JP2000321697A - Silver halide emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material which is small in performance fluctuation at high illuminance and low illuminance and is good in latent image stability, heat resistant stability and dependence on moisture at the time of exposure. SOLUTION: This silver halide agent is a silver halide agent having an average silver chloride content of >=95%. The agent is a mixture composed of the silver halide agents having plural sensitivities. The silver halide agent described above is characterized as follows: A straight line passing the point at which a density 0.5 is given on a characteristic curve obtained by subjecting the silver halide photographic sensitive material having a photosensitive layer containing the silver halide agent (S) having the maximum sensitivity and a nonphotosensitive layer to exposure for <=10-6 seconds, then forming an image thereon by color development and a point at which a density 1.5 is given is drawn. The average gradient (γS) thereof is smaller than the average gradient (γM) obtained from the silver halide photographic sensitive material of the case the silver halide agent (M) having the minimum sensitivity is used. Both average gradients have the following relation: I<γM/γS<1.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion, and more particularly to a silver halide emulsion which can be optimally used for color photographic paper.

[0002]

2. Description of the Related Art In recent years, there has been a remarkable development of technology for rapid processing and processing stability of color photographic paper, but on the other hand, with the development of computer technology, images captured by a scanner have been processed on a computer to achieve desired results. Images can be easily obtained. Along with this, a method of exposing a silver halide photographic material with a digital scanning exposure apparatus using a semiconductor laser, a light emitting diode or the like as a light source in a short time and with high illuminance is becoming popular.

[0003] Therefore, it is necessary to provide color photographic paper with exposure performance that can correspond to the above-described exposure method.

It is generally known that doping an iridium compound is effective in improving reciprocity failure of a silver halide emulsion. For example, Japanese Patent Publication No. 43-4935 discloses that the addition of an iridium compound during the preparation of silver halide grains has the effect of reducing fluctuations in gradation over a wide exposure time range. JP-A-3-18837 discloses that the incorporation of an iridium compound and an iron compound on the surface of silver halide grains improves reciprocity failure and latent image stability.

However, in these techniques, it is difficult to obtain the desired performance only by the above-described metal complex doping technique alone under short-time and high-illumination exposure conditions such as scanning exposure using a new light source in recent years. It is becoming.

As described above, high-intensity scanning exposure is becoming the mainstream of exposure on color photographic paper. However, the stability and high cost of light sources hinder the spread of printers equipped with these light sources, and non-scanning exposure Image formation by the method still exists. Therefore, in order for color photographic paper to meet the needs of the market, it is necessary to be able to handle both digital and analog, that is, to obtain stable photographic performance regardless of the length of exposure time, that is, to have excellent reciprocity failure characteristics. Becomes However, as a result of investigations by the present inventors, it has been found that by further improving the reciprocity failure characteristic, performance at the time of exposure, stability of a latent image, and the like are deteriorated.

[0007] Emulsions having different sensitivities are used in a mixture in order to extend the exposure latitude or to control the gradation of the silver halide emulsion. Generally, the color photographic paper having a high silver chloride halogen composition is mainly used for the latter than for the former. JP-A-7-301875 discloses that in order to provide a wide exposure latitude, in an emulsion containing a mixture of at least two kinds of silver halide emulsions having different grain sizes, the grain size ratio and the gold sensitizer amount ratio are changed. The defining technology is disclosed. JP-A-10-307364 discloses that
In order to increase the efficiency of preparing silver halide emulsions and reduce costs, in emulsions containing a mixture of at least two types of photographic emulsions, at least two types of emulsion grains are the same, and at least one of them is a compound that reduces sensitivity. Processing techniques are shown. Japanese Patent Application Laid-Open No. 4-157449 discloses a technique in which a silver halide having a smaller grain size contains a stabilizer having a larger pKsp when silver halide grains having different grain sizes are mixed and used. ing. As described above, the purpose of these technologies is latitude and gradation control, and the effect is not suggested for the performance stability at the time of high illuminance exposure. Japanese Patent Laid-Open No. 3-2 discloses a technique for mixing and using an emulsion containing a metal complex.
No. 41342 discloses a technique of mixing and using emulsions having different Ir complex contents for the purpose of improving reciprocity high illuminance failure. A similar technique is disclosed in Japanese Patent Laid-Open No.
No. 1730 also discloses a technique in which an Ir compound and another metal compound are contained in silver halide grains, and an emulsion is mixed and used.

[0008]

Although the effect can be confirmed with respect to the performance stability at the time of high illuminance exposure by these techniques, the performance stability is remarkably reduced due to the time change from exposure to development. It became clear by the examination of those.

The present invention has been made in view of the above circumstances, and has as its object to excel in reciprocity failure from ultra-high illuminance to low illuminance, such as scanning exposure, in addition to the latent image stability and the humidity dependence during exposure. An object of the present invention is to provide a silver halide emulsion having excellent heat resistance and heat fogging resistance.

