JP3409224B2 - Silver halide emulsion - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention is capable of rapid processing,
In addition, the present invention relates to a silver halide emulsion capable of stably obtaining a high-quality color print when producing a plurality of color prints from the same negative.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials, particularly silver halide color photographic light-sensitive materials, are widely used today because of their high sensitivity and excellent gradation. However, the development processing of a silver halide color photographic light-sensitive material is a so-called wet processing, and it takes time to prepare a processing solution, it becomes dirty, a waste solution containing various chemicals is discharged, a dark room is required, and after the operation is started. There were drawbacks such as the long time it took to obtain the first print. In order to make up for these drawbacks and make full use of the advantages of the silver halide color photographic light-sensitive material described above, a system in which a skilled engineer concentrates from the development of color negatives to the production of color prints in a few large development laboratories. Has been taken.

This system is a so-called negative-positive system in which a silver halide photographic light-sensitive material for printing is exposed and developed through an image recorded on a color negative film, which is due to excess or deficiency of exposure and difference in illumination when photographing with a color negative. Since it is possible to correct the color misregistration at the time of printing, it has become possible to stably provide a high-quality printed image.

However, although the essence of wet processing has not changed in recent years, improvements in equipment such as printers and automatic processors, improvements in developing solutions, improvements in silver halide color photographic light-sensitive materials and their packaging forms have been accumulated. Therefore, a so-called minilab, which is capable of consistently performing color negative development to color print production in a small space such as at a photo shop, is rapidly becoming popular. For this reason, the demand for stable provision of high-quality printed images, even for non-skilled engineers, has increased significantly.

Under these circumstances, a high chloride silver halide emulsion consisting of a high concentration of silver chloride has come to be used for color paper. The currently used method of printing an image recorded on a color negative on color paper is extremely excellent in that it can form an image easily at high speed, but it uses a high chloride silver halide emulsion. The conventional color paper has a drawback that the finish thereof varies when an attempt is made to obtain the same print from the same color negative. This phenomenon is mitigated by lengthening the time interval when exposing the same pattern, but the effect is not sufficient, and it is not possible to realize it because it causes a significant decrease in productivity.

The inventors of the present invention have disclosed, in Japanese Patent Laid-Open No. 5-204071, at least one of a silver halide emulsion containing 98 mol% to 99.9 mol% of silver chloride having a silver bromide-containing phase of 30 mol% or more and a specific compound. It has been disclosed that the silver halide photographic light-sensitive material used in combination with the above can improve the density fluctuation when forming a plurality of prints of the same pattern, and can obtain a color print excellent in whiteness and sharpness. Further, the inventors of the present invention disclosed in JP-A-6-59364 that 90 mol% or more of silver chloride is chemically sensitized with a specific sulfur compound and a gold compound for an unchemically sensitized emulsion satisfying specific requirements. Have disclosed that variations in gradation that occur when a roll-shaped silver halide photographic light-sensitive material using this silver halide emulsion is continuously processed are improved.

However, even if these techniques are used, the effect is still insufficient, and further improvement has been desired.

By incorporating the compound represented by formula (I) of the present invention into a silver halide photographic light-sensitive material,
It is disclosed that sensitivity, fog, storability with time, and latent image stability are improved. For example, JP-A-3-219232 discloses a combination with a cyanine dye, JP-A-3-219233 describes a combination with two kinds of oxacarbocyanines, and JP-A-6-194780 describes a combination with a solid dispersion of a sensitizing dye. Combinations are disclosed. However, in those proposals, only a silver halide emulsion mainly composed of silver bromide is described, and when applied to a high silver chloride emulsion system having a very high silver chloride content like the present invention, However, it does not teach at all about the effect of reducing the density variation between color prints.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to produce a color image when making multiple color prints from the same negative of a silver halide emulsion containing a high concentration of silver chloride capable of rapid processing. To provide a silver halide emulsion that does not cause fluctuations in

[0010]

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

1. The silver halide emulsion wherein the silver chloride content is 95 mol% or more, and the ratio of the decay time of Denver electromotive force at a relative humidity of 20% and 80% are _{0.9 ≦ τ 20 / τ 80 ≦} 1.1 .

Here, τ ₂₀ and τ ₈₀ are relative humidity of 20%, respectively.
It represents the decay time of the Denver electromotive force at 80%, and the signal intensity is (peak intensity + signal intensity 0.003 seconds after the peak) based on the time when the signal of Denver electromotive force peaks.
It is the time that becomes / 2.

2. The silver chloride content is 95 mol% or more, τ
_A silver halide emulsion characterized in that the ratio of the signal intensities of Denver electromotive force of 20% relative humidity and 80% at 80 hours is 0.9 ≦ I ₂₀ / I ₈₀ ≦ 1.3.

3. 20% relative humidity at the time of τ ₈₀
When halogen Kaginchichi according to the 1 80% of Denver electromotive force intensity ratio of signals is characterized in that it is a _{0.9 ≦ I 20 / I 80 ≦} 1.3
Agent. 4. 4. The silver halide emulsion as described in any one of 1 to 3 above , which contains a compound represented by the following general formula (I).

[0015]

[Chemical 2]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ , R ₆ , R ₇ and R 4 Each ₈ represents a substituent. L ₁ and L ₂ each represent a methine group, and Z ₁
Is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, -C
_{(R 9) (R 10)} - or -N (R ₉₎ - represents a. R ₉ and R ₁₀ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Also, R ₁
And R ₂ , R ₃ and R ₄ , R ₉ and R ₁₀ may be bonded to each other to form a ring.

5. The silver chloride content is 98-99.9%
The HA according to any one of 1 to 4 above,
Silver rogenide emulsion. 6. Containing a dye represented by the general formula (SPS-I)
6. The halogen according to any one of 1 to 5 above,
Silver halide emulsion. Hereinafter, the details of the present invention will be described.

Regarding the method for measuring the Denver electromotive force of a silver halide emulsion, Photographic Science and Engineering, Vol. 15, page 279 (B. Levy, Photographic Science and Engineering)
15 , 279 (1971)) and Photographic Science and Engineering by Levy, Lindsey, and Dixon, page 17, 115 (B.Levy, M.Lindsey, an
d CR Dickson, Photographic Science and Engine
ering 17 , 115 (1973)) and the like. Generally, the sample is inserted between the electrodes and one of the electrodes emits light having a wavelength having a large absorption coefficient (hence, one of the electrodes is exposed to light of a predetermined wavelength to be used). A transparent conductive electrode is often used), and a sample due to the difference in diffusion rate of charge carriers (free electrons and holes in the case of silver halide) generated by light irradiation. The internal electric polarization is detected as a potential difference between the electrodes.

Denver electromotive force of a silver halide emulsion is usually due to free electron diffusion (when free electron diffusion rate> hole diffusion rate) and hole diffusion (when hole diffusion rate> free electron diffusion rate). According to the present invention, the decay time of the Denver electromotive force refers to the decay time of the electromotive force generated by free electron diffusion.

