JPH07253640A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material good in sharpness and reduced in fluctuation of sharpness in mass production. CONSTITUTION:This silver halide photographic sensitive material has a substrate and at least one silver halide emulsion layer At least one hydrophilic colloid layer contg. white pigment is interposed between the substrate and emulsion layer. The variation coefficient S/R (S is the standard deviation of the occupancy area ratio per unit area, and R is the average area ratio per unit area) of the occupancy area ratio (%) per unit area of the white pigment is controlled to <=0.25, and a high-b.p. org. compd. having >=150 deg.C b.p. is incorporated into the hydrophilic colloid layer contg. the white pigment.

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 forming an image with good sharpness.

[0002]

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

Sharpness is an important item as the image quality performance required for a silver halide photographic light-sensitive material, and if this is impaired, the commercial value will be lost. Therefore, many sharpness improving techniques have been proposed. As a method for improving the sharpness of a silver halide photographic light-sensitive material, a method of adding or increasing a water-soluble coloring dye for preventing irradiation, and a coloring-containing layer such as black colloidal silver for preventing halation are provided. There is a method of adding a white pigment to the reflective support and increasing the amount thereof.

However, when the present inventors try to improve the sharpness by increasing the addition amount by these methods,
It was found that there are problems that the color tone on the image changes, the whiteness deteriorates, and the gloss deteriorates. Therefore, as a result of examining a method for reducing these problems and improving sharpness, there was a method of coating a hydrophilic colloid layer containing a white pigment between the support and the silver halide emulsion layer. As a result of studying this method, the authors have found that this method improves the sharpness to some extent, but is still insufficient, and that the sharpness varies with the passage of time during mass production of silver halide photographic light-sensitive materials. I also found a new problem that would arise.

[0005]

In view of the above problems, the first object of the present invention is to provide a silver halide photographic light-sensitive material having good sharpness, and the second object is mass production production. Sometimes to provide a silver halide photographic light-sensitive material with little fluctuation in sharpness.

[0006]

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

1. In a silver halide photographic light-sensitive material having a support and at least one silver halide emulsion layer,
A hydrophilic colloid layer containing at least one white pigment is provided between the support and the silver halide emulsion layer, and the variation coefficient S of the occupied area ratio (%) per unit area of the white pigment is S.
/ R (S is the standard deviation of the occupied area ratio per unit area, R
Represents an average area ratio per unit area) is 0.25 or less, and the boiling point of the hydrophilic colloid layer containing the white pigment is 15
1. A silver halide photographic light-sensitive material containing an organic compound having a high boiling point of 0 ° C or higher. 2. The silver halide photographic light-sensitive material as described in 1 above, wherein the hydrophilic colloid layer containing the white pigment contains gelatin and a high-boiling organic solvent having a boiling point of 300 ° C. or higher. 3. The silver halide photographic light-sensitive material as described in 1 or 2 above, wherein the total weight of the high boiling point organic solvent is 10% to 100% of the weight of gelatin in the hydrophilic colloid layer containing the white pigment.

The details of the present invention will be described below.

In the silver halide photographic light-sensitive material of the present invention, at least one layer containing a white pigment is provided between the support and at least one silver halide emulsion layer to effectively bring out the effect of the present invention. Needed in. The hydrophilic colloid layer containing the white pigment of the present invention will be described below.

The white pigment used in the hydrophilic colloid layer (hereinafter referred to as the white pigment layer) containing the white pigment of the present invention is, for example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, Alumina, zirconium oxide, kaolin and the like can be used, but titanium dioxide is preferable among them for various reasons. The white pigment is dispersed in a water-soluble binder of hydrophilic colloid such as gelatin so that the treatment liquid can permeate, and applied as a white pigment layer. Coating with the amount of white pigment, preferably in the range of ^{0.5g / m 2 ~50g / m 2} , more preferably in the range of ^{1g / m 2 ~20g / m 2} .

The white pigment layer of the present invention can be provided between the support and the silver halide emulsion layer closest to the support. Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment layer, an undercoat layer may be provided on the support, or a non-photosensitive hydrophilic layer such as an intermediate layer may be provided at any position. A colloidal layer can be provided.

The white pigment layer of the present invention preferably has a porosity of 5 to 30% by weight based on the hydrophilic colloid layer. The porosity is obtained from the specific gravity, the film thickness and the like.

In the white pigment layer of the present invention, in addition to the white pigment,
Coloring agents such as yellow, gray, blue, and black colloidal silver, inorganic colored pigments, organic colored pigments, dyes and the like can be added.

A colorant-containing hydrophilic colloid layer can be coated between the white pigment layer of the present invention and the support. As the colorant, various known filter dyes can be used in addition to yellow, gray, blue, and black colloidal silver. As such a light-absorbing substance, it is possible to use a substance that absorbs only light in the entire visible spectrum region, or a substance that selectively absorbs light in a certain part of the region as necessary. You can choose. The transmittance of the colorant-containing hydrophilic colloid layer is preferably 50% or less, particularly preferably 30% or less.