[0010]

The above object of the present invention has been attained by the following constitutions.

1. In a silver halide emulsion having an average silver chloride content of 95% or more, the emulsion is a mixture of silver halide emulsions having a plurality of sensitivities and containing a silver halide emulsion (S) having a maximum sensitivity. Layer, and a silver halide photographic material having a non-photosensitive layer,
After exposure for 10 ^-6 seconds or less, a line passing through a point giving a density of 0.5 and a point giving a density of 1.5 on a characteristic curve obtained by color development and image formation is drawn, and the average gradient (γS )But,
When a silver halide emulsion (M) having the minimum sensitivity is used, the average gradient (γ) obtained from a silver halide photographic material is
M) a silver halide emulsion characterized in that the average gradients of the two have the following relationship:

1 <γM / γS <1.5 In a silver halide emulsion having an average silver chloride content of 95% or more, the emulsion is a mixture of silver halide emulsions having a plurality of sensitivities, and is used for preparing a silver halide emulsion (S) having a maximum sensitivity. pAg (M) for preparing silver halide emulsion (M) having a minimum sensitivity of pAg (S)
A silver halide emulsion characterized by having the following relationship:

0 <pAg (S) -pAg (M) <1.5 3. In a silver halide emulsion having an average silver chloride content of 95% or more, the emulsion is a mixture of silver halide emulsions having a plurality of sensitivities, and the silver halide emulsion (M) having a minimum sensitivity is dye or polarographic. A silver halide emulsion prepared by adding a desensitizing dye having a positive sum of an anodic potential and a polarographic cathode potential to 10 mg or less per 1 mol of silver halide.

Hereinafter, the present invention will be described in detail.

(1) Silver halide emulsion according to claim 1 The characteristic curve according to claim 1 of the present invention refers to an image obtained by color development after high illuminance exposure of 10 ^-6 seconds or less.
This is a curve in which log E (E is the exposure amount) is plotted on the horizontal axis and D (density) is plotted on the vertical axis. The average gradient at that time means a gradient obtained by drawing a straight line passing through a point giving a density of 0.5 and a point giving a density of 1.5 on a characteristic curve obtained by color development after exposure.

In order to obtain the effects of the present invention, the silver halide emulsion (S) having the maximum sensitivity (also simply referred to as the maximum sensitivity emulsion (S)) and the silver halide emulsion (M) having the minimum sensitivity (simply having the minimum sensitivity) When the above average gradient of the emulsion (M) is γS and γM, respectively, 1 <γM / γS <
It needs to be 1.5.

The light source for exposing the silver halide photographic light-sensitive material obtained by using the emulsion of the present invention (also simply referred to as a light-sensitive material) to high illuminance includes Xe flashlight,
Examples include a light-emitting diode, a gas laser, a solid-state laser, a semiconductor laser, a He-Ne laser, an Ar laser, and a dye laser. Further, it can be used in any of the vertical single mode and the horizontal multi mode, and a light source modulated by electric modulation by high frequency superposition and SHG (second harmonic element) may be used. Particularly, in order to design an apparatus which is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

The exposure time in such scanning exposure is as follows:
When the pixel size when the pixel density is 400 dpi is defined as the exposure time, it is preferably 10 ^-6 seconds or less.

(2) Silver halide emulsion according to claim 2 In preparing the silver halide emulsion according to claim 2 of the present invention, in order to obtain the effects of the present invention, pAg during chemical ripening is required.
It is necessary to prepare an emulsion while keeping the maximum sensitivity emulsion high relative to the minimum sensitivity emulsion. Specifically, pA
g (maximum sensitivity emulsion) -pAg (minimum sensitivity emulsion) is required to be larger than 0 and smaller than 1.5, but is preferably 0.5 to 1.

(3) Silver halide emulsion according to claim 3 The desensitizing dye according to claim 3 of the present invention is a compound in which the sum of the polarographic anode potential and cathode potential is positive.
Many such compounds are described in patents or literature and any desensitizing dye can be used. For example, Japanese Patent Publication Nos. 36-17595, 39-20261 and 4
Nos. 0-26751, 43-13167, and 45-8
No. 833, No. 47-8746, No. 47-0197,
Nos. 50-37530, JP-A-48-24734, 49-84639, 56-142525, and 61
-26041 and 63-306436, and U.S. Pat. Nos. 2,271,458 and 2,541,47.
No. 2, 3,035,917 and 3,062,6
No. 51, No. 3,124,458 and No. 3,326
687, 3,671,254 and the like.

As the dye according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of known compounds can be used. Particularly, as dyes having absorption in the visible region, JP-A-3-251840 3
Dyes of AI-1 to 11 described on page 08 and JP-A-6-3
No. 770 is preferably used. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication.