The following can be given as a specific example of the measuring method for obtaining the decay time of the Denver electromotive force. As the irradiation light source, a laser beam having a wavelength of 337.1 nm, a pulse width of about 2 nm and an irradiation light intensity of 50 μJ / cm ² was used, and the sample sandwiched between two electrodes (one of which was a transparent electrode) facing each other from the transparent electrode side. Sampling oscilloscope of the induced voltage generated in the sample by irradiating with pulsed light (Oscilloscope sampling frequency band DC to 20 MHz, input impedance 1 MΩ or more)
And measure the transient time response of the induced voltage.

The decay time is preferably such that the time constant of the measurement system is about 50 nanoseconds. If a device with a small time constant is used, information on the change in the induced voltage for an extremely short time can be obtained, which is preferable for analysis, but the fluctuation due to the influence of the measurement conditions also becomes large, and the conditions under which the effect of the present invention can be obtained A time constant of about 50 nanoseconds is preferable for identification.

The sample used for measuring the Denver electromotive force may be a silver halide emulsion in the form of a thin film of several hundred μm or less. Further, a silver halide emulsion sample coated on a support such as triacetyl cellulose or polyethylene terephthalate may be used, but in this case, the thickness of the sample is preferably about 1 mm or less. An insulating thin film is inserted between the thin film surface of the silver halide emulsion and the electrode and, if the support is conductive, between the support and the electrode. In the present invention, as a characteristic value derived from the decay time of the Denver electromotive force, the intensity of the signal is (peak intensity + signal intensity 0.003 seconds after the peak) with reference to the time at which the signal of the Denver electromotive force peaks.
Use the ratio of time τ that becomes / 2. The sample is left for about 4 hours under the conditions of relative humidity of 20% and 80%, and τ measured using the sample is set as τ ₂₀ and τ ₈₀ , respectively, and τ ₂₀ / τ ₈₀ is obtained. At this time, measurement may be performed at a plurality of points sandwiching the relative humidity of 20 and 80%, and the values at the relative humidity of 20 and 80% may be estimated by interpolating from the results. The temperature at this time may be in the range of 10 to 50 ° C, but is preferably 20 to 30 ° C.

As another characteristic value, in the present invention, the signal intensity I ₂₀ at t = τ ₈₀ is based on the signal I of the Denver electromotive force measured at a relative humidity of 20% and the measurement result of the time t.
And the signal intensity I ₈₀ at t = τ ₈₀ under the condition of relative humidity 80%, the signal intensity ratio I ₂₀ / I ₈₀ is determined.

The silver halide emulsion according to the present invention is characterized by satisfying either of the following two relationships.

[0025] _{0.9 ≦ τ 20 / τ 80 ≦} 1.1 0.9 ≦ I 20 / I 80 ≦ 1. 3 the two characteristic values satisfy both often two conditions to substantially the same motion but only one condition There may be cases where they do not meet. The effect of the present invention can be obtained in any case, but a silver halide emulsion satisfying both of the two conditions is more effective and preferable.

The ratio (τ ₂₀ / τ ₈₀ ) is more preferably 0.95 to 1.08, still more preferably 0.97 to 1.05.

The value of (I ₂₀ / I ₈₀ ) is more preferably 0.95 to 1.25, further preferably 0.97 to 1.20.

Next, the compound represented by the general formula (I) will be described.

R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom,
Alkyl group, alkenyl group, alkynyl group, aryl group or represents a heterocyclic group, and R ₅ , R ₆ , R ₇ and R ₈ each represent a substituent. L ₁ and L ₂ each represent a methine group, Z ₁ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, —C.
_{(R 9) (R 10)} - or -N (R ₉₎ - represents a. R ₉ and R ₁₀ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R ₁ and R ₂ , R ₃ and R ₄ , and R ₉ and R ₁₀ may be bonded to each other to form a ring. Examples of the alkyl group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₉ , and R ₁₀ include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl,
Each group such as cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl and the like can be mentioned. These alkyl groups may be further substituted by halogen atom, alkoxy group, aryloxy group, aryl group, alkoxycarbonyl group, aryloxycarbonyl group, alkenyl group, heterocyclic group, alkynyl group, amino group, cyano group, sulfonamide group, etc. It goes without saying that they may be replaced.

Examples of the alkenyl group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₉ and R ₁₀ include a vinyl group and an allyl group.

Examples of the alkynyl group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₉ and R ₁₀ include a propargyl group.

Examples of the aryl group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₉ and R ₁₀ include phenyl and naphthyl groups.

The heterocyclic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₉ and R ₁₀ includes, for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, thienyl group and pyrrolyl group. Group, pyrazinyl group, pyrimidinyl group,
Examples thereof include a pyridazinyl group, a selenazolyl group, a sulforanyl group, a piperidinyl group, a pyrazolyl group and a tetrazolyl group.

The above alkenyl group, alkynyl group, aryl group and heterocyclic group are all R ₁ , R ₂ , R ₃ , R ₄ and
Needless to say, the alkyl group represented by R ₉ and R ₁₀ and the same groups as the substituents of the alkyl group can be substituted.

The substituent represented by R ₅ , R ₆ , R ₇ and R ₈ is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group or an alkoxy group. Carbonyl group, aryloxycarbonyl group, sulfonamide group, sulfamoyl group, ureido group, acyl group, carbamoyl group, amide group, sulfonyl group, amino group, cyano group, nitro group, mercapto group, alkylthio group, arylthio group, alkenylthio group Represents a group, a heterocyclic thio group, a hydrogen atom and the like. These groups can be substituted with the same groups as the alkyl groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₉ and R ₁₀ and the groups shown as the substituents of the alkyl groups.

Examples of the ring formed by R ₁ and R ₂ include benzene, naphthalene, thiophene, pyridine, furan, pyrimidine, cyclohexene, pyran, pyrrole,
Examples include rings such as pyrazine and indole.

Examples of the ring formed by R ₃ and R ₄ include rings such as piperidine, pyrrolidine, morpholine, pyrrole, pyrazole and piperazine.

Examples of the ring formed by R ₅ and R ₆ and R ₇ and R ₈ include rings such as benzene, naphthalene, thiophene, pyridine, furan, pyrimidine, cyclohexene, pyran, pyrrole, pyrazine and indole. .

The above rings have R ₁ , R ₂ , R ₃ , R ₄ , R ₉ and
It can be substituted with the same groups as the alkyl group represented by R ₁₀ and the substituents of the alkyl group.

The methine group represented by L ₁ and L ₂ may have a substituent, and examples of the substituent include an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group and an aryl group. An oxycarbonyl group and the like can be mentioned. These groups are further represented by R ₁ , R ₂ , R
_The alkyl group represented by ₃ , R ₄ , R ₉ , and R ₁₀ and a group similar to the groups shown as the substituent of the alkyl group can be substituted.