The coefficient of variation of the occupied area, which indicates the dispersity of the white pigment of the present invention, must be 0.25 or less. To measure the dispersity of the coated white pigment particles, the white pigment layer of the silver halide photographic light-sensitive material is dissolved with a proteolytic enzyme and the resulting white pigment is photographed with an electron microscope. Can be obtained and evaluated by the coefficient of variation of the occupied area ratio (%). The coefficient of variation of white pigment is 0.25
The following adjustment method can be achieved by sufficiently kneading a white pigment in the presence of a surfactant. It can also be obtained by removing the large particle component and the small particle component using centrifugation or the like. The occupied area ratio (%) per unit area of the white pigment is most typically the observed area is divided into contiguous unit areas of 6 μm × 6 μm, and the occupied area of particles projected on the unit area. It can be determined by measuring the ratio (%) (Ri). The variation coefficient of the occupied area ratio (%) can be obtained by the ratio S / R of the standard deviation S of Ri to the average value (R) of Ri. The number (n) of the target unit areas is preferably 6 or more. Therefore, the coefficient of variation S /
R is

[0016]

[Equation 1]

It can be determined by

In the present invention, when the coefficient of variation of the occupied area of the white pigment is 0.25 or less, the effect of the present invention that stable sharpness performance can be obtained even in mass production is obtained, but it is more effective. Therefore, it is preferably 0.20 or less, more preferably 0.15 or less. It is more preferably 0.10 or less.

The amount of the white pigment added to the white pigment layer of the present invention is preferably 20 to 90% by weight, more preferably 40 to 90% by weight, in order to effectively obtain the effects of the present invention. % Is more preferable. Most preferred is 50-80% by weight. Generally, if the addition density is low, it is difficult to obtain a sample with good sharpness. When the addition density is large, the sharpness improving effect is large, but in contrast to the new problem that a stable and sharp sample is difficult to obtain, in the constitution of the present invention, the sharpness is stable even when the addition density is large. Performance is obtained. Further, if the addition density becomes higher and approaches 100%, the physical properties of the film, such as the deterioration with the film on the support, will deteriorate, which is not preferable.

Further, it is preferable that the hydrophilic colloid layer containing the white pigment of the present invention contains hollow polymer particles because the effect of the present invention is great. Hollow polymer particles are those in which the inside of the polymer particles is not a polymer but a cavity. This is more preferable because the fine particles of bubbles can be stably present and the light reflectance can be improved. The average particle size of the hollow polymer particles is preferably 0.1 μm to 1.0 μm. As a material for the hollow polymer, a highly crosslinkable polymer is preferable in order to maintain cavities. As the hollow polymer, for example, a hollow polymer of styrene-acrylic resin manufactured by Nippon Synthetic Rubber Co., Ltd. can be used.

In the present invention, it is necessary to add a high boiling point organic compound having a boiling point of 150 ° C. or higher to the white pigment layer. It may be a compound that decomposes at high temperature when measuring the boiling point, but
It is more preferable that the organic solvent has a high boiling point of 300 ° C. or higher. A high-boiling organic solvent having a vapor pressure at 100 ° C. of 0.5 mmHg or less is also preferable.

The boiling point of 150 ° C. or higher means that the boiling point at 1 atm is 150 ° C. or higher. Further, the high boiling point organic compound of the present invention is preferably a liquid at 1 atm and 50 ° C.

Examples of the high boiling point organic compounds of the present invention include phthalic acid esters, phosphoric acid esters, fatty acid esters, organic acid amides, ketones, hydrocarbon compounds, and the like, and JP-A-1-156748. The organic compounds described on page 34, H-1 to H-20, and the like can also be used.

The high boiling point organic compound that can be used in the present invention is preferably an organic compound having 20 or more carbon atoms (branched,
Or optionally substituted by a substituent), more preferably an organic compound having 24 or more carbon atoms (branched or optionally substituted by a substituent), particularly preferably those organic compounds are saturated It is a hydrocarbon compound (which may be branched or may be substituted with a substituent). Most preferably, it is paraffin. Specific examples of the high boiling point organic compound of the present invention are shown below, but the present invention is not limited thereto.

Compound Example O-1 di-n-octyl phthalate O-2 di-i-decyl phthalate O-3 tri-n-nonyl phosphate O-4 di (ω-butyl-di (ethyleneoxy)) adipate O- 5 Di-n-octyl sebatate O-6 Glycerine triacetate O-7 Di-n-octyl fumarate O-8 Trioctyl trimellitate O-9 Tridodecyl phosphate O-10 Trioctyl-phosphine oxide O-11 n-hexadecane O- 12 n-aicosan O-13 n-docosan O-14 n-tetracosane O-15 n-hexacosane O-16 Sansosizer E-200 (manufactured by Shin Nippon Rika Co., Ltd.) O-17 Sansosizer P-1500A (new Nippon Rika Co., Ltd.
O-18 liquid paraffin No150-S (manufactured by Sanko Chemical Industry Co., Ltd.) The high-boiling organic compound of the present invention may be used alone or 2
You may use together 1 or more types.