The dyes and desensitizing dyes according to the present invention need to be added in an amount of 10 mg or less, preferably 5 mg or less per mol of silver halide.

The dye and the desensitizing dye according to the present invention are preferably added during chemical ripening, and more preferably at the end of chemical ripening. or,
It is not preferable to add the same dye or the same dye to a coating solution prepared when coating on a support after preparing the emulsion, because it becomes impossible to achieve both high illuminance exposure suitability and other properties.

As described above, the constitutions of claims 1 to 3 of the present invention provide a silver halide emulsion which is excellent in reciprocity failure, and is also excellent in latent image stability, exposure humidity dependency and heat fog resistance. be able to.

(4) Common to claims 1 to 3 The composition of the silver halide emulsion used in the present invention is characterized in that the silver chloride content is 95 mol% or more. Any of silver bromide, silver iodochloride, silver chlorobromide and silver chloride, and silver chlorobromide emulsion having a localized phase having a silver bromide content of 30 mol% or more should be used. Can be.

The portion containing silver bromide at a high concentration may form a layer as a so-called core-shell emulsion,
A region having a partially different composition may be present without forming a complete layer due to epitaxy bonding to the silver halide emulsion grains. The portion where silver bromide is present in high concentration may be made in the stage of forming silver halide grains,
It may be made in a subsequent chemical ripening stage or a coating solution preparation stage. Also, when the composition of the inside of the particle and the surface are different
The composition may change continuously or discontinuously.

Although it depends on the composition of the whole silver halide emulsion grains, when the content of silver bromide relative to the total silver halide is about 1 mol%, the silver bromide containing silver bromide in a high concentration is used. The content is preferably 40 mol% or more. In order to form such a localized phase of silver bromide, a so-called conversion method may be used in which an aqueous solution of a water-soluble bromide salt such as potassium bromide is added, or a double-mixing method or a bromide prepared in advance. A method of adding silver fine particles and utilizing a recrystallization process may be used. Examples of such silver halide grains are described in JP-A-58-95736 and JP-A-58-1085.
No. 33 and particles described in JP-A-1-183647.

The silver bromide content of the portion containing silver bromide at a high concentration can be determined by the method described in the upper right column of page 22 of JP-A-1-183647. When the thus obtained silver bromide content has a range, the silver bromide content of the portion containing silver bromide at a high concentration in the present invention means the maximum value.

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

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

When the heavy metal ion forms a complex, the ligand may be a cyanide ion, thiocyanate ion, isothiocyanate ion, cyanate ion, or the like.
Examples include chloride ion, bromide ion, iodide ion, carbonyl, ammonia and the like. 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, during, and after the formation of 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 conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 ^-9 per mol of silver halide.
１1 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁸ -5
× 10 ^-5 mol is preferred.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface.
U.S. Pat. Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-B-55-42
No. 737 and The Journal of Photographic Science (J. Photogr. Sci.) 2
1, 39 (1973), and the like, particles having an octahedral, tetradecahedral, dodecahedral, etc. shape can be produced and used. 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 is preferably 0.1 to 1.2 μm in consideration of other photographic properties such as rapid processing property and sensitivity.
m, more preferably in the range of 0.2 to 1.0 μm.

The grain size distribution of the silver halide grains of the present invention is preferably a monodispersed silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably 0. .15 or less is added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / RS S represents the standard deviation of the particle size distribution, and R represents the average particle size.

The particle size as used herein refers to the diameter of spherical silver halide grains, or the diameter of a projected image converted to a circular image of the same area for cubic or non-spherical grains. Represents the diameter of Various methods known in the art can be used as the apparatus and method for preparing a silver halide emulsion.

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

The form of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. 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 JP-A-57-92523.
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 described in, for example, German Offenlegungsschrift 2,921,164. And a device for continuously adding an aqueous solution of a water-soluble halide salt while changing its concentration, Japanese Patent Publication No. 56-5
No. 01776 or the like, a reaction mother liquor may be taken out of the reactor and concentrated by an ultrafiltration method to form a grain while keeping the distance between silver halide grains constant.

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 chemical sensitizer according to the present invention can be used in combination with a sensitization method using a gold compound and a sensitization 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, but a 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.

As the gold sensitizer according to the present invention, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole.

The silver halide emulsion according to the present invention is intended to prevent fogging during the preparation process of the silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fogging during development. And known antifoggants and stabilizers can be used. Examples of preferred compounds that can be used for such purposes include JP-A-2-146.
No. 036, page 7, lower column, compounds represented by general formula (II) can be mentioned, and more preferred specific compounds are (IIa-1) to (IIa-1) to (II) described on page 8 of the same publication. II
a-8), the compounds of (IIb-1) to (IIb-7), and 1
Compounds such as-(3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned. These compounds are added in a step of preparing silver halide emulsion grains, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution or the like according to the purpose. When chemical sensitization is performed 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, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol. . In the step of preparing a coating solution, when adding to the silver halide emulsion layer, 1 × 10 ⁻⁶ per mole of silver halide is used.
The amount is preferably about 1 × 10 ^-1 mol, and 1 × 10 ^-5 to ¹ mol.
× 10 ^-2 mol is more preferred. 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 to 1 × 10 ^-3 mol per 1 m ² .