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

[0042]

[Chemical 3]

[0043]

[Chemical 4]

[0044]

[Chemical 5]

[0045]

[Chemical 6]

[0046]

[Chemical 7]

[0047]

[Chemical 8]

[0048]

[Chemical 9]

[0049]

[Chemical 10]

[0050]

[Chemical 11]

As a specific synthetic example method of the compound of the general formula (I) according to the present invention (hereinafter, also simply referred to as the compound of the present invention), the synthetic method described on page 12 of JP-A-6-194780 can be mentioned. You can

The compound of the present invention is preferably added in an amount of 2 × 10 ^-7 to 1 × 10 ^-2 mol, and more preferably 2 × 10 ^{-7 to} 5 × 10 ^-3 mol per mol of silver halide. Is preferred.

As a method for adding the compound of the present invention to a silver halide emulsion, a method well known in the art can be used. For example, the compound can be dispersed directly in the emulsion, or dissolved in a water-soluble solvent such as pyridine, methanol, ethanol, methyl cellosolve, acetone, fluorinated alcohol, dimethylformamide, or a mixture thereof, or diluted with water. Alternatively, it can be dissolved in water and added to the emulsion in the form of a solution.
Ultrasonic vibration can also be used during the dissolution process.

Also, the compounds of the present invention were prepared according to US Pat.
Dissolved in a volatile organic solvent as described in No. 987,
A method in which a dispersion prepared by dispersing this solution in a hydrophilic colloid is added to an emulsion, and the compound of the present invention is dispersed in a water-soluble solvent without being dissolved, as described in JP-B-46-24185. A method of adding this dispersion to an emulsion can also be used.

Further, the compound of the present invention can be added to the emulsion in the form of a dispersion prepared by an acid solution dispersion method.

The compound represented by the general formula (I) may be added at any time from the formation of silver halide grains to the preparation of a coating solution, but from the start to the end of chemical sensitization. It is particularly preferable to add it in between. The compound represented by formula (I) may be added to the silver halide emulsion together with the sensitizing dye at the same time or separately.

The silver halide emulsion according to the present invention contains silver chloride.
It is characterized by containing 95 mol% or more, but if it satisfies this condition, it may have any halogen composition such as silver chloride, silver chlorobromide, silver chloroiodobromide, and silver chloroiodide. . Silver chlorobromide containing silver chloride in an amount of 95 mol% or more and substantially free of silver iodide (the content of silver iodide is 0.1 mol% or less) is preferable, more preferably 97 mol% or more, and further preferably 98 mol%.
Silver halide emulsions containing ~ 99.9 mol% silver chloride are preferred.

In order to obtain the silver halide emulsion according to the present invention, a silver halide emulsion having a portion containing a high concentration of silver bromide is particularly preferably used. In this case, the portion containing 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 preferably the surface of the silver halide grain, and particularly preferably the apex of the crystal grain.

In order to obtain the silver halide emulsion according to the present invention, it is advantageous to contain a heavy metal ion. Heavy metal ions that can be used for such purposes include iron,
Iridium, platinum, palladium, nickel, rhodium,
Group 8-10 metals such as osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury;
Lead, rhenium, molybdenum, tungsten, gallium,
Each ion of chromium can be mentioned. Of these, metal ions of iron, iridium, platinum, ruthenium, gallium, 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, its ligand or ion is cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl. , Ammonia, and the like. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

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

The amount of the above-mentioned 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 preferably 1 × 10 ⁻⁸ mol, per mol of silver halide.
It is preferably not less than 5 mol and not more than 5 × 10 ⁻⁵ mol.

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, etc., and the Journal of Photographic Science (J.Photog
r.Sci.) 21 , 39 (1973) and the like, particles having an octahedral shape, a tetradecahedral shape, a dodecahedron shape and the like can be prepared and used. Further, grains having twin planes may be used.

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

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

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

The particle 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,
Particularly preferably, two or more monodisperse emulsions having a coefficient of variation of 0.15 or less are added to 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 / R (where S is the standard deviation of the grain size distribution and R is the average grain size.) The grain size as used herein means the diameter of spherical silver halide grains. Further, in the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having the same area.

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

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The 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, 57-92524, etc., published in Germany An apparatus for continuously changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Patent 2,921,164, etc., and taking out the reaction mother liquor from the reactor described in JP-B-56-501776 and the like, 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 according to the present invention can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

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

The addition amount of the sulfur sensitizer used in the present invention is preferably changed depending on the kind of silver halide emulsion to be applied and the magnitude of expected effect, but it is 5 × per mol of silver halide. A range of 10 ^{−10 to} 5 × 10 ⁻⁵ mol,
The range of 5 × 10 ^{−8 to} 3 × 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 the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but is usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol of silver halide.
It is preferably molar. More preferably 1 × 10 ^-5
The molar amount is 1 × 10 ⁻⁸ mol.

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

The silver halide emulsion according to the present invention has the purpose of preventing fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuations during storage, and preventing fog that occurs during development. Known antifoggants and stabilizers can be used. Examples of preferred compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A 2-146036, page 7, lower column, and more preferred specific compounds Are described in (IIa-1) to (IIa-
8), compounds of (IIb-1) to (IIb-7) and compounds such as 1- (3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole be able to.

These compounds are added in the steps such as the step of preparing silver halide emulsion grains, the step of chemical sensitization, the end of the chemical sensitization step and the step of preparing a coating solution, 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 mol to 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, 1 × 10 ^-6 mol to 1 mol per mol of silver halide
It is preferably an amount of about × 10 ^-2 mol, 1 × 10 ^-5 mol to 5 × 10 ^-3.
Molar is more preferred. When 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.
More preferably, it is from x10 ^-5 mol to 1 x 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 per 1 m ² .

In the silver halide photographic light-sensitive material using the silver halide emulsion of the present invention, dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used, but in particular, as the dye having absorption in the visible region, the dyes of AI-1 to 11 and the dyes disclosed in JP-A-3-251840, page 308 The dyes described in JP-A-6-3770 are preferably used. As the infrared absorbing dye, the general formula described in JP-A 1-280750, page 2, lower left column
(I), (II), the compound represented by (III) has preferable spectral characteristics, without affecting the photographic characteristics of the silver halide emulsion,
Further, there is no contamination due to residual color, which is preferable. Specific examples of preferable compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column.

For the purpose of improving the sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of the untreated sample of the light-sensitive material is 0.7 or more, more preferably 0.8 or more. .

It is preferable to add a fluorescent whitening agent to the silver halide photographic light-sensitive material using the silver halide emulsion of the present invention because the whiteness can be improved. Examples of the compounds preferably used include the compounds represented by the general formula II described in JP-A No. 2-232652.

Regarding the sensitizing dye used in the present invention,
Any known compound can be preferably used.
Preferred compounds include the following general formula (SPS-I) to general formula
(SPS-III) The compound shown can be mentioned.

[0086]

[Chemical 12]

In the formula, Z ₁₁ and Z ₁₂ are oxazole nucleus, thiazole nucleus, selenazole nucleus, pyridine nucleus, benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus and naphtho group, respectively. It represents a group of atoms necessary for forming a selenazole nucleus, a naphthimidazole nucleus, or a quinoline nucleus.

R ₁₁ and R ₁₂ each represent an alkyl group, an alkenyl group or an aryl group.

