when using a silver halide photographic light-sensitive material containing a silver halide emulsion containing silver chlorobromide which does not contain silver chloride at a high concentration, which is not suitable for processing with shortened development processing time. However, there is a problem that the same scene has different finishes depending on the environmental conditions of exposure. As a result of analyzing these problems, it was found that the finish differs depending on the humidity condition during exposure.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material capable of obtaining stable finish (especially stable print finish) with less performance fluctuation due to humidity change during exposure.

[0007]

The inventors of the present invention have made intensive studies on silver halide photographic emulsions for use in silver halide photographic light-sensitive materials, and have found that the above-mentioned objects of the present invention can be achieved by the following constitution. The present invention has been completed.

That is, the above objects of the present invention are: A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, comprising at least one compound represented by the following general formula 1 Photosensitive material,

[0009]

Embedded image [In the formula, R ₁ and R ₂ may be the same or different,
Each represents an alkyl group, an aryl group or a heterocyclic group, X represents an oxygen atom or a sulfur atom, and m and n each independently represent 0 or 1. However, both m and n are 0
Never be. ] 2. In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has a silver chloride content of 90.
At least one compound represented by the general formula 1 is contained in the silver halide emulsion layer or another hydrophilic colloid layer having a water-permeability relationship with the silver halide emulsion layer which contains mol% or more of silver halide grains. 2. A silver halide photographic light-sensitive material characterized by containing: A silver halide photographic light-sensitive material as described in 2 above, which contains silver halide grains having a silver chloride content of 95 mol% or more.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below.
In the compound represented by the general formula 1 according to the present invention, R ₁
The alkyl group, aryl group, and heterocyclic group represented by R ₂ and R ₂ may be substituted or unsubstituted, and each preferably has 1 to 10 carbon atoms. Examples of preferable alkyl groups include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of preferable aryl groups include a phenyl group and a naphthyl group. Preferred heterocyclic groups include, for example, pyridyl group,
Examples thereof include an imidazolyl group.

Next, specific representative examples of the compound represented by the general formula 1 used in the present invention (hereinafter referred to as the compound according to the present invention) are shown, but the present invention is not limited thereto.

[0012]

Embedded image

Specific examples of the method for synthesizing the compound of the present invention are shown below. Synthesis of Compound (5) 4-Phenylsemicarbazide (PhNHCONHN
H ₂ ) 1.51 g (0.01 mol) and ethyl isothiocyanate (1.00 g, 0.015 mol) were added to 10 ml of tetrahydrofuran and heated to form a uniform solution. Was deposited. The reaction solution was refluxed for another 30 minutes, then cooled to room temperature, and 10 ml of N-hexane was added to promote precipitation of the product. The obtained crude product was filtered off and recrystallized from acetonitrile to obtain 1.88 g of compound (5) (yield 79%). The melting point was 211.5-211.9 ° C.

Synthesis of Compound (6) Benzohydrazide (PhCONHNH ₂ ) 1.36 g
(0.01 mol) was treated with ethyl isothiocyanate in the same manner as above, and the resulting crude product was recrystallized from ethanol to give 2.13 g of compound (6) (yield 95
%) Obtained. The melting point was 185 to 186 ° C.

Synthesis of compound (7) 4-phenylthiosemicarbazide (PhNHCSNHN
H ₂ ) 1.67 g (0.01 mol) was treated with ethyl isothiocyanate in the same manner as above, and the obtained crude product was recrystallized from acetonitrile to give 2.28 g of compound (7) (yield: 90%) was obtained. Melting point 180.5
It was -181.5 ° C. Other compounds can be synthesized in the same manner as above.

The above-mentioned compound in the present invention is a silver halide emulsion layer of a light-sensitive material and other hydrophilic colloid layers having a water-permeable relationship therewith (intermediate layer, filter layer, antihalation layer, protective layer, undercoat layer, etc.). ) In at least one layer. A particularly preferred layer is a silver halide emulsion layer.

The addition amount of the compound according to the present invention is not uniform depending on the kind of the light-sensitive material and the compound, but the compound represented by the formula 1 is 0.01 mg per mol of silver halide.
It is preferable to use it in the range of ~ 1,000 mg, more preferably 0.05 mg to 500 mg. The amount added to the hydrophilic colloid layer is 0.1 mg per 1 m ² of coating.
It is preferably used in the range of 2,000 mg, more preferably 10 mg to 1,000 mg.