(5) Silver halide photographic light-sensitive material The light-sensitive material obtained by using the emulsion of claims 1 to 3 of the present invention will be described.

In the silver halide photographic light-sensitive material, as a dye to be added for the purpose of preventing irradiation or halation, a compound to be added when preparing the silver halide emulsion according to the present invention can be used as it is. For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of an unprocessed sample of the light-sensitive material is 0.7 or more, more preferably 0.8 or more. preferable.

It is preferable to add a fluorescent whitening agent to the light-sensitive material because whiteness can be improved. The compound preferably used is a compound represented by the general formula described in JP-A-2-232652.
Compounds represented by II are mentioned.

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

As the spectral sensitizing dye used in the silver halide emulsion of the present invention, any known compounds can be used, and as the blue-sensitive sensitizing dye, JP-A-3-251.
No. 840, page 28, BS-1 to 8 can be preferably used alone or in combination. As green-sensitive sensitizing dyes, GS-1 to GS-5 described on page 28 of the same publication are preferably used. As the red-sensitive sensitizing dye, RS-1 to 8 described on page 29 of the same publication are preferably used. In the case of performing image exposure from infrared light using a semiconductor laser or the like, an infrared-sensitive sensitizing dye must be used. No. 6
The dyes of IRS-1 to 11 described on page 8 are preferably used. Also, these infrared, red, green and blue-sensitive sensitizing dyes include supersensitizers SS-1 to SS-9 described on pages 8 to 9 of JP-A-4-285950 and JP-A-5-66515. ~ 1
It is preferable to use compounds S-1 to S-17 described on page 7 in combination.

The amount of the sensitizing dye to be added depends on the type of the sensitizing dye, the halogen composition of the silver halide emulsion to be applied, the particle size, etc., but is preferably 5 per mol of silver halide.
× 10 ⁻⁵ to 4 × 10 ⁻³ mol, more preferably 1 × 10 ⁻⁴
It is used in the range of 1 to 10 ³ mol.

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 as a solution by dissolving in water or a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone or dimethylformamide, or as a solid dispersion. Although it may be added, it is preferable to add it as a solid dispersion because the effect of the present invention is enhanced.

As a method for dispersing the sensitizing dye, other than a method of mechanically pulverizing and dispersing fine particles of 1 μm or less in an aqueous system by using a high-speed stirring type disperser, see JP-A-58-105141.
As described in JP-B-60-6496, a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system under conditions of pH 6 to 8 and 60 to 80 ° C., and a surface tension of 38 dyne / cm described in JP-B-60-6496. For example, a method of dispersing in the presence of a surfactant suppressed below can be used.

Examples of the dispersing device that can be used for preparing the dispersion include a high-speed stirring type dispersing device shown in FIG. 1 of JP-A-4-125563, a ball mill, a sand mill, an ultrasonic dispersing device, and the like. Can be mentioned. or,
In using these dispersing apparatuses, Japanese Patent Laid-Open No.
As described in No. 5632, a method in which pre-treatment such as dry pulverization is performed in advance and then wet dispersion may be performed.

When a plurality of sensitizing dyes are used in combination, the two sensitizing dyes may be added separately or may be added after mixing in advance.

As the coupler used for the light-sensitive material,
340n after coupling reaction with oxidized form of color developing agent
Any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than m can be used, but a typical example is a wavelength range of 350 to 5
Yellow dye-forming coupler having a spectral absorption maximum wavelength at 00 nm, magenta dye-forming coupler having a spectral absorption maximum wavelength at 500 to 600 nm, wavelength range 600 to 600 nm
Typical are those known as cyan dye-forming couplers having a spectral absorption maximum wavelength at 750 nm.

Examples of the cyan coupler which can be preferably used in the light-sensitive material include couplers represented by formulas (C-I) and (C-II) described in JP-A-4-114154, page 5, lower left column. Can be.

As magenta couplers which can be preferably used for photosensitive materials, JP-A-4-1141544
Couplers represented by general formulas (MI) and (M-II) described in the upper right column of the page can be mentioned. More preferred among the above magenta couplers are couplers represented by the general formula (MI) described in the upper right column on page 4 of the publication, among which the RM of the above general formula (MI) is tertiary. Couplers that are alkyl groups are particularly preferred because of their excellent light resistance.