[0089] X ^- represents an anion, m represents 0 or 1.

In the general formula (SPS-I), the heterocyclic nucleus represented by Z ₁₁ and Z ₁₂ is a thiazole nucleus, a selenazole nucleus,
A benzothiazole nucleus, a benzoselenazole nucleus, and a naphthothiazole nucleus are preferable, and a benzothiazole nucleus and a naphthothiazole nucleus are more preferable.

The heterocyclic group represented by Z ₁₁ and Z ₁₂ may have a substituent, and a preferable substituent is a halogen atom, a hydroxyl group, a cyano group, an aryl group, an alkyl group, an alkoxy group or the like. Can be mentioned.

A chlorine atom is particularly preferable among the halogen atoms, and a phenyl group is preferable as the aryl group.

As the alkyl group, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and each group such as methyl, ethyl, propyl, i-propyl, butyl and the like can be mentioned. Among them, the methyl group is preferable. .

The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and examples thereof include methoxy, ethoxy, and propoxy groups, and among them, a methoxy group is preferable.

The alkyl group represented by R ₁₁ and R ₁₂ is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and methyl, ethyl, propyl, i-propyl and the like groups are preferable. These alkyl groups may be substituted, and preferable substituents include sulfo group, carboxyl group, hydroxyl group, alkoxycarbonyl group, alkylsulfonylamino group and the like.

Specifically, groups such as 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl, carboxymethyl, 2-carboxyethyl, 2-ethoxycarbonylethyl, 2-hydroxyethyl, 2-methylsulfonylaminoethyl and the like. Is.

As the alkyl group represented by R ₁₁ and R ₁₂ , an alkyl group substituted with a sulfo group or a carboxyl group is preferable.

The sulfo group, the carboxyl group and the like may form a salt with an organic cation such as a pyridinium ion and a triethylammonium ion or an inorganic cation such as an ammonium ion, a sodium ion and a potassium ion.

[0099] X ^- include anions represented by the chloride, bromide, and iodide ion or p- toluenesulfonate ion are preferred, the halide salt ions.

When forming an intramolecular salt, an anion may not be contained, and in that case, m represents 0.

[0101]

[Chemical 13]

Z ₂₁ and Z ₂₂ are oxazole nucleus, thiazole nucleus, selenazole nucleus, pyridine nucleus, benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus and naphthoselena, respectively. It represents a group of atoms necessary for forming a azole nucleus, a naphthimidazole nucleus, or a quinoline nucleus.

R ₂₁ and R ₂₂ are the same as R ₁₁ and R ₁₂ in the general formula (SPS-I), and X ⁻ and m are the same as those in the general formula (SPS-I).

R ₂₃ represents a hydrogen atom, an alkyl group or an aryl group.

The heterocyclic nucleus represented by Z ₂₁ and Z ₂₂ includes a benzothiazole nucleus, a benzoselenazole nucleus, a benzoxazole nucleus, a benzimidazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus, a naphthoselenazole nucleus and a naphthimidazole nucleus. preferable. The heterocyclic group represented by Z ₂₁ and Z ₂₂ may have a substituent, and preferable examples of the substituent include the same groups as those described for Z ₁₁ and Z ₁₂ in the general formula (SPS-I). Can be mentioned.

The alkyl group represented by R ₂₃ is preferably an ethyl group or a propyl group, and the aryl group is preferably a phenyl group.

[0107]

[Chemical 14]

Z ₃₁ and Z ₃₂ each represent an atomic group necessary for forming a benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus, naphthoselenazole nucleus or quinoline nucleus. .

R ₃₁ and R ₃₂ are the same as R ₁₁ and R ₁₂ in the general formula (SPS-I), and X ⁻ and m are the same as those in the general formula (SPS-I). n represents 1 or 2.

R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ and R ₃₇ represent a hydrogen atom, an alkyl group or an aryl group. When n represents 2, R ₃₆ and R ₃₇ may be the same or different.

The heterocyclic nucleus represented by Z ₃₁ and Z ₃₂ is preferably a benzothiazole nucleus, a benzoselenazole nucleus, a benzoxazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a quinoline nucleus.

The heterocyclic group represented by Z ₃₁ and Z ₃₂ may have a substituent, and a preferable substituent is the above general formula (S
The same groups as those mentioned for Z ₁₁ and Z ₁₂ in PS-I) can be mentioned.

The alkyl group represented by R _{33 to} R ₃₇ is preferably a methyl group or an ethyl group, and R ₃₄ and R ₃₆ may form a ring.

The above compounds are generally known, and are easily synthesized by the method described in, for example, Harmer, "The Cyanine Soybean and Relayed Compounds" (Interscience Publishers, New York, 1969). be able to.

The sensitizing dye used in the present invention is selected from the types of sensitizing dyes, the halogen composition of the silver halide emulsion to be applied,
Depending on the grain size and the like, it is preferably 5 × 10 ^-5 to 2 × 10 ^-3 mol, and more preferably 1 × 10 5 mol per mol of silver halide.
It is used in the range of ^{-4 to} 7 x 10 ^-4 mol.

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 dispersing the sensitizing dye, other than the method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system using a high-speed stirring type disperser, as described in JP-A-58-105141. A method of mechanically pulverizing and dispersing fine particles of 1 μm or less in a water system under conditions of pH 6 to 8 and 60 to 80 ° C.
The method of dispersing in the presence of a surfactant which suppresses the surface tension to 38 dyne / cm or less described in No. 6496 can be used.

As a dispersion device that can be used to prepare a dispersion liquid, for example, Japanese Patent Laid-Open No. 4-125631 can be used.
In addition to the high-speed stirring type disperser shown in the figure, a ball mill, a sand mill, an ultrasonic disperser, etc. may be mentioned.

When using these dispersing devices, as described in Japanese Patent Laid-Open No. 4-125632, a method of performing wet dispersion after performing pretreatment such as dry pulverization in advance may be adopted.

The sensitizing dye used in the present invention may be a combination of a plurality of sensitizing dyes as long as the effects of the present invention are not impaired. In this case, the two sensitizing dyes may be added separately, or they may be mixed in advance and then added.

Hereinafter, the above general formulas (SPS-I), (SPS-II) and (SP
Representative specific examples of the sensitizing dye represented by S-III) are shown below.

[0122]

[Chemical 15]

[0123]

[Chemical 16]

[0124]

[Chemical 17]

[0125]

[Chemical 18]

[0126]

[Chemical 19]

[0127]

[Chemical 20]

[0128]

[Chemical 21]

[0129]

[Chemical formula 22]

[0130]

[Chemical formula 23]

[0131]

[Chemical formula 24]

[0132]

[Chemical 25]

The spectral sensitizing dye represented by the general formula (SPS-III) includes, as a supersensitizer, the supersensitizers SS-1 to SS-1 described in JP-A-4-285950, pages 8 to 9. It is preferable to use SS-9 in combination.

The effect of the present invention is preferable since it is highly effective when used for the sensitizing dye represented by the general formula (SPS-I).