These compounds are dissolved in water or a hydrophilic organic solvent (eg methanol, dimethylformamide, etc.) and added to the required constituent layers.

In the case of silver halide emulsions, they are added during chemical ripening, after chemical ripening, and / or immediately after emulsion coating, more preferably at the end of chemical ripening of silver halide emulsions. Is.

The fog inhibitor of the present invention can be applied to various types of light-sensitive materials such as the following. For example, a light-sensitive material for general-purpose black and white, X-ray recording, plate making, color positive, color negative, color paper, reverse color, direct positive, heat development, or surface latent image type silver halide grains. US Pat. Nos. 2,996,382 and 3,178 using silver halide grains having internal fog nuclei.
Although it can be used for the light-sensitive material according to the method described in JP-A No. 282, the application to a color light-sensitive material having a multilayer structure is particularly advantageous.

The silver halide emulsion used in the present invention is a conventional silver halide such as silver bromide, silver chloride, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloroiodobromide as silver halide. Any of those used in emulsions can be used.

The silver halide grains used in the silver halide emulsion are core / shell grains having a different silver halide composition between the inside and the surface layer of the grain even if they have a uniform silver halide composition distribution within the grain. It may be.

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide emulsion may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

The composition of the silver halide photographic emulsion according to the present invention is preferably silver chlorobromide containing substantially no silver iodide and containing 90 mol% or more, particularly 95 mol% or more of silver chloride. From the viewpoint of rapid processability and process stability, preferably 97 mol% or more, more preferably 98 to 99.9 mol%.
Particularly preferred are silver halide emulsions containing silver chloride.

In order to obtain the preferred silver halide emulsion according to the present invention, a silver halide emulsion having a portion containing a high concentration of silver bromide 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 a preferred silver halide emulsion according to the present invention, it is advantageous to contain a heavy metal ion. Examples of heavy metal ions that can be used for such purposes include iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt and the like.
Examples thereof include Group 10 metals, 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 ligands are cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl and ammonia. Etc. can be mentioned. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to make the silver halide emulsion according to the present invention contain a heavy metal ion, the heavy metal compound is physically added before forming silver halide grains, during silver halide grains, and after forming silver halide grains. What is necessary is just to add in arbitrary places of each process during ripening. 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 over the whole or part of the grain forming process.

When the above heavy metal ions are added to the silver halide emulsion, the amount is 1 × 10 1 per mol of silver halide.
More preferably ^-9 mol or more and 1 x 10 ^-2 mol or less,
Particularly, it is preferably 1 × 10 ⁻⁸ mol or more and 5 × 10 ⁻⁵ mol or less.

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. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666.
No. 5, JP-A-55-26589, JP-B-55-4273
No. 7 and The Journal of Photographic
Science (J. Photogr. Sci.) 21, 3
It is also possible to prepare particles having a shape such as an octahedron, a tetradecahedron, a dodecahedron, and the like by the method described in the literature such as 9 (1973). Further, particles having a twin plane may be used.

The grain size of the silver halide grains according to the present invention is not particularly limited, but considering other photographic performance 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.

The term "particle size" as used herein means the diameter of spherical silver halide grains, and the particle size of cubes or grains other than spherical grains when the projected image is converted into a circular image of the same area. Represents the diameter of.

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

The grain size distribution of the silver halide grains of 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 a coefficient of variation of 0 is particularly preferred. It is to add two or more monodisperse emulsions of 0.15 or less to the same layer. Here, the coefficient of variation is defined by the following equation, which is a coefficient representing the breadth of the particle size distribution.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution, and R is the average grain size.) Various devices known in the art can be used as the apparatus and method for preparing the silver halide emulsion. Any method 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 grains may be grown at one time, or may be grown after the seed grains are formed. 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 a method 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 arranged in a reaction mother liquor, and a water-soluble silver salt and a water-soluble solution described in German Patent Publication No. 292,164. Apparatus for continuously changing the concentration of an aqueous halide salt solution, JP-B-56-50
The reaction mother liquor was taken out of the reactor described in No. 1776, etc.,
You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

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 depending on the type of silver halide emulsion to be applied and the magnitude of the expected effect, but 5 × 10 5 per mol of silver halide. The range of ^{−10 to} 5 × 10 ⁻⁵ mol is preferable, and the range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol is preferable.