As a yellow coupler which can be preferably used for a light-sensitive material, JP-A-4-114154-3
The coupler represented by the general formula (Y-I) described in the upper right column of the page can be used. Specific compounds include those described as YC-1 to YC-9 in the lower left column on page 3 of the publication. In particular, the general formula [Y
The coupler of the formula (I-1) wherein RY1 is an alkoxy group or the coupler represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone, and is therefore preferable. Further, compounds represented by the general formula [Y-1] described in JP-A-4-81847, page 1 and JP-A-4-81847, can also be used.

When an oil-in-water emulsion dispersion method is used to add a coupler or other organic compound used in a light-sensitive material, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher, if necessary. To dissolve in combination with a low boiling point and / or water-soluble organic solvent, and emulsify and disperse 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 simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be added. As a high boiling organic solvent that can be used to dissolve and disperse the coupler, dioctyl phthalate, diisodecyl phthalate,
Phthalates such as dibutyl phthalate and phosphates such as tricresyl phosphate and trioctyl phthalate are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0.
Two or more high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

As a compound preferable as a surfactant used for dispersing a photographic additive or 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 in one molecule are preferable. Containing. Specifically, A-1 to A-11 described in JP-A-64-26854
Is mentioned. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution after the addition are preferably 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

It is preferable to use an anti-fading agent 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 are those represented by general formulas I and II described in JP-A-2-66541, page 3.
A phenyl ether compound represented by the formula:
A phenolic compound represented by the general formula IIIB described in JP-A-4150, an amine-based compound represented by the general formula A described in JP-A-64-90445, and a general formula XII, XIII, XIV described in JP-A-62-182741; The metal complex represented by XV is particularly preferred for magenta dyes. JP-A-1-196
The compounds represented by the general formula I 'described in JP-A-549 and the compounds represented by the general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and compound (A'-1) described in the lower left column of page 10 of the same publication are disclosed. And the like. In addition, a fluorescent dye releasing compound described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or added to a silver halide emulsion layer to improve fog and the like. Is preferred. As the compound for this, a hydroquinone derivative is preferred, and more preferably 2,5-
Dialkyl hydroquinones such as di-t-octyl hydroquinone.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or improve the light fastness of the dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are those represented by the general formula III-3 described in JP-A-1-250944 and those represented by the general formula III described in JP-A-64-66646. Compounds described in JP-A-63-187240, UV-1L to UV-27L, JP-A-4-1633
Compound represented by general formula I described in JP-A-5-165
No. 144, compounds represented by formulas (I) and (II).

It is advantageous to use gelatin as a binder in the light-sensitive material. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other high polymers, proteins other than gelatin, sugar derivatives, cellulose A hydrophilic colloid such as a derivative, a single or a copolymer, or a synthetic hydrophilic polymer substance can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-24
It is preferable to use the compounds described in JP-A Nos. 9054 and 61-245153. It is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability. In order to improve the physical properties of the surface of the light-sensitive material or the processed sample, a protective layer is disclosed in
It is preferable to add a slip agent or a matting agent described in No. 8543 or JP-A-2-73250.

As the support used for the photosensitive material, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, and white pigment. For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. may be used. Among them, a support having a water-resistant 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 silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

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

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

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

The photosensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, on the support surface, and then directly or undercoating (adhesion, antistatic property, dimensional stability on the support surface). , Abrasion resistance, hardness, antihalation properties, frictional properties and / or other properties.

In applying the composition to the support, a thickener may be used to improve the applicability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

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 applied to a light-sensitive material which directly forms an image for 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 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-ethoxy) aniline CD-11) 4-amino-3-methyl-N-ethyl-
N- (γ-hydroxypropyl) aniline In the present invention, the above color developer can be used in any pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

The processing temperature of color development according to the present invention is 35
~ 70 ° C is preferred. 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, it is preferable that the temperature is not too high.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.

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

After the color development, the light-sensitive material is subjected to a bleaching process and a fixing process. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed.

The developing device used for developing the photosensitive material may be a roller transport type in which the photosensitive material is transported between rollers disposed in a processing tank, or may be transported with the photosensitive material fixed to a belt. An endless belt method may be used, but a processing tank is formed in a slit shape, a processing liquid is supplied to the processing tank and a photosensitive material is conveyed and a processing liquid is sprayed.
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid can also be used. In the case of processing in large quantities, it is usual to perform a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible.
As a replenishment method, a processing agent is added in the form of a tablet, and the method described in JP-A-94-16935 is most preferable.