The high-boiling organic compound of the present invention is used in combination with a low-boiling organic solvent and / or a water-soluble organic solvent, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution to obtain a stirrer, a homogenizer, a colloid mill, It is emulsified and dispersed using a dispersing means such as a flow jet mixer or an ultrasonic device, and then added to the desired hydrophilic colloid layer. When the hydrophilic colloid is present in the non-photosensitive hydrophilic colloid layer on the side closer to the support from the gelatin aqueous solution-containing layer, gelatin is preferably used as the hydrophilic colloid.

The addition amount of the high-boiling point organic compound of the present invention is preferably 5 to 200% by weight based on the amount of the binder in the hydrophilic colloid layer containing the high-boiling point organic compound, More preferably, it is 10 to 100%.

The silver halide photographic emulsion used in the present invention has any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferable. The present invention is a technique relating to characteristics during exposure, and it is preferable to use it in combination with a technique capable of obtaining stable characteristics during processing. From this viewpoint, it is preferably 97 mol% or more, more preferably 98 to 99.9 mol. Silver halide emulsions containing% silver chloride are preferred.

To obtain the silver halide emulsion used in 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 silver bromide in a high concentration may be either epitaxy bonded to the silver halide emulsion grains or a so-called core-shell emulsion, or may not form a complete layer and may be partially formed. There may be only regions having different compositions. The composition may change continuously or discontinuously. The portion where silver bromide is present at a high concentration is particularly preferably the apex of crystal grains on the surface of silver halide grains.

In order to obtain the silver halide emulsion used in the present invention, it is advantageous to contain heavy metal ions. Heavy metal ions that can be used for such purpose include iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt and the like VIII
Examples thereof include group metals, group II transition metals such as cadmium, zinc, and mercury, and ions of lead, rhenium, molybdenum, tungsten, and chromium. Of these, transition metal ions of iron, iridium, platinum, ruthenium and osmium are preferable. 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, examples of the ligand include cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, ammonia and the like. be able to. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to incorporate heavy metal ions into the silver halide emulsion used in the present invention, the heavy metal ions are added before the formation of silver halide grains, during the formation of silver halide grains,
It may be added at any place in each step during physical ripening after the formation of silver halide grains. 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 more preferably 1 × 10 ^-9 mol or more and 1 × 10 ^-2 mol or less, and particularly 1 × 10 ⁹ mol or less, per mol of silver halide.
^It is preferably ^-8 mol or more and 5 × 10 ^-5 mol or less.

The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a (100) plane as a crystal surface.
Also, U.S. Pat.Nos. 4,183,756 and 4,225,666, JP-A-55
-26589, Japanese Patent Publication No. 55-42737, and The Journal of Photographic Science (J.Photogr.Sci.)
Particles having a shape such as an octahedron, a tetradecahedron, and a dodecahedron can be prepared by the method described in the literature such as 21, 39 (1973) and the like, and used. Further, grains having twin planes may be used.

The silver halide grains used in the present invention are
Although grains having a single shape may be used, 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 grains used in the present invention is not particularly limited, but in view of other photographic performance such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm.
m, more preferably 0.2 to 1.0 μm. The 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 used in 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 of 0.15 or less. It is to add two or more kinds of the monodisperse emulsion in the same layer. Here, the coefficient of variation is a coefficient representing the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = S ₁ / R ₁ (where S ₁ is the standard deviation of the grain size distribution and R ₁ is the average grain size.) The grain size as used herein means that of spherical silver halide grains. 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 used in the present invention is
It 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 for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt with 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, the pAg controlled double jet method described in JP-A-54-48521 can be used as one type of the simultaneous mixing method.

Further, 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 the reaction mother liquor described in JP-A-57-92523 and 57-92524, published in Germany An apparatus for continuously adding and changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Japanese Patent No. 2921164, and the reaction mother liquor is taken out of the reactor described in Japanese Patent Publication No. 56-501776. You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

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 and used during the formation of silver halide grains or after the completion of grain formation.

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

As the chalcogen sensitizer applied to the silver halide emulsion used in the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used.
Sulfur sensitizers are preferred. As the sulfur sensitizer, thiosulfate, allylthiocarbamidothiourea, allylisothiacyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine and inorganic sulfur. The addition amount of the sulfur sensitizer used in the present invention is preferably changed depending on the type of silver halide emulsion to be applied and the magnitude of expected effect, but it is 5 × per mol of silver halide.
The range is 10 ^{-10 to} 5 × 10 ^-5 mol, preferably 5 × 10 ^{-8 to} 3
The range of × 10 ^-5 mol is preferable.