The coupler used when the silver halide emulsion of the present invention is used in a silver halide photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material), has a coupling reaction with an oxidant of a color developing agent, and a wavelength of 340 nm or less. Although any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a long wavelength region can be used, a typical example thereof is a yellow dye having a spectral absorption maximum wavelength in a wavelength region of 350 to 500 nm. Forming coupler, a magenta dye forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm,
The one known as a cyan dye forming coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm is typical.

As a cyan coupler which can be preferably used in the above-mentioned silver halide photographic light-sensitive material, JP-A-4-
The general formulas (CI) and (C-
The coupler represented by II) can be mentioned. Specific compounds are described in the lower right column on page 5 to the lower left column on page 6 of the same publication.
The compounds described as CC-1 to CC-9 can be mentioned.

As magenta couplers that can be preferably used in the above-mentioned silver halide photographic light-sensitive material, there are disclosed in
The general formula (MI) described in the upper right column on page 4 of 4-114154 Publication,
The coupler represented by (M-II) may be mentioned. Specific compounds include those described as MC-1 to MC-11 in the same publication, page 4, lower left column to page 5, upper right column. More preferable among the above-mentioned magenta couplers are couplers represented by the general formula (MI) described in the upper right column of page 4 of the same publication, of which RM of the general formula (MI)
A coupler in which is a tertiary alkyl group is particularly preferable because it has excellent light resistance. MC-8 to M described in the upper column of page 5 of the same publication
C-11 is preferable because it has excellent reproduction of colors from blue to purple and red, and also has excellent detail descriptive power.

A yellow coupler which can be preferably used in the silver halide photographic light-sensitive material is described in JP-A-
The coupler represented by the general formula (Y-1) described in the upper right column of page 3 of 4-114154 can be mentioned. Specific compounds include those described as YC-1 to YC-9 in the lower left column of page 3 of the same publication.

Among them, the coupler represented by the general formula [Y-1] in which RY ₁ is an alkoxy group or the coupler represented by the general formula [I] described in JP-A-6-67388 can reproduce a preferable yellow color tone. preferable. Of these, particularly preferable examples of compounds include YC-8 and YC-9 described in JP-A-4-114154, page 4, lower left column, and JP-A-6-67388.
The compounds represented by Nos. (1) to (47) on page 14 can be mentioned. The most preferred compounds are disclosed in JP-A-4-81847, page 1 and page 11,
It is a compound represented by the general formula [Y-1] on page 17.

When the oil-in-water type emulsion dispersion method is used to add the coupler or other organic compound used in the silver halide photographic light-sensitive material, a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher is usually used. If necessary, 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 to dissolve and disperse the coupler, dioctyl phthalate,
Phthalic acid esters such as diisodecyl phthalate and dibutyl phthalate, and phosphoric acid esters such as tricresyl phosphate and trioctyl phthalate are preferably used. Also, the dielectric constant of the high boiling point organic solvent is 3.5 to 7.0.
Is preferred. It is also possible to use two or more high boiling point organic solvents in combination.

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

Preferred compounds as a surfactant used for dispersing the additives for silver halide photographic light-sensitive materials and adjusting the surface tension at the time of coating are those having 8 to 8 carbon atoms in one molecule.
Examples thereof include those containing 30 hydrophobic groups and sulfonic acid groups or salts thereof. Specific examples thereof include A-1 to A-11 described in JP-A 64-26854. A surfactant having a fluorine atom substituted in the alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion.
Also, it is preferable that the time from the addition to the coating liquid to the coating is short, preferably within 10 hours, more preferably within 3 hours and within 20 minutes.

An anti-fading agent is preferably used in combination with each of the above-mentioned couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferable compounds include phenyl ether compounds represented by the general formulas I and II described in JP-A-2-66541, page 3, JP-A-3-17
A phenolic compound represented by the general formula IIIB described in JP 4150A, an amine compound represented by the general formula A described in JP-A 64-90445, and a general formula XI described in JP 62-182741.
The metal complexes represented by I, XIII, XIV and XV are particularly preferable for magenta dyes. Further, the compound represented by the general formula I ′ described in JP-A 1-196049 and the compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in JP-A-4-114154, page 9, lower left column, the compound (A'-, described in page 10, lower left column of the same publication). Compounds such as 1) can be used. Other than this, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

In the silver halide light-sensitive material, a compound which reacts with an oxidized product of a developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, and more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are the compounds represented by the general formula II described in JP-A No. 4-133056, and the compounds II-1 to II described on pages 13 to 14 of the same.
-Compound 1 described on pages 14 and 17 can be mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or improve the light resistance of the dye image. Examples of preferred ultraviolet absorbers include benzotriazoles, and particularly preferred compounds include compounds represented by the general formula III-3 described in JP-A-1-250944, and general formula III described in JP-A-64-66646. Compounds represented by, UV-1L ~ JP-A-63-187240
UV-27L, a compound represented by the general formula described in JP-A-4-1633, general formula (I), (II) described in JP-A-5-165144
The compound shown by is mentioned.

For the silver halide photographic light-sensitive material, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin are used. A hydrophilic colloid such as a sugar derivative, a cellulose derivative, a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.

As a hardener for these binders, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination. JP 61-249054
It is preferable to use the compounds described in JP-A No. 61-245153. Further, it is preferable to add an antiseptic agent and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of molds and bacteria which adversely affect the photographic performance and image storability. Further, in order to improve the physical properties of the surface of the light-sensitive material or the sample after processing, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.

Any material may be used as the support for the silver halide photographic light-sensitive material. Paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet. Polypropylene, which may contain a white pigment, polyethylene terephthalate support, baryta paper and 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, more preferably 15% by weight in order to improve the sharpness.

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

In the silver halide photographic light-sensitive material, 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, antistatic property). , One or more subbing layers for improving dimensional stability, abrasion resistance, hardness, antihalation property, frictional properties and / or other properties).

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

Using the above silver halide photographic light-sensitive material,
To form a photographic image, use the image recorded on the negative,
The image may be optically imaged and printed on the silver halide photographic light-sensitive material to be printed, or the image may be once converted into digital information and then the image may be imaged on a CRT (cathode ray tube). May be imaged and printed on the silver halide photographic light-sensitive material to be printed, or may be printed by changing the intensity of the laser light based on digital information and scanning.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and particularly preferably applied to a light-sensitive material for forming an image for direct viewing. Examples thereof include color papers, color reversal papers, light-sensitive materials for forming positive images, light-sensitive materials for displays, and light-sensitive materials for color proofs. In particular, it is preferably applied to a light-sensitive material having a reflective support.

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

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD- 6) 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD- 8) N, N-Dimethyl-p-phenylenediamine CD-9) 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10) 4-Amino-3-methyl-N-ethyl-N -(Β-Ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline In the present invention, the above uses the color developer in an arbitrary pH range. Yes, but quick From the viewpoint, it is preferably pH 9.5 to 13.0, and more preferably used in the range of pH 9.8 to 12.0.