[0086]

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 (Regarding Claim 1) (Preparation of Red-Sensitive Silver Halide Emulsion) Preparation of silver halide emulsion (S) having maximum sensitivity and its performance evaluation In 1 liter of a 2% aqueous gelatin solution kept at 40 ° C., the following (solution A) and (solution B) were pAg = 7.3, pH = 3. .
0 and added simultaneously over 30 minutes.
Solution) and (Solution D) were added simultaneously over 150 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 the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.40 g Potassium bromide 0.06 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.2 g K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ⁻⁵ mol / mol Ag Potassium bromide 2.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the average particle diameter is 0.40 μm, the coefficient of variation is 0.08, and the silver chloride content is 99.0% (silver bromide). 1%) of a monodispersed cubic emulsion EMP-1.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. In this case, pA
g was controlled at 7.0.

Sodium thiosulfate (STS) 1.6 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 Mol AgX stabilizer 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 For a red-sensitive emulsion, SS-1 was used per mole of silver halide. 2.0 × 10 ^-3 mol was added.

[0091]

Embedded image

High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to produce a paper support. 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 corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further provided, and a sample was prepared using the red-sensitive silver halide emulsion EMP-1 prepared above. The coating solution was prepared as shown in Table 1.

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

[0094]

[Table 1]

[0095]

Embedded image

SU-2: di (2-ethylhexyl) sulfosuccinate-sodium salt SU-3: di (2,2,3,3,4,4, sulfosuccinate)
5,5-octafluoropentyl) -sodium salt DBP: dibutyl phthalate DOP: dioctyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine-sodium HQ -1: 2,5-di-t-octylhydroquinone For the sample prepared as described above, an optical system using a gallium aluminum arsenide semiconductor laser (about 780 nm) has a beam diameter of about 80 μm, and a scanning speed using a polygon mirror. 160 m / sec, exposure time per pixel is 5 ×
Wedge-like exposure was performed under the conditions of 10 ^-7 seconds, and processing was performed under the following conditions.

Processing conditions Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 45 seconds 80ml Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds 120ml Stabilization 30-34 ° C 60 seconds 150 ml Drying 60-80 ° C 30 seconds The composition of the developing solution is shown below.

Color developing solution 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 Diethylenetriamine pentaacetate 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 Add water to make the total volume 1 liter. pH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fix bath solution and replenisher diammonium ferric diethylenetriaminepentaacetate dihydrate 65 g diethylenetriaminepentaacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 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 g ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water is added to make up to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or ammonia water.

For the processed sample, the gradient between the densities of 0.5 and 1.5 in the sensitometric curve was measured for the shoulder gradation γS at high illuminance exposure.

2. Preparation of Silver Halide Emulsion (M) Having Minimum Sensitivity Next, the addition time of the sample (Solution A) and (Solution B), the (Solution C) and ( A monodisperse cubic emulsion having an average particle size of 0.38 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.5% was prepared in the same manner as in EMP-1, except that the addition time of Solution D) was changed. For this, similarly to EMP-1, optimal chemical sensitization was performed at 60 ° C. to obtain EMP-1S. EMP-1 obtained
For S, the gradient between the densities 0.5 and 1.5 of the sensitometric curve was measured for shoulder gradation γM in high-illuminance exposure in the same manner as in EMP-1.

3. Preparation of Mixed Emulsion and Performance Evaluation Using EMP-1 and EMP-1S, γM (EMP-1
Six emulsions EMP-2S so that the ratio of (S) / γS (EMP-1) is obtained as shown in Table 2.
~ EMP-7S was prepared by optimizing chemical ripening conditions.

The γM (EMP-1S) / γS (EMP-1) of the obtained silver halide emulsions (S) and (M) are shown in Table 2 below.

EMP-1 and EMP-1 thus prepared
The emulsions were mixed so that the ratio of S to EMP-7S was 1: 1.
Was prepared.

[Evaluation] Sample 101 was prepared using the above exposure system.
To 107 were evaluated as follows. Table 2 shows the results.

Suitability for High Illumination Exposure The shoulder gradation γ was evaluated by the above exposure system.

-Low illumination exposure suitability Wedge-like exposure was performed for 0.5 seconds and 16 seconds using an exposure apparatus using a tungsten lamp as a light source while changing the exposure distance so that the exposure amount was the same. The sample was developed in the same manner as described above. It also calculated similarly gamma ₁ values were compared the difference [Delta] [gamma] ₁ value of 0.5 seconds and 16 seconds in the following manner.

Δγ ₁ = γ ₁ (16 s) −γ ₁ (0.5 s) • Suitability for latent image stability Using the same exposure system as used for evaluating low illuminance exposure suitability,
0.5 second wedge-like exposure, immediately developed sample,
The gradient value γ _{2 of a} straight line connecting the densities of 0.2 and 0.5 of the sample developed after processing the sample left in the dark for 60 minutes after exposure.
Is calculated, and the difference Δγ ₂ is shown as follows.