As the gold sensitizer used in 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, thiocyanate, mercaptotetrazole,
Examples thereof include mercaptotriazole. The amount of gold compound used varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol of silver halide.
It is preferably molar. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

The chemical sensitization method of the silver halide emulsion used in the present invention may be a reduction sensitization method. The silver halide emulsion used in the present invention is for the purpose of preventing fogging that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuations during storage, and preventing fogging that occurs during development. Known antifoggants and stabilizers can be used. Examples of compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A No. 2-146036, page 7, lower column, and specific examples thereof include , (IIa-1) to (IIa-8), (IIb-1) to (IIa-1) described on page 8 of the publication.
The compound of (IIb-7) or 1- (3-methoxyphenyl) -5-
Mercaptotetrazole, 1- (4-ethoxyphenyl) -5-
Examples thereof include compounds such as mercaptotetrazole. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, 1 × 10 ^-6 mol to 1 × 10 ^-2 mol per mol of silver halide
An amount of about mol is preferable, and 1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol is more preferable. When it is added to the silver halide emulsion layer in the coating solution preparation step, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide, and 1 ×
More preferably, it is 10 ⁻⁵ mol to 1 × 10 ⁻² mol. When it is 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.

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

As the amount of these dyes added, the spectral reflection density at 680 nm of an untreated sample of a normal silver halide photographic light-sensitive material is high. In terms of color variability, it is favorable and preferable. The spectral reflection density at 680 nm of silver halide photographic light-sensitive materials currently on the market is usually 0.8 or more, but in the present invention, it is preferably low, and 0.70 or less is preferable. More preferably, it is 0.50 or less.

When the silver halide photographic light-sensitive material of the present invention is used as a color photographic light-sensitive material, it is combined with a yellow coupler, a magenta coupler and a cyan coupler.
It has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm. The above 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 used in the present invention, and as the blue-sensitive sensitizing dye, JP-A-3-251840 is known. BS-1 to 8 described on page 28 can be preferably used alone or in combination. As the green-sensitive sensitizing dye, GS described on page 28 of the same publication
-1 to 5 are preferably used. As the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. Further, when performing image exposure with infrared light such as using a semiconductor laser, it is necessary to use an infrared-sensitive sensitizing dye, as the infrared-sensitive sensitizing dye,
IRS-1 described in JP-A-4-285950, pages 6 to 8
The dyes of to 11 are preferably used. Further, the same publications 8 to 9
The supersensitizers SS-1 to SS-9 described on the page are preferably used in combination with these dyes. The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization. As a method of adding a sensitizing dye, methanol, ethanol, fluorinated alcohol, acetone, may be added as a solution by dissolving in water-miscible organic solvent such as dimethylformamide or water,
It may be added as a solid dispersion.

The coupler used in the silver halide photographic light-sensitive material of the present invention forms a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Although any compound to be obtained can be used, particularly typical ones include a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, and a wavelength. The one known as a cyan coupler having a spectral absorption maximum wavelength in the region of 600 to 750 nm is typical.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include general formulas (CI) and (C) described in JP-A-4-114152, page 17.
-II) can be mentioned. Specific compounds include those described as CC-1 to CC-9 on pages 18 to 21 of the same patent.

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention, the general formula (MI) described in JP-A-4-114152, page 12,
The coupler represented by (M-II) may be mentioned.
Specific compounds are described in MC-1 on pages 13 to 16 of the above patent.
~ MC-11 can be mentioned. Among them, MC-8 to MC-11 described on pages 15 to 16 of the above-mentioned patent are preferable because they are excellent in the reproduction of colors from blue to purple and red and are excellent in the depiction of details.

Examples of yellow couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include couplers represented by formula (YI) described on page 8 of JP-A-4-114152. it can. Specific compounds include those described as YC-1 to YC-9 on pages 9 to 11 of the same patent. Among them, YC-8 and YC-9 described on page 11 of the above patent
Is preferable because it can reproduce a preferable yellow color.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually necessary to use a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. According to the above, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. 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 the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high boiling point organic solvent that can be used for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and a water-insoluble and organic solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. At this time, the water-insoluble organic solvent-soluble polymer used is poly (Nt-
Butyl acrylamide) and the like.

The compound (d-1) described on page 33 of JP-A-4-114152 is used for the purpose of shifting the absorption wavelength of the color forming dye.
1), compounds such as the compound (A'-1) described on page 35 of the patent can be used. Other than this, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

The silver halide photographic light-sensitive material of the present invention comprises
It is advantageous to use gelatin as the binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, homopolymers or copolymers. A hydrophilic colloid such as a synthetic hydrophilic polymer substance can also be used.

Any material may be used as the support for the silver halide photographic light-sensitive material of the present invention. Paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, chloride A vinyl sheet, a polypropylene which may contain a white pigment, a polyethylene terephthalate support, a 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 is preferably 13% by weight or more, and further,
15% by weight is preferred.