As the gold sensitizer according to the present invention, various gold complexes other than chloroauric acid, gold sulfide and the like can be added. 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 1 mol per mol of silver halide.
It is preferably ^-8 mol. More preferably 1 × 1
0 ^-5 mol to 1 × ^{10 -8} mol.

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

In the silver halide photographic light-sensitive material of the present invention, dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used, but in particular, as a dye having absorption in the visible region,
JP-A-3-251840, A described on page 308
The dye of I-1-11 and the dye described in the specification of JP-A-6-3770 are preferably used. As the infrared absorbing dye, the general formula (I shown in the lower left column of page 1-2 of JP-A-1-280750) is used. ), (II) and (III) have preferable spectral characteristics, and they are preferable because they do not affect the photographic characteristics of the silver halide photographic emulsion and do not cause contamination due to residual color. Specific examples of preferable compounds include Exemplified Compounds (1) to (45) listed in page 3, lower left column to page 5, lower left column of the same publication.

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

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention because the whiteness can be improved. Examples of the compounds preferably used include the compounds represented by the general formula II described in JP-A-2-232652.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, a silver halide emulsion spectrally sensitized in an arbitrary wavelength range by combining with a yellow coupler, a magenta coupler and a cyan coupler is used. Having a layer containing. 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 in JP-A-251840, page 28 can be preferably used alone or in combination. Examples of the green photosensitive sensitizing dye include G
S-1 to S-5 are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. Further, the red, green and blue photosensitive sensitizing dyes have the supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and JP-A-5-66515, 15 to 17. The compounds S-1 to S-17 described on the page 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 or dimethylformamide or water to add it as a solution, or by adding it as a solid dispersion. Although it may be added, it is preferably added as a solid dispersion.

As the coupler used in the silver halide photographic light-sensitive material according to the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength region 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 50
Typical examples are magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of 0 to 600 nm, and cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
The couplers represented by the general formulas (C-I) and (C-II) described in the lower left column of page 5 of JP-A-4-114154 can be mentioned. Specific compounds are described in the same specification at page 5, lower right column to page 6, lower left column, CC-1 to C
The thing described as C-9 can be mentioned.

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, the general formulas (MI) and (M) described in the upper right column of page 4 of JP-A-4-114154 are disclosed. A coupler represented by -II) may be mentioned. Specific compounds are described in MC-1 in the lower left column on page 4 to the upper right column on page 5 of the specification.
~ MC-11 can be mentioned. More preferable among the above magenta couplers are those represented by the general formula (M-
Among them, the couplers represented by I), of which the RM of the general formula (M-I) is a tertiary alkyl group, are particularly preferable because of their excellent light resistance. 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 silver halide photographic light-sensitive material of the present invention, known yellow couplers such as pivaloylacetanilide type yellow couplers and benzoylacetanilide type yellow couplers can be used.

For the silver halide photographic light-sensitive material according to the present invention, a coupler represented by the general formula (YI) described in JP-A-4-114154, page 3, upper right column is used. You can Specific compounds include those described as YC-1 to YC-9 in the lower left column of page 3 of the same publication. Further, a coupler represented by the general formula [I] described in the specification of JP-A-6-67388 can also be used, and specifically, it is described in the lower left column on page 4 of the specification of JP-A-4-114154. YC-8, YC-9, and JP-A-6-6738.
No. 1 described on pages 13 to 14 of Japanese Patent Publication No. 8
The compound shown by (47) can be mentioned. Further, compounds represented by the general formula [Y-I] described in JP-A-4-81847, page 1 and page 11, page 17 to page 17 can also be used.

When the oil-in-water type emulsion dispersion method is used to add the coupler or other organic compound used in the silver halide photographic light-sensitive material of the present invention, it is usually highly water-insoluble with a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or water-soluble organic solvent may be used in combination with the boiling point organic solvent to dissolve, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. 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 decompose and disperse the coupler, dioctyl phthalate, diisodecyl phthalate, phthalates such as dibutyl phthalate, tricresyl phosphate, phosphates such as trioctyl phthalate,
Is preferably used. The high-boiling point organic solvent preferably has a dielectric constant of 3.5 to 7.0. It is also possible to use two or more high boiling point organic solvents 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 optionally added 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 organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

As a compound preferable as a surfactant used for dispersing the photographic additives and adjusting the surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof are contained 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. A surfactant having a fluorine atom substituted in the alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is preferable that the time from the dispersion to the addition to the coating solution and the time from the addition to the coating solution and the coating are short, respectively. It is preferably within the time, 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 the general formulas I and II described in JP-A-2-66541, page 3, and the general formula III described in JP-A-3-174150.
A phenolic compound represented by B, JP-A-64-904
45, an amine compound represented by the general formula A,
General formula XII described in JP-A-62-182741,
The metal complexes represented by XIII, XIV and XV are particularly preferable for the magenta dye. Also, Japanese Patent Laid-Open No. 1-19604
The compound represented by the general formula I ′ described in JP-A No. 9 and the compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the color forming 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. A compound such as (A′-1) can be used. In addition to this, US Pat.
The fluorescent dye-releasing compounds described in No. 74187 can also be used.

The silver halide light-sensitive material of the present invention comprises
It is preferable to add a compound that reacts with an oxidized product of a developing agent to a layer between the light-sensitive layers to prevent color turbidity, or to a silver halide emulsion layer to improve fog and the like.
The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone.
A particularly preferable compound is a compound represented by the general formula II described in JP-A-4-133056, and compounds II-1 to II-14 described on pages 13 to 14 of the specification of the same publication.
And compound 1 described on page 17.

It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog and improve the light resistance of dye images. 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, compounds represented by formula I described in JP-A-4-1633, and compounds represented by formulas (I) and (II) described in JP-A-5-165144.

For the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin, etc. 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-61-2
It is preferable to use the compounds described in JP-A Nos. 49054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to a colloid layer for preventing the growth of mold and bacteria which adversely affect photographic performance and image storability. Further, in order to improve the physical properties of the surface of the light-sensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.

As the support used in the silver halide photographic light-sensitive material of the present invention, any material can 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, polyethylene terephthalate support, cellulose triacetate, baryta paper, etc. 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 thereof include titanium, zinc oxide, talc, clay and the like. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the waterproof resin layer on the surface of the support is 13% by weight in order to improve the sharpness.
The above is preferred, and more preferably 15% by weight.

The dispersity 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 center surface average roughness (SRa) of the support is 0.15 μm or less, and more preferably 0.12 μm or less because the effect of good gloss can be obtained. In addition, in order to improve the whiteness by adjusting the spectral reflection density balance of the white background after treatment in the water-resistant resin containing white pigment of the reflective support or in the applied hydrophilic colloid layer, trace amounts of ultramarine blue, oil-soluble dyes, etc. It is preferable to add a bluing agent and a reddishing agent.

In the silver halide photographic light-sensitive material according to the present invention, the support surface is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or undercoat layer (adhesiveness of the support surface, 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 simultaneously applied, are particularly useful as an application method.

To form a photographic image using the silver halide photographic light-sensitive material of the present invention, 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 after the image is once converted into digital information, the image is formed on a CRT (cathode ray tube) and then formed on the silver halide photographic light-sensitive material to be printed. Printing may be performed, or the scanning may be performed by changing the intensity of the laser light based on digital information and scanning.

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 particularly preferably to a light-sensitive material for forming an image for direct viewing. Examples thereof include 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. 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 can be mentioned as an example 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 above-mentioned color developing solution can be used in any pH range, but from the viewpoint of rapid processing, the pH of the color developer is 9.
It is preferably 5 to 13.0, more preferably p
H is used in the range of 9.8 to 12.0.

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.

The color development time is conventionally about 3 minutes and 30 seconds, but in the present invention, it is preferably 40 seconds or less, more preferably 25 seconds or less.

To the color developing solution, known developer component compounds 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.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Moreover, you may perform a stabilization process as an alternative of a washing process. 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 system in which it is fixed and conveyed, but by forming the processing tank in a slit shape,
It is also possible to use a method of supplying the processing solution to the processing tank and conveying the photosensitive material, a spray method of spraying the processing solution, a web method by contact with a carrier impregnated with the processing solution, a method of using a viscous processing solution, etc. You can In the case of processing a large amount, it is usually a running process using an automatic processor, but at this time, the smaller the replenishing amount of the replenisher is, the more preferable the processing form from the environmental suitability is the tablet as a replenishing method. Is to add a treating agent in the form of
Most preferred is the method described in Published Technique 94-16935.

[0085]

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 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.

23.4 g of a yellow coupler (Y-1),
Dye image stabilizer (ST-1) 3.34 g, (ST-
2) 3.34 g, (ST-5) 3.34 g, stain inhibitor (HQ-1) 0.34 g, image stabilizer A 5.0 g,
60 ml of ethyl acetate was added to and dissolved in 3.33 g of the high boiling organic solvent (DBP) and 1.67 g of the high boiling organic solvent (DNP), and this solution was added with 7 ml of 20% surfactant (SU-1).
A yellow coupler dispersion was prepared by emulsifying and dispersing it in 220 ml of a 10% gelatin aqueous solution containing a using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

This dispersion was mixed with a silver halide emulsion (Em-B101) (containing 8.50 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The second layer coating liquid was also prepared in the same manner as the first layer coating liquid. Further, (H-1) was added to the second layer as a hardener. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

Sample 101 was prepared as described above.
The layer structure is shown in Table 1 below. The added amount of the blue-sensitive emulsion is shown in terms of silver.

[0089]

[Table 1]

[0090]

Embedded image

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) · sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane HQ-1: 2,5-di-t-octylhydroquinone DBP: dibutylphthalate DNP: dinonylphthalate Image stabilizer A: pt-octylphenol

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

(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 K ₂ IrCl ₆ 4 × 10 ^-8 mol K ₄ Fe (CN) ₆ 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g Water was added to 600 ml (D liquid) Silver nitrate 300 g Water was added to 600 ml After the addition was completed, Kao Atlas Co., Ltd. Demol N 5 was added. % Aqueous solution and magnesium sulfate 20% aqueous solution for desalting, and then mixed with gelatin aqueous solution to obtain an average particle size of 0.71μ.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

(Preparation of Silver Chlorobromide Monodisperse Emulsion (EMP-2)) In the preparation of the high silver chloride monodisperse emulsion (EMP-1), (C liquid) and (D liquid) were replaced with the following (C2 liquid). And (D
Average particle size is 0.71μ
A monodisperse cubic emulsion EMP-2 having m, a coefficient of variation of particle size distribution of 0.07, and a silver chloride content of 90 mol% was obtained. (C2 liquid) Sodium chloride ^{_{92.9g K 2 IrCl 6 4 × 10}} -8 mol / mol _{Ag K 4 Fe (CN) 6} 2 × 10 -5 mol / mol Ag Potassium bromide 21.0g Water to make 600 ml ( D2 solution) Silver nitrate 300 g Water is added to 600 ml

(Preparation of Silver Chlorobromide Monodisperse Emulsion (EMP-3)) In the preparation of high silver chloride monodisperse emulsion (EMP-1), (C liquid) and (D liquid) were replaced with the following (C3 liquid). And (D
Average particle size is 0.71μ
A monodisperse cubic emulsion EMP-3 having m, a coefficient of variation of particle size distribution of 0.07, and a silver chloride content of 80 mol% was obtained. (C3 solution) Sodium chloride ^{_{82.6g K 2 IrCl 6 4 × 10}} -8 mol / mol _{Ag K 4 Fe (CN) 6} 2 × 10 -5 mol / mol Ag Potassium bromide 42.0g Water to make 600 ml ( D3 solution) Silver nitrate 300 g Water is added to 600 ml

(Preparation of blue-sensitive silver halide emulsion) E above
The following compounds were optimally chemically sensitized to MP-1 and MP2 at 60 ° C. to obtain a blue-sensitive silver halide emulsion (Em-B
101) to (Em-B102) were obtained.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-4 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 STAB-4: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazindene The sensitizing dyes BS-1 and BS-2 are , Japanese Patent Application No. 5-98
The sensitizing dye obtained by the method described on page 87 of the No. 094 specification was added by an addition liquid in the form of solid fine particles.

(Preparation of Green-Sensitive Silver Halide Emulsion) E above
MP-1 was optimally chemically sensitized at 55 ° C. using the following compound to obtain a green-sensitive silver halide emulsion (Em-G10
1) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-4 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX Here, the sensitizing dye GS-1 was added by an additive solution in which the sensitizing dye obtained by the method described on page 87 of Japanese Patent Application No. 5-98094 is present as solid fine particles.

(Preparation of Red-Sensitive Silver Halide Emulsion) E above
The following compounds were optimally chemically sensitized to MP-1 to MP-3 at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-R
101) to (Em-R103) were obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-4 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 Further, SS-1 was added to the red-sensitive emulsion in an amount of 2.0 × 10 ⁻³ per mol of silver halide.

Here, the sensitizing dyes RS-1 and RS-2 are prepared by the addition liquid in which the sensitizing dye obtained by the method described on page 87 of Japanese Patent Application No. 5-98094 is present as solid fine particles. Was added.

(Preparation of Infrared Sensitive Silver Halide Emulsion) The above compound EMP-1 was optimally chemically sensitized at 60 ° C. to obtain an infrared sensitive silver halide emulsion (Em-I).
R101) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-4 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye IRS-1 2 × 10 ⁻⁴ mol / mol AgX Here, the sensitizing dye IRS-1 was added by an additive solution in which the sensitizing dye obtained by the method described on page 87 of Japanese Patent Application No. 5-98094 is present as solid fine particles.

[0105]

[Chemical 6]

[0106]

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In the preparation of Sample 101, the silver halide emulsion (Em-B101) was changed as shown in Table 2 below.
Samples 102 to 120 were prepared in the same manner except that the compound shown in 1 was dissolved in ethanol and added. Sample 101-
120 was kept in an atmosphere of 25 ° C.-30% RH and 25 ° C.-80% RH, and light wedge exposure was performed by an ordinary method at an exposure time of 0.5 seconds, and then development processing was performed in the following development processing step.

Processing Step Processing Temperature Time Replenishment Amount Color Development 38.0 ± 0.3 ° C. 45 seconds 80 cc Bleach-fix 35.0 ± 0.5 ° C. 45 seconds 120 cc Stabilization 30-34 ° C. 60 seconds 150 cc Dry 60-80 ℃ 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 10.0 g diethylenetriaminepentaacetic 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 30 g 30 g Water was added to make the total volume 1 liter, and the tank liquid had pH = 10. .10, the replenisher had a pH of 10.60. Adjust to

Bleach-fixing solution Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-Amino-5-mercapto-1,3,4-thiadiazole 2 0.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing liquid tank liquid and replenishing liquid o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 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 1 0.0 g Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g Nitrilotriacetic acid trisodium salt 1.5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or ammonia water.

The blue density of the obtained material was measured using a PDA-65 densitometer (manufactured by Konica Corporation). Sensitivity is defined based on the reciprocal of the exposure dose giving a density of 0.75,
Regarding the sensitivity of -30 ° C RH, sample 101 is used in the case of a sample using a blue-sensitive silver halide emulsion, sample 109 is used in the case of a sample using a green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion. In the case of a sample using
Sample 1 using infrared-sensitive silver halide emulsion
19 was designated as 100 and expressed as a relative value. Also, 25 ° C-8
For the sensitivity of 0% RH, the same sample at 25 ° C-30% R
The sensitivity of H was set to 100 and expressed as a relative value. Table 2 shows the results.

[0113]

[Table 2]

As can be seen from the above results, by using the compound of the present invention, it is possible to improve the decrease in sensitivity that occurs when exposed to high humidity in a sample using a high silver chloride emulsion.

Example 2 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 shown in Tables 3 and 4 below.

Further, as hardeners (H-1), (H-
2) was added. As a coating aid, a surfactant (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 was 0.04 g / m ² .

[0117]

[Table 3]

[0118]

[Table 4] The amount of silver halide emulsion added is shown in terms of silver.

PVP: Polyvinylpyrrolidone DOP: Dioctylphthalate DIDP: Di-i-decylphthalate PVP: Polyvinylpyrrolidone H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-2: 2,5- Di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1, 1-dimethyl-4-hexyloxycarbonyl) butyl hydroquinone

[0120]

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[0121]

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[0122]

Embedded image

[0123]

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(Preparation of blue-sensitive silver halide emulsion) By the method described in Example 1, the average grain size was 0.71 μm, the variation coefficient of grain size distribution was 0.07, and the silver chloride content was 99.5 mol%. A dispersed cubic emulsion EMP-1 was obtained. Next, (solution A) and (B
The average particle size was 0.64 in the same manner as EMP-1 except that the addition time of (solution) and the addition time of (solution C) and (solution D) were changed.
μm, variation coefficient of particle size distribution 0.07, silver chloride content 9
A 9.5 mol% monodisperse cubic emulsion EMP-1B was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization 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

(Preparation of green-sensitive silver halide emulsion) (A
(Solution) and (solution B), and (C solution) and (solution D), except that the addition time was changed, the average particle size was 0.40 μm, the coefficient of variation was 0.08, and silver chloride was the same as EMP-1. Content rate 9
A 9.5% monodisperse cubic emulsion EMP-4 was obtained. Next, a monodisperse cubic emulsion EMP-4B having an average grain size of 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above EMP-4 was optimally chemically sensitized at 55 ° C. using the following compounds. Also EMP-4B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-4 and EMP-4B were mixed in 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) (A
(Solution) and (solution B), and (C solution) and (solution D), except that the addition time was changed, the average particle size was 0.40 μm, the coefficient of variation was 0.08, and silver chloride was the same as EMP-1. Content rate 9
A 9.5% monodisperse cubic emulsion EMP-5 was obtained. Further, a monodisperse cubic emulsion EMP-5 having an average grain size of 0.38 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The EMP-5 was optimally chemically sensitized at 60 ° C. using the following compounds. Also EMP-5B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-5 and EMP-5B were mixed at a ratio of 1: 1 in terms of silver amount 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 Further, for the red-sensitive emulsion, SS-1 was added at 2.0 × 10 ⁻³ per mol of silver halide.

In the preparation of these emulsions, the sensitizing dye was added in the same manner as in Example 1 with the addition liquid in which the sensitizing dye was present as solid fine particles.

In this way, the sample 401 was manufactured. Samples 202 to 20 were prepared in the same manner as in Sample 201, except that the compounds shown in Table 5 were added.
9 was produced.

[0135]

[Table 5]

Samples 201 to 209 were exposed and developed in the same manner as in Example 1, and the obtained material was measured for blue, green and red densities by using a PDA-65 densitometer (manufactured by Konica Corporation). It evaluated similarly to. Table 6 shows the results.

In Table 6, the blue sensitivity, green sensitivity, and red sensitivity are shown as relative values with the sensitivity of Sample 201 at 25 ° C.-30% RH as 100.

[0138]

[Table 6]

As can be seen from the above, it can be seen that the sample to which the compound of the present invention is added shows the improvement effect even in the multi-layer.

Example 3 Samples 201, 204, 206 and 20 prepared in Example 2
8 was exposed and developed through Konica Color LV-400 which had been developed using an automatic processor (NPS-868J manufactured by Konica Corporation; ECOJET-P was used as a processing chemical). This automatic processor has been modified to measure the temperature and humidity in the exposed area. This automatic processor was installed in a room where the temperature and humidity could be set to a constant value, and the temperature of the room was kept constant, and the humidity was varied, and printing was performed from negative film in the same scene. When the prints developed during this period were viewed, Sample 201 showed a shift toward yellow when the humidity of the exposed portion increased. Samples 204, 20 of the present invention
Nos. 6 and 208 showed no change in the print color regardless of the humidity of the exposed portion, and it was found that a stable print finish was obtained.

[0141]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which has a small performance fluctuation due to a change in humidity at the time of exposure and can obtain a stable finish.

Continuation of front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location G03C 7/00 550 G03C 7/00 550 (72) Inventor Yoshihiko Suda 1 Sakura-cho, Hino-shi, Tokyo Konica Stock Company (72) Inventor Tsuyoshi Ikeda, Konica Co., Ltd. 1 Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Takahiko Nojima 1 Sakura-cho, Hino-shi, Tokyo Konica stock company

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, which contains at least one compound represented by the following general formula 1. A silver halide photographic light-sensitive material. Embedded image [In the formula, R ₁ and R ₂ may be the same or different,
Each represents an alkyl group, an aryl group or a heterocyclic group, X represents an oxygen atom or a sulfur atom, and m and n each independently represent 0 or 1. However, both m and n are 0
Never be. ] 2. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has a silver chloride content of 90 mol% or more. Characterized in that it contains at least one compound represented by the following general formula 1 in the silver halide emulsion layer or in another hydrophilic colloid layer having water permeability with the silver halide emulsion layer. And a silver halide photographic light-sensitive material. Embedded image [In the formula, R ₁ and R ₂ may be the same or different,
Each represents an alkyl group, an aryl group or a heterocyclic group, X represents an oxygen atom or a sulfur atom, and m and n each independently represent 0 or 1. However, both m and n are 0
Never be. ] 3. The silver halide photographic light-sensitive material according to claim 2, which contains silver halide grains having a silver chloride content of 95 mol% or more.