Δγ ₂ = γ ₂ (60 ′) − γ ₂ (0 ′)

[0111]

[Table 2]

As is evident from Table 2, in high-illumination exposure suitability, samples 101 and 102 exhibited γM (EMP-
The [gamma] ratio of 1S) / [gamma] S (EMP-1) was small, and the gradation in high illuminance exposure after mixing the emulsion was very low, indicating that the composition was not suitable for this evaluation. In Sample 103, an increase in the gradation value was observed, and this tendency can be recognized as an improvement effect of the high illuminance exposure suitability even at 103 to 107 where the γ ratio of the emulsion increased.

For low light exposure suitability, γM (EM
Sample 10 having a low γ ratio of (P-1S) / γS (EMP-1)
At 1 and 102, Δγ1 has a large negative value, and it can be seen that softening during low-illuminance exposure is large. On the other hand, in the samples 103 to 105, the value is small, and the gradation difference from the 0.5 second exposure is small.
However, the samples 106 and 1 with the γ ratio increased to 1.6 or more were used.
At 07, the gradation difference becomes large again, and it can be seen that the low illuminance exposure suitability is lacking.

Further, in terms of the stability of the latent image, γM (EMP-
Sample 10 having a γ ratio of 1S) / γS (EMP-1) of 1 or less
It can be seen that the values of Samples 104 and 105 decrease with respect to the values of 1 to 103, and the performance fluctuation of the latent image stability with respect to the time from exposure to development is improved. On the other hand, in the samples 106 and 107 in which the γ ratio is further increased, the value is increased again, and the performance is deteriorated.

Example 2 (Regarding Claim 2) The p of the emulsion EMP-1 used in Example 1 was chemically ripened.
Emulsions EMP-2S-1 and EMP-2S-1 which were optimally chemically ripened by changing the pAg value as shown in Table 3 based on the Ag value
EMP-2S-8 was prepared. Emulsions EMP-1 and EMP
-2S-1 to EMP-2S-8 were mixed with each other in an emulsion ratio of 1: 1, and coated samples 201 to 20 in the same manner as in Example 1.
No. 8 was prepared, and the same performance evaluation (high illuminance exposure suitability, low illuminance exposure suitability) and heat fog resistance evaluation shown below as in Example 1 were performed. Table 3 summarizes the obtained results.

Evaluation of heat fog resistance Each sample was stored for 1 week in an environment of 65 ° C./60% RH.
The fog density of the unexposed portion with respect to the comparative sample stored in the refrigerator was evaluated. The processing was the same as in the previous examples.

[0117]

[Table 3]

As is clear from Table 3, regarding the suitability for exposure to high illuminance, the difference between the pAg values of the samples 201 and 202 was minus, that is, EMP-2S-1 and EMP-2S-.
Sample No. 2 has a higher pAg during chemical ripening than EMP-1, but in this case, the gradation value at the time of high illuminance exposure is small, and it can be seen that it is not suitable for this exposure condition.
On the other hand, in Samples 203 to 208, the difference in pAg value changes from 0 to a positive value, and as the value increases, the gradation value increases and satisfactory performance can be obtained.

Regarding suitability for low-illumination exposure, samples 201 to 201
In FIG. 203, it can be seen that the gradation difference becomes smaller as the difference in pAg value becomes smaller, but it is still not at a satisfactory level. On the other hand, it can be seen that in Samples 204 to 207, as the difference in pAg value turned positive and increased, the gradation difference was further reduced, and the samples had low illuminance exposure suitability.
However, it can be seen that in the sample 208 having the difference in pAg value of 2.0, the gradation difference increases again and the low illuminance exposure suitability deteriorates.

Further, regarding the evaluation of heat fog resistance, Sample 20 was used.
Reference numerals 1 to 203 indicate regions where the difference in pAg value is minus to 0. Here, it can be seen that a large increase in the fog density is observed. On the other hand, Sample 20 in which the pAg value turned positive
4 to 208, it can be seen that the rise in fog is suppressed even when stored at 65 ° C./60% RH.

Example 3 (Regarding Claim 3) Emulsions EMP-1 and EMP-1 prepared in Example 1
Of the S, the desensitizing dye D-1 was added to EMP-1S only after the completion of chemical ripening in the preparation of the emulsion in the amount shown in Table 4, and emulsions EMP-3S-2 to EMP-3S-7 were added. Prepared. Using these, coating samples 301 to 307 were produced under the same conditions as before. EMP-1, EMP-1
The emulsion of S was mixed, and D-1 was added in the amount shown in Table 4 at the time of preparing the coating solution at the time of preparing the coating sample, whereby Samples 308 and 309 were prepared. Samples 301 to 307 were prepared in the same manner as in Samples EMP-E except that the emulsion to which D-1 was added was changed to EMP-1.
3-10 and EMP-3-11 were prepared. Using these, coating samples 310 and 311 were prepared in the same manner.
Performance evaluation similar to (high-light exposure suitability, low-light exposure suitability)
And the following humidity dependency during exposure were performed. Table 4 summarizes the obtained results.