The dispersity of the white pigment in the water resistant resin layer of the paper support used in 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, and even more preferably 0.10 or less as the coefficient of variation described in the above patent. It is more preferable that the center surface average roughness (SRa) of the paper support is 0.15 μm or less, and further 0.12 μm or less because not only glossiness but also sharpness can be obtained.

In the silver halide photographic light-sensitive material of 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 support surface, charging It may be applied via one or more undercoat layers for improving anti-preventive property, dimensional stability, abrasion resistance, hardness, antihalation property, frictional property and / or other property). .

When coating a silver halide photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

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 formed on the silver halide photographic light-sensitive material to be printed. The image may be printed on the CRT (cathode ray tube) after being converted into digital information, and then the image is formed on the silver halide photographic light-sensitive material to be printed. It may be printed, or may be printed by changing the intensity of the laser light based on digital information and scanning.

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- (β-butoxyethyl) aniline In the present invention, the above is color development. Although be used in any pH range is preferably pH9.5~13.0 in view of rapid processing, preferably used in the range of PH9.8～12.0.

The processing temperature of the color developing solution used in the present invention is preferably 35 ° C. or higher and 70 ° C. or lower. The higher the temperature, the shorter the treatment time is, which is preferable, but it is preferable that the temperature is not so high in view of the stability of the treatment liquid, and the treatment is preferably performed at 37 ° C or higher and 60 ° C or lower.

The color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably 40 seconds or less.
It is even more preferable to perform the treatment within a range of 25 seconds.

To the color developing solution, a known developer component compound can be added in addition to the above color developing agent. Usually, an alkaline agent having a pH buffering action, a development inhibitor such as chloride ion and benzotriazole, a preservative,
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,
Usually, a washing process is performed. Further, 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 above-mentioned light-sensitive material sandwiched between rollers arranged in a processing tank, It may be an endless belt method in which the photosensitive material is fixed and conveyed, but a processing tank is formed in a slit shape, a processing solution is supplied to the processing tank and the photosensitive material is conveyed, and the processing solution is sprayed. It is also possible to use a spray method for forming a shape, a web method by contact with a carrier impregnated with a treatment liquid, a method with a viscous treatment liquid, and the like.

[0073]

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

Example 1 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 where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support.

Each layer having the following constitution was coated on this reflection support to prepare a multilayer color photographic light-sensitive material. The coating liquid was prepared as follows.

First layer coating solution 23.4 g of yellow coupler (Y-1), 3.34 g of dye image stabilizer (ST-1), dye image stabilizer (ST-2) 3.
34 g, stain inhibitor (HQ-1) 0.33 g, compound A and high boiling point organic solvent (DBP) 5.0 g were dissolved by adding 60 ml of ethyl acetate, and this solution was dissolved in 20% surfactant (SU-1) 7
A yellow coupler dispersion was prepared by emulsifying and dispersing 220 ml of a 10% gelatin aqueous solution containing 10 ml using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a coating solution for the first layer.

The coating liquids for the second to seventh layers were 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, as a hardener (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 .

[0079]

[Table 1]

[0080]

[Table 2]

SU-1: sodium tri-i-propylnaphthalene sulfonate SU-2: sulfosuccinic acid di (2-ethylhexyl) ester sodium salt SU-3: sulfosuccinic acid di (2,2,3,3, 4,4,5,5-Octafluoropentyl) ester / sodium salt DBP: Dibutylphthalate DOP: Dioctylphthalate DIDP: Di-i-decylphthalate PVP: Polyvinylpyrrolidone H-1: Tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-triazine
Sodium Compound A: pt-octylphenol

[0082]

[Chemical 1]

[0083]

[Chemical 2]

[0084]

[Chemical 3]

[0085]

[Chemical 4]

[0086]

[Chemical 5]

[0087]

[Chemical 6]

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

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water added 200 ml (Solution B) Silver nitrate 10 g Water added 200 ml (Solution C) K ₂ IrCl ₆ 2 × 10 ^-8 mol / mol Ag Chloride Sodium 102.7g K ₄ Fe (CN) ₆ 1 × 10 ^-5 mol / mol Ag Potassium bromide 1.0g Water added 600ml (D liquid) Silver nitrate 300g Water added 600ml After addition, Kao Atlas Demol N 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate were used for desalting, and then mixed with an aqueous solution of gelatin to obtain a single particle having an average particle size of 0.85 μm, a particle size distribution variation coefficient of 0.07, and a silver chloride content of 99.5 mol%. A dispersed cubic emulsion EMP-1 was obtained.

The following compounds were used for EMP-1.
Optimal chemical sensitization was performed at 60 ° C. to obtain a blue-sensitive silver halide emulsion for comparison (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-3 8 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX (preparation of green-sensitive silver halide emulsion) (solution A) and solution B
A monodisperse cubic emulsion E having an average grain size of 0.43 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (C liquid) are changed.
MP-2 was obtained.