The processing temperature for color development 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 conventionally 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 developing solution component compound can be added in addition to the above color developing agent. Usually, an alkaline agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazole, a preservative,
A chelating agent or the like is used.

The silver halide photographic light-sensitive material is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Further, as a substitute for the water 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, even if it is a roller transport type which conveys the light-sensitive material by sandwiching it between rollers arranged in a processing tank, the light-sensitive material is fixed to a belt. Although it may be an endless belt system that conveys by a process, a processing tank is formed in a slit shape, a processing solution is supplied to the processing tank and a photosensitive material is conveyed, and a spray method in which the processing solution is sprayed, A web method by contact with a carrier impregnated with a treatment liquid, a method by a viscous treatment liquid, or the like can also be used. When processing a large amount, it is usually a running process using an automatic processor, but at this time, the smaller the replenishing amount of the replenisher is, the more preferable the processing form from the environmental suitability is the tablet as a replenishing method. The method described in Published Technique 94-16935 is the most preferable.

[0164]

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 silver halide emulsion (Em-B101) prepared under the following conditions was mixed on a 120 μm-thick triacetyl cellulose film and mixed with an aqueous gelatin solution, and coated so that (gelatin / silver) = 0.60. A liquid was prepared. A surfactant (SU-2) was added as a coating aid to adjust the surface tension. Using this coating solution, coating was carried out so that the coating amount as silver was 1.2 g / m ² to prepare Denver electromotive force measurement sample 101.

SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt (preparation of blue-sensitive silver halide emulsion) 2% kept at 40 ° C.
The following (solution A) and (B
Solution) is added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) are added to pAg = 8.0, pH.
It was added simultaneously over 180 minutes while controlling to 5.5. At this time,
Control of pAg is carried out by the method described in JP-A-59-45437.
Control of H was performed using sulfuric acid or sodium hydroxide aqueous solution.

(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) Sodium chloride 102.7 g K ₂ IrCl ₆ 4 × 10 ^-8 mol K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol Potassium bromide 1.0 g Water added to 600 ml (D solution) Silver nitrate 300 g Water added to 600 ml After the addition was completed, a 5% aqueous solution of Demol N manufactured by Kao Atlas and sulfuric acid were added. After desalting with a 20% aqueous magnesium solution, it was mixed with an aqueous gelatin solution to obtain a monodispersed cubic emulsion (EMP- with an average grain size of 0.71 μm, a variation coefficient of grain size distribution of 0.07, and a silver chloride content of 99.5 mol%). I got 101).

The following compounds were used for the above (EMP-101):
Optimal chemical sensitization was performed at 0 ° C. to obtain a blue-sensitive silver halide emulsion (Em-B101).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB −3 3 × 10 ^-4 mol / mol AgX sensitizing dye (SPS-I-3) 4 × 10-4 mol / mol AgX sensitizing dye (SPS-I-11) 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 Next, blue sensitivity In the preparation of a silver halide emulsion (Em-B101), the compound (I-4) was added to the silver halide 1 immediately before the end of the chemical sensitization.
Blue sensitive silver halide emulsions (Em-B102) and (Em-B103) were prepared by adding 1 × 10 ⁻⁵ mol and 3 × 10 ⁻⁵ mol per mol. Furthermore, the compound was changed to (I-26) and (I-58) (Em-B104), (Em-B
105), (Em-B106) and (Em-B107) were prepared.

In preparing the silver halide photographic light-sensitive material sample 101, the blue-sensitive emulsion (Em-B101) was replaced with (Em-B102) to (Em-B10).
Samples 102 to 107 were prepared in the same manner except that the procedure was changed to 7).

(Measurement of Denver electromotive force) Each sample is 35 mm ×
It was cut into a size of 145 mm and left for 4 hours under the conditions of relative humidity of 20% and 80%. At this time, the temperature was about 26 ° C. The humidity-controlled sample was inserted between the electrodes, and the Denver electromotive force was measured. The irradiation light source of the Denver electromotive force measuring device has a wavelength of 337.1 nm, a pulse half width of about 2 nm, and an irradiation light intensity of 50 μm.
Using a J / cm ² laser, the sample sandwiched between two opposing electrodes (one transparent electrode) is irradiated with pulsed light from the transparent electrode side, and the induced voltage generated in the sample is input to the sampling oscilloscope. The transient time response of induced voltage was measured. The time constant of the measurement system was about 50 nanoseconds. Relative humidity 20
% And 80% of the two samples, the signal intensity 0.003 seconds after the peak of the induced voltage and the signal intensity of the peak were read from the data obtained, and the average value of these two signal intensities was calculated. , The time to give this intensity was calculated based on the time to give the peak of the signal (τ
₂₀ , τ ₈₀ ).

Next, based on the measurement data of 20% relative humidity, τ
Read the intensity I ₂₀ at a time corresponding to _80, read the intensity I ₈₀ corresponding to tau ₈₀ simultaneously from a relative humidity of 80% of the data.

For each sample (τ ₂₀ / τ ₈₀ ), (I ₂₀ /
I ₈₀ ) was calculated and summarized in Table 1 below.

[0174]

[Table 1]

When the compound (I-4) was used, the condition of the present invention was not satisfied at 1 × 10 ^-5 mol, but the compound of the increased amount satisfied the condition of the present invention. Although (Em-B106) does not satisfy the condition of the present invention with respect to τ, it is understood that the silver halide emulsion of the present invention is satisfied with respect to the condition of (I ₂₀ / I ₈₀ ). Thus, by using the compound of the general formula (I), it is possible to prepare an emulsion satisfying the conditions of the present invention.

Example 2 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side 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. After subjecting this reflective support to corona discharge treatment, a gelatin subbing layer was provided, and then each layer having the constitution shown below was coated to prepare a silver halide photographic light-sensitive material. The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34 g, (ST-5)
3.34 g, stain inhibitor (HQ-1) 0.34 g, image stabilizer A 5.0 g, high boiling organic solvent (DBP) 3.33 g and high boiling organic solvent (DNP) 1.67 g were dissolved by adding 60 ml of ethyl acetate. 7 ml of 20% surfactant (SU-1)
A yellow coupler dispersion liquid was prepared by emulsifying and dispersing in 220 ml of a 10% gelatin aqueous solution containing a using an ultrasonic homogenizer. This dispersion was mixed with the blue-sensitive silver halide emulsion (Em-B101 to Em-B107) prepared in Example 1 to prepare a coating solution for the first layer.

The coating solution for the second layer was prepared in the same manner as the coating solution for the first layer.

Further, as a hardening agent (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 .

[0180]

[Table 2]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-3: Di (2,2,3,3,4,4,5,5-octafluoropentyl) sulfosuccinate sodium salt DBP: Dibutyl phthalate DNP: Dinonyl phthalate H-1: Tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine
Sodium HQ-1: 2,5-di-t-octylhydroquinone Image stabilizer A: pt-octylphenol

[0182]

[Chemical formula 26]

The prepared silver halide photographic light-sensitive material (201-
207) is cut to a width of 120 mm, NPS-602QA (manufactured by Konica Corporation)
Konica color developed using the printer processor
Thirty sheets were continuously printed through LV-400 film to obtain a yellow dye image. The development process was carried out according to the following steps.