[0122]

Embedded image

Evaluation of Humidity Dependence at Exposure Each sample was measured at 25 ° C./40% RH and 25 ° C./80% RH.
Wedge-like exposure was performed under an environment of 0.5 seconds with an exposure time of 0.5 seconds, and the same processing as before was performed. Relative sensitivity at 25 ° C./80% RH when the amount of light required to obtain a density of 0.8 of the sample exposed in an environment of 25 ° C./40% RH is calculated from a sensitometric curve and is set as a reference sensitivity of 100. Of the variation ΔS ₂ (%) was determined as follows.

ΔS ₂ (%) = sensitivity (%) at 25 ° C./80% RH−sensitivity (%) at 25 ° C./40% RH

[0125]

[Table 4]

As is clear from Table 4, the desensitizing dye was compared with the comparative sample 301 with respect to the high illuminance exposure suitability.
Samples 302 to 307 added to MP-1S all have high gradation values, indicating that they have excellent high illuminance exposure suitability. Among them, samples 303 and 304 have high values. You can see that. On the other hand, 3
It can be seen that the values of 08 and 309 still show a high value for the comparative sample 301, but are slightly lower than the values for 302 to 307. Further, in Samples 310 and 311 in which desensitizing dye D-1 was added to EMP-1, the value was further decreased, and deterioration in performance can be recognized.

Regarding the suitability for low-illumination exposure, Comparative Sample 3
In contrast to Sample 01, Samples 302 to 305 show little change in gradation due to the difference in exposure time, and have excellent reciprocity failure characteristics in addition to the above-mentioned evaluation of high illuminance exposure suitability. On the other hand, sample 30 in which the amount of desensitizing dye was further increased
Samples Nos. 6 and 307, Samples 308 and 309 to which the coating solution was added, and Samples 310 and 311 to the emulsion EMP-1 all had a large softening due to a long exposure time, and their performance deteriorated.

Regarding the humidity dependency at the time of exposure, it can be seen that samples 302 to 305 have smaller sensitivity fluctuations with respect to the reference sample 301, and the performance fluctuation with respect to the change of humidity at the time of exposure is small and excellent. On the other hand, samples 306 and 30
When the amount of the desensitizing dye was further increased as in Sample No. 7, Sample 30
It can be seen that in both cases where the coating liquids such as Nos. 8 and 309 were added and when the emulsion was added to the emulsion EMP-1, there was a large fluctuation in performance with respect to the change in humidity during exposure.

Example 4 (Relating to Claim 3) Emulsion and coating samples 401 to 4 were prepared in the same manner as in Example 3 except that the desensitizing dye to be added was changed to Dye R-1.
11 was produced. Using these samples, the suitability for high illuminance and low illuminance exposure and the humidity dependency during exposure were evaluated in the same manner as in Example 3. Table 5 shows the results.

[0130]

Embedded image

[0131]

[Table 5]

As is apparent from Table 5, almost the same effects as in Example 3 could be confirmed.

[0133]

According to the present invention, it is possible to provide a silver halide photographic emulsion which has small fluctuations in performance at high and low illuminances, and has good latent image stability, heat-resistant storage stability, and good humidity dependency during exposure. It has excellent effects.

Claims (3)

[Claims] 1. A silver halide emulsion having an average silver chloride content of 95% or more, wherein the emulsion is a mixture of silver halide emulsions having a plurality of sensitivities, and the silver halide emulsion (S) having a maximum sensitivity A silver halide photographic material having a photosensitive layer containing
0 ^-6 seconds after following exposure, pull the color development was a straight line passing through a point giving the points and density of 1.5 giving a density 0.5 on the obtained characteristic curve was imaged, the average gradient (gammaS ) Is the average gradient (γ) obtained from the silver halide photographic material when the silver halide emulsion (M) having the minimum sensitivity is used.
M) a silver halide emulsion characterized in that the average gradients of the two have the following relationship: 1 <γM / γS <1.5 2. A silver halide emulsion having an average silver chloride content of 95% or more, wherein the emulsion is a mixture of silver halide emulsions having a plurality of sensitivities, and the silver halide emulsion (S) having the maximum sensitivity PAg (S) when preparing a silver halide emulsion (M) having the minimum sensitivity.
A silver halide emulsion which is higher than Ag (M) and has the following relationship. 0 <pAg (S) -pAg (M) <1.5 3. A silver halide emulsion having an average silver chloride content of 95% or more, wherein the emulsion is a mixture of silver halide emulsions having a plurality of sensitivities, and a silver halide emulsion (M) having a minimum sensitivity Wherein the silver halide emulsion is prepared by adding a dye or a desensitizing dye having a positive sum of the polarographic anode potential and the polarographic cathode potential in an amount of 10 mg or less per mol of silver halide.