The following compounds were used for EMP-2.
Optimal chemical sensitization was carried out at 55 ° C. 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 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 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)
A monodisperse cubic emulsion E having an average grain size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1 except that the addition time of (C solution) and the addition time of (C solution) are changed.
MP-3 was obtained.

The following compounds were used for EMP-3.
Optimal chemical sensitization was carried out at 60 ° C. 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 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 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

[0096]

[Chemical 7]

The sample thus prepared was designated as Sample 101.

In Sample 101, each silver halide photographic light-sensitive material having a white pigment layer shown in Tables 3 and 4 between the support and the blue light-sensitive layer was prepared.

As the preparation method for applying the white pigment layer, for example, in the case of Sample 103, the high boiling point organic compound O-1 is used.
To a solution of 16 L of 8 and 32 L of ethyl acetate, gelatin 1
An aqueous solution in which 0.6 kg and 1.2 kg of the surfactant dodecylbenzene sulfonic acid were dissolved was added and emulsified and dispersed by a homogenizer. This solution was added to an aqueous solution of titanium oxide (average particle size 0.35 μm) and gelatin prepared so as to have the following coating amount to prepare a coating solution.

[0100] In the mass production of titanium oxide 2.00 g / m ² Gelatin ^{1.43g / m 2 O-18 0.57g} / m 2 each sample was used for the coating solution is stagnant at 35 ° C.. At this time, the sample prepared immediately after preparation was compared with the sample prepared after 10 hours of stagnation.

A resolution test chart was printed on each sample with red light, and the following development processing steps were performed, and the obtained images were subjected to density measurement with a microdensitometer PDM-5D (manufactured by Konica Corporation). Then, the sharpness value shown below was calculated.

Sharpness (%) = (Dmax-Dmin of 3 lines / mm dense line printed image) / (Dmax-Dmin in large area) where Dmax: maximum density Dmin: minimum density , Showing that the sharpness is excellent.

Processing process Temperature Time Replenishment amount Color development 38 ± 0.3 ℃ 22 seconds 81ml Bleaching fixing 35 ± 0.5 ℃ 22 seconds 54ml Stabilization 30-34 ℃ 60 seconds 150ml Dry 60-80 ℃ 40 seconds Composition of developing solution is as follows. Shown in.

Color developing solution and replenishing solution Tank solution Replenishing solution 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 6.0g 10.5g N, N-diethylhydroxylamine 3.5g 6.0g N, N-bis (2-sulfoethyl) hydroxylamine 3.5g 6.0g triethanolamine 10.0g 10.0g diethylenetriamine Sodium pentaacetate 2.0g 2.0g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to make the total volume 1 liter.
Adjust to 10 and replenisher to pH = 10.60.

Bleach-fixing solution tank solution and replenishing solution tank solution replenishing solution diethylenetriamine pentaacetate ammonium ferric dihydrate 100 g 65 g diethylenetriamine pentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml 2-amino-5-mercapto-1 2,3,4-thiadiazole 2.0g 1g Ammonium sulfite (40% aqueous solution) 50m
25 ml of water was added to make the total volume 1 liter, and the pH of the tank solution was adjusted to 7.0 and the replenisher was adjusted to pH = 6.5 with potassium carbonate or glacial acetic acid.

Stabilizer tank and replenisher Orthophenylphenol 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 Fluorescence enhancement Whitening agent (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g PVP (polyvinylpyrrolidone) 1.0 g Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g Ethylenediaminetetraacetic acid 1.0 g Ammonium sulfite (40% Aqueous solution) Add 10 ml water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia. The results are shown in Tables 3 and 4.

[0107]

[Table 3]

[0108]

[Table 4]

Comparative compounds: C ₂ H ₅ OH (boiling point 78 ° C.), O-1
(Boiling point 390 ° C), O-11 (boiling point 287 ° C), O-18 (boiling point 34 ° C)
5 ° C. or higher) As shown in Tables 3 and 4, the samples of the present invention are superior to the comparative samples in sharpness immediately after coating, and the variability in sharpness after stagnating the coating liquid for mass production is high. It turns out that was very small.

Example 2 Polyethylene was laminated on one side of a paper support, and polyethylene containing titanium oxide was laminated on the first layer side of the other side. A 110 μm-thick support was coated with each layer of the following constitution. Then
A multilayer color photographic light-sensitive material was prepared.

(Preparation of Emulsion EM-1) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5). ) Is added at the same time by the control double jet method to obtain a particle size of 0.30
A μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so as to obtain a cubic particle shape. An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 40: 60) were simultaneously added to the obtained core emulsion by the control double jet method to obtain average grains. Diameter 0.42 μm
The shell was formed until At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-1. The breadth of distribution of this emulsion EM-1 was 8%.