[0184] Treatment process Treatment temperature Time Replenishment amount Color development 38.0 ± 0.3 ℃ 45 seconds 80cc Bleach-fixing 35.0 ± 0.5 ℃ 45 seconds 120cc Stabilized 30-34 ℃ 60 seconds 150cc Dry 60-80 ℃ 30 seconds The composition of the developing solution is shown below.

Color developing solution tank solution and replenishing solution tank solution replenishing solution 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 pentaacetic acid sodium salt 2.0 g 2.0 g Fluorescence enhancement Whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to bring the total volume to 1 liter.
At 0, the replenisher is adjusted to pH = 10.60.

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

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

In the obtained image, a place having a density of about 1.0 was selected and the blue density of a PDA-65 densitometer (manufactured by Konica Corp.) was measured to obtain the difference between the maximum density and the minimum density. . The results are shown in Table 3 below.

[0189]

[Table 3]

Emulsion columns in Table 3, such as B-101, B
-301 represents Em-B101 and Em-B301. Others are the same.

In the case of the samples using the comparative silver halide emulsions, there was a density difference of 0.1 or more, whereas in the samples using the silver halide emulsion of the present invention, there was a difference in the density.
It was 0.07 or less, and it was found that the fluctuation of the concentration was small. However, the effect of the present invention was small in Sample 206, which was outside the conditions of the present invention under the condition of (τ ₂₀ / τ ₈₀ ).

Then, prints were similarly continuously produced by the short-time development processing in which the conditions of the processing liquid were changed as described below, and the fluctuation of the density was evaluated.

[0193] Treatment process Treatment temperature Time Replenishment amount Color development 38.0 ± 0.3 ℃ 22 seconds 81ml Bleach-fixing 35.0 ± 0.5 ℃ 22 seconds 54ml Stabilized 30-34 ℃ 25 seconds 150ml Dry 60-80 ℃ 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution replenisher pure water 800 ml 800 ml 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-methanesulfonamide Ethyl) -3-methyl-4-aminoaniline sulfate 6.5 g 10.5 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxyamine 3.5 g 6.0 g triethanolamine 10.0 g 10.0 g Diethylenetriaminepentaacetic acid sodium salt 2.0g 2.0g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to make the total volume 1 liter. Ten.
Adjust pH 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 100g 50g Diethylenetriamine pentaacetic acid 3g 3g Ammonium thiosulfate (70% aqueous solution) 200ml 100ml 2-Amino-5-mercapto-1 2,3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml Add water to make the total volume 1 liter. Add potassium carbonate or glacial acetic acid to the tank solution at pH = 7.0 and the replenisher to pH = 6.5. adjust.

Stabilizer tank solution and replenisher o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g 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) 10 ml Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

It was confirmed that the effects of the present invention can be effectively obtained even by such short-time development processing.

Example 3 A blue-sensitive silver halide emulsion was prepared by changing the addition timing of the compound (I-26), and the blue-sensitive silver halide emulsion was changed by changing the kind of the compound of the general formula (I) and the addition timing. A silver halide emulsion was prepared. At this time, if added before the completion of chemical sensitization, the addition amount is 3 × 10 ^-5 mol per mol of silver halide, and if added immediately after the start of chemical sensitization, it is 1 × 10 ^-5 mol. ,
When added at the time of preparing the coating solution, it was 4 × 10 ⁻⁵ mol.
The blue-sensitive silver halide emulsion was evaluated in the same manner as in Example 1 and Example 2, and the results shown in Table 4 below were obtained.

[0199]

[Table 4]

The emulsion column in the table, for example B301, is Em-.
It represents B301. Others are the same.

It can be seen that the samples satisfying the conditions of the present invention have a small concentration difference regardless of the type of compound and the time of addition. However, the silver halide emulsion (Em-B302), (Em-B30), which satisfies the condition τ but not the condition I,
It can also be seen that in (6) and (Em-B308), the density difference is slightly large. Example 4 In the preparation of the blue-sensitive silver halide emulsion (Em-B105) of Example 1, the sensitizing dye was changed as shown in Table 5 (Em-B401) to
(Em-B405) was prepared and evaluated in the same manner as in Example 1 and Example 2. At this time, when only one kind of sensitizing dye was used, the amount was increased so that the total amount became constant.

[0202]

[Table 5]

The emulsion column in the table, for example B-401, is Em.
Represents B401. Others are the same.

As shown in Table 5, the silver halide emulsion according to the present invention can obtain the effects of the present invention regardless of the type of sensitizing dye, and the fluctuation of density when printed continuously can be reduced. I understand.

Example 5 In Examples 1 to 4, a blue-sensitive silver halide emulsion was evaluated, but the compound of the general formula (I) was used in an amount of 3 per mol of silver halide before the completion of chemical sensitization. In addition to the addition of × 10 ^-5 mol, silver halide emulsions with different grain sizes were used. Also, green-sensitive and red-sensitive silver halide emulsions were prepared using various sensitizing dyes, and using this, the Denver electromotive force was used. A measurement sample and a monochrome sample for printing were prepared.

(Preparation of green-sensitive silver halide emulsion) (A
(Solution) and (solution B) and (C solution) and (solution D) addition time was changed to the same as (EMP-101) average particle size 0.40μm, coefficient of variation 0.08, silver chloride content A monodisperse cubic emulsion (EMP-601) having a rate of 99.5% was obtained.

The following compounds were used for the above (EMP-601):
Optimal chemical sensitization was performed at 5 ° C. to obtain a green-sensitive silver halide emulsion.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB −3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye 4 × 10 ⁻⁴ mol / mol AgX (preparation of red-sensitive silver halide emulsion) (solution A) and (solution B)
A monodisperse cube with an average particle size of 0.40 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% as in (EMP-101), except that the addition time of (C liquid) and the addition time of (C liquid) are changed. Emulsion (EMP
-602) was obtained.

The following compounds were used for the above (EMP-602):
Optimal chemical sensitization was performed at 0 ° C. to obtain a red-sensitive silver halide emulsion. However, when the sensitizing dye was used in combination, it was used in an equimolar combination, and the total amount was kept at the following amount.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB −3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye 2 × 10 ⁻⁴ mol / mol AgX In addition, for red-sensitive emulsion, SS-1 was added per mol of silver halide.
2.0 × 10 ^{−3 was} added.

In the single-color sample for printing, the green-sensitive silver halide emulsion was combined with a magenta coupler as shown in Table 6 below, and the red-sensitive silver halide emulsion was combined with a cyan coupler as shown in Table 7 below.

[0212]

[Table 6]

[0213]

[Table 7]

[0214]

[Chemical 27]

[0215]

[Chemical 28]

DIDP: Di-decyl phthalate DOP: Dioctyl phthalate Evaluation was carried out in the same manner as in Examples 1 and 2. Green density was measured in the sample using the magenta coupler and red density was measured in the sample using the cyan coupler. did. The results are summarized in Table 8 below.