(Preparation of Emulsion EM-2) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate and potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5). ) Is added at the same time by the control double jet method to obtain a particle size of 0.18
A μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so as to obtain a cubic particle shape. An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 40: 60) were simultaneously added to the obtained core emulsion by the control double jet method to obtain an average grain size. The shell was formed to a diameter of 0.25 μm. At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-2. The breadth of distribution of this emulsion EM-2 was 8%.

(Preparation of Blue Sensitive Emulsion EM-B) EM-1
After sensitizing the dye by adding the sensitizing dye D-1, to 600 mg of T-1 was added per mol of silver to prepare a blue-sensitive emulsion EM-B.

(Preparation of Green Sensitive Emulsion EM-G) A green sensitive emulsion EM-G was prepared in the same manner as the blue sensitive emulsion except that the sensitizing dye D-2 was added to EM-2 for color sensitization.

(Preparation of Red-Sensitive Emulsion EM-R) A red-sensitive emulsion EM-R was prepared in the same manner as the blue-sensitive emulsion except that sensitizing dyes D-3 and D-4 were added to EM-2 for color sensitization. It was made.

(Preparation of pan-sensitive emulsion EM-P) Same as the blue-sensitive emulsion except that sensitizing dyes D-1, D-2, D-3 and D-4 were added to EM-1 for color sensitization. Pan-sensitive emulsion EM-
P was prepared.

T-1: 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene

[0120]

[Chemical 8]

EM-B, EM-G, EM-R, EM
Sample of color photographic light-sensitive material having the following constitution using -P
201 was produced. The first to ninth layers were coated on the front surface of the support in the following constitution, and the tenth layer was coated on the back surface side. still,
Sample 1 was prepared using SU-2 and SU-3 as coating aids and H-1 and H-2 as hardeners.

Layer composition Coating amount (g / m ² ) Ninth layer Gelatin 0.78 (UV absorbing layer) UV absorber (UV-1) 0.065 UV absorber (UV-2) 0.120 UV absorber (UV-3) ) 0.160 Solvent (SO-2) 0.1 Silica matting agent 0.03 Eighth layer Gelatin 1.43 (blue sensitive layer) Blue sensitive emulsion EM-B (coated silver amount) 0.4 Normal sensitive emulsion EM-P (coated silver amount) 0.1 Yellow coupler ( YC-1) 0.82 Anti-stain agent (AS-2) 0.025 Solvent (SO-1) 0.82 Inhibitor (ST-6, ST-7, T-1) 7th layer Gelatin 0.54 (Intermediate layer) Anti-color mixture (HQ) -1, 2, 3, 4, 5 equivalents) 0.055 Solvent (SO-2) 0.072 6th layer Gelatin 0.42 (Yellow colloidal silver layer) Yellow colloidal silver 0.1 Anti-color mixing agent (HQ-1, 2, 3, 4, 5 equivalents) 0.04 Solvent (SO-2) 0.049 Polyvinylpyrrolidone (PVP) 0.04 7 Anti-irradiation dye (AI-6) 0.03 5th layer Gelatin 0.54 (Intermediate layer) Color mixture inhibitor (HQ-1, 2, 3, 4, 5 equivalents) 0.055 Solvent (SO-2) 0.072 4th Layer Gelatin 1.43 (green sensitive layer) Green sensitive emulsion EM-G (coated silver amount) 0.40 Normal sensitive emulsion EM-P (coated silver amount) 0.10 Magenta coupler (MC-1) 0.25 Yellow coupler (YC-2) 0.06 Stain prevention Agent (AS-2) 0.019 Solvent (SO-1) 0.31 Inhibitor (ST-6, ST-7, T-1) Third layer Gelatin 0.75 (Intermediate layer) Color mixture inhibitor (HQ-1, 2, 3, 4, 5 equivalents) 0.055 Solvent (SO-2) 0.072 Anti-irradiation dye (AI-4) 0.01 Anti-irradiation dye (AI-5) 0.01 Second layer Gelatin 1.38 (Red-sensitive layer) Red-sensitive emulsion EM-R (Amount of coated silver) 0.30 Normal sensitive emulsion EM-P (Amount of coated silver) 0.06 Uncoupler (CC-2) 0.44 Solvent (SO-1) 0.31 Anti-staining agent (AS-2) 0.015 Inhibitor (ST-6, ST-7, T-1) First layer Gelatin 1.0 (White pigment layer) Anatase Type titanium dioxide 3.0 10th layer gelatin
6.00 (back surface layer) Silica matting agent 0.65 The amount of silver coated is in terms of silver SO-1: trioctyl phosphate SO-2: dioctyl phthalate AS-2: 2,4-di-t-butylhydroquinone ST-6 : 1- (3-acetamidophenyl) -5-mercaptotetrazole ST-7: N-benzyladenine

[0123]

[Chemical 9]

[0124]

[Chemical 10]

In the sample 201 obtained as described above, the same samples were prepared except that the first white pigment layer was changed as shown in Table 5. On each of these samples, a resolution test chart was printed with red light, and green light and blue light were exposed over the entire surface so that the minimum density was minimized. After the following development process, the density of the obtained image was measured with a Microdensitometer PDM-5D (manufactured by Konica Corp.), and the sharpness value was calculated in the same manner as in Example 1. The results are shown in Table 5.