[0217]

[Table 8]

Emulsion in the table, for example G-601, is Em.
-Represents G601. The same applies hereinafter.

As can be seen from Table 8, silver halide emulsions satisfying the conditions of the present invention, regardless of whether they are green-sensitive silver halide emulsions or red-sensitive silver halide emulsions, have the effect of reducing density fluctuation during print production. I found out.

The magnitude of the concentration fluctuation varies depending on (τ ₂₀ / τ ₈₀ ) and (I ₂₀ / I ₈₀ ), but the general formula (SPS-
(Em-B105) using the dye of I) and the general formula (SPS-I)
(Em-G602) using the dye of I), the general formula (SPS-II
As can be seen from the comparison with (Em-R603) using the dye of I), silver halide emulsions using the dye of the general formula (SPS-I) are most preferable because of their large effect.

Example 6 In Examples 1 to 5, the evaluation was carried out by using the monochromatic samples, but a multilayer sample was prepared by combining these and evaluated.

(Preparation of Blue-Sensitive Silver Halide Emulsion) In the preparation of (EMP-101) of Example 1, (A solution) and (B solution)
A monodispersed cubic emulsion having an average grain size of 0.64 μm, a variation coefficient of grain size distribution of 0.07, and a silver chloride content of 99.5 mol% in the same manner except that the addition time of the solution and the addition time of the solutions (C) and (D) were changed. (EMP-701) was obtained. (Em-B101), (Em-B105) of Example 1
(Em-B701) and (Em-B702) were prepared in the same manner except that (EMP-101) was changed to (EMP-701) in the above preparation.

(Em-B101) and (Em-B701) were mixed in a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B). Similarly, (Em-B105) and (Em-B702) were mixed in a silver amount of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B ′).

(Preparation of Green-Sensitive Silver Halide Emulsion) In the preparation of (EMP-601) of Example 5, addition time of (A solution) and (B solution) and addition of (C) solution and (D) solution were added. The average particle size is 0.50 μm, the coefficient of variation is 0.08, except that the time is changed.
A monodisperse cubic emulsion (EMP-702) having a silver chloride content of 99.5% was obtained. In the preparation of (Em-G601) and (Em-G602) of Example 5, (E
(Em-601) was changed to (EMP-702) above, and (Em-
G701) and (Em-G702) were prepared.

(Em-G601) and (Em-G701) were mixed in a silver ratio of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G). Similarly, (Em-G602) and (Em-G702) were mixed in a silver ratio of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G ').

(Preparation of Red-Sensitive Silver Halide Emulsion) In the preparation of (EMP-602) of Example 5, the addition time of (Solution A) and (Solution B) and the addition of Solution (C) and Solution (D). The average particle size is 0.38 μm, the coefficient of variation is 0.08, except that the time is changed.
A monodisperse cubic emulsion (EMP-703) having a silver chloride content of 99.5% was obtained. In the preparation of (Em-R601) and (Em-R602) of Example 5, (E
(MP-602) is changed to (EMP-703) above, and (Em-
R701) and (Em-R702) were prepared.

(Em-R601) and (Em-R701) were mixed in a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R). Similarly, (Em-R602) and (Em-R702) were mixed in a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R ').

When these emulsions were evaluated in the same manner as in Example 1, (Em-B), (Em-G) and (Em-R) were comparative silver halide emulsions not satisfying the conditions of the present invention. Yes, (Em-B '),
It was found that (Em-G ') and (Em-R') are silver halide emulsions satisfying the conditions of the invention. Sample 701 was prepared according to the configurations shown in Tables 9 and 10 below, and a silver halide emulsion (Em-B) was prepared.
From (Em-G), (Em-R) to (Em-B '), (Em-G'), (Em-G ')
R ′) was changed to prepare Sample 702.

[0229]

[Table 9]

[0230]

[Table 10]

PVP: Polyvinylpyrrolidone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec- Tetradecyl hydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butyl hydroquinone

[0232]

[Chemical 29]

Next, the samples 701 and 702 were cut into a roll shape, and after adjusting the printing conditions with each color photographic paper,
Color prints were continuously prepared in the same manner as in Example 2. The best print quality was almost the same for all samples, but when looking at all prints, sample 702 showed some color balance deviations, but corrected the color deviations. It was possible to obtain an excellent quality color print that does not need to be processed.
The color variation was noticeable at a color balance close to gray. It was confirmed that a high-quality color print can be stably obtained with the color photographic paper produced using the silver halide emulsion according to the present invention.

Further, as an automatic developing machine, manufactured by Konica Corporation
NPS-868J, ECOJET-P was used as a treatment chemical, and running treatment was performed according to process name CPK-2-J1. Using this development processing line, a print was prepared and evaluated in the same manner as above, and it was confirmed that the effects of the present invention were obtained.

[0235]

INDUSTRIAL APPLICABILITY The silver halide emulsion according to the present invention is capable of producing a color image when a plurality of color prints are prepared from the same negative of a silver halide emulsion containing a high concentration of silver chloride capable of rapid processing. An excellent image that does not fluctuate can be obtained.

─────────────────────────────────────────────────── --Continued from the front page (56) References JP-A-2-124567 (JP, A) JP-A-2-139552 (JP, A) JP-A-3-219232 (JP, A) JP-A-6- 194780 (JP, A) Special table Sho 63-502222 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/34 G03C 1/015 G03C 1/035

Claims (6)

(57) [Claims] 1. A silver chloride content of 95 mol% or more, and a ratio of decay time of Denver electromotive force at relative humidity of 20% and 80% is 0.9 ≦ τ ₂₀ / τ ₈₀ ≦ 1.1. Silver halide emulsion. Here, τ ₂₀ and τ ₈₀ represent the decay time of Denver electromotive force at relative humidity of 20% and 80%, respectively, and the signal intensity is (peak intensity + peak intensity + (Signal intensity 0.003 seconds after peak)
It is the time that becomes / 2. 2. The silver chloride content is 95 mol% or more, and τ ₈₀
The silver halide emulsion ratio of the intensities of the relative humidity of 20% and 80% of the Denver electromotive force signal at times is equal to or is _{0.9 ≦ I 20 / I 80 ≦} 1.3. 3. A relative humidity of 20% at the time of τ ₈₀
Silver halide according to claim 1, characterized in that the ratio of the signal intensities of the 80% Denver electromotive force is 0.9 ≤ I ₂₀ / I ₈₀ ≤ 1.3.
emulsion. 4. A compound represented by the following general formula (I) is included.
It has, It describes in any one of Claims 1-3 characterized by having.
The listed silver halide emulsion. [Chemical 1] [Wherein R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom or an alkyl group]
Group, alkenyl group, alkynyl group, aryl group or compound
Represents a cyclic group, and R ₅ , R ₆ , R ₇ and R ₈ each represent a substituent.
You L ₁ and L ₂ each represent a methine group, and Z ₁ is an oxygen source
Child, sulfur atom, selenium atom, tellurium atom, -C (R ₉ ).
(R ₁₀₎ - or -