[0126]

[Table 5]

As is clear from Table 5, the sample of the present invention was superior to the comparative sample in sharpness immediately after coating, and the variability in sharpness was very small after the coating solution stagnated. Recognize.

The exposed sample was processed under the following processing conditions to obtain an image.

The conditions of the developing treatment and the prescription of the treatment liquid are as follows.

Processing Step-1 Temperature Time Immersion (Developer) 37 ° C 12 seconds Fog exposure-12 seconds (1 lux) Development 37 ° C 95 seconds Bleach-fixing 35 ° C 45 seconds Stabilization 25-30 ° C 90 seconds Dry 60- 85 ° C 40 seconds Processing solution composition (color developer) Benzyl alcohol 15.0ml Cerium sulfate 0.015g Ethylene glycol 8.0ml Potassium sulfite 2.5g Potassium bromide 0.6g Sodium chloride 0.2g Potassium carbonate 25.0g T-1 0.1g Hydroxylamine Sulfate 5.0 g Sodium diethylenetriaminepentaacetate 2.0 g 4-Amino-N-ethyl-N- (β-hydroxyethyl) 4.5 g Aniline sulfate Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0 g Water Potassium oxide 2.0 g Diethylene glycol 15.0 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.15.

(Bleach-fixing solution) diethylenetriaminepentaacetic acid ferric ammonium 90.0 g diethylenetriaminepentaacetic acid 3.0 g ammonium thiosulfate (70% aqueous solution) 180 ml ammonium sulfite (40% aqueous solution) 27.5 ml 3-mercapto-1,2,4-triazole Adjust the pH to 7.1 with 0.15 g potassium carbonate or glacial acetic acid and add water to bring the total volume to 1 liter.

(Stabilizing solution) o-Phenylphenol 0.3 g Potassium sulfite (50% aqueous solution) 12 ml Ethylene glycol 10 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.5 g Bismuth chloride 0.2 g Zinc sulfate heptahydrate 0.7 g Water Ammonium oxide (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Fluorescent brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0 g Add water to bring the total volume to 1 liter and add ammonium hydroxide or Adjust the pH to 7.5 with sulfuric acid. The stabilization process is 2
A counter-current system with a tank configuration was adopted.

The prescription of the replenisher for running is shown below.

(Color development replenisher) Benzyl alcohol 18.5 ml Cerium sulfate 0.015 g Ethylene glycol 10.0 ml Potassium sulfite 2.5 g Potassium bromide 0.3 g Sodium chloride 0.2 g Potassium carbonate 25.0 g T-1 0.1 g Hydroxylamine sulfate 5.0 g Sodium diethylenetriaminepentaacetate 2.0 g 4-Amino-N-ethyl-N- (β-hydroxyethyl) 5.4 g Aniline sulfate Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 18.0 ml Add water to make the total volume 1 liter and adjust to pH 10.35.

(Bleach-fixing solution replenishing solution) Same as the above-mentioned bleach-fixing solution (Stabilizing solution replenishing solution) Same as the above-mentioned stabilizing solution. The replenishing amount is the same for the developing solution replenishing solution, the bleach-fixing solution and the stabilizing solution. The amount was 320 ml per 1 m ² .

When the original document with halftone dots is closely contacted and exposed, the sample of the present invention can obtain a sharp image which is advantageous in reproducibility of small dots and has a stable color reproducibility. Was given.

[0137]

INDUSTRIAL APPLICABILITY The silver halide photographic light-sensitive material according to the present invention is excellent in sharpness and can produce an image with little fluctuation in sharpness during mass production.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having a support and at least one silver halide emulsion layer, wherein a hydrophilic colloid layer containing at least one white pigment between the support and the silver halide emulsion layer. And the variation coefficient S / of the occupied area ratio (%) per unit area of the white pigment
R (S is the standard deviation of the occupied area ratio per unit area, R is the average area ratio per unit area) is 0.25 or less, and the boiling point of the hydrophilic colloid layer containing the white pigment is 15
A silver halide photographic light-sensitive material characterized by containing an organic compound having a high boiling point of 0 ° C. or higher. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the hydrophilic colloid layer containing the white pigment contains gelatin and a high-boiling organic solvent having a boiling point of 300 ° C. or higher. 3. The total weight of the high-boiling organic solvent is 10% to the weight of gelatin in the hydrophilic colloid layer containing the white pigment.
3. The silver halide photographic light-sensitive material according to claim 1, which is 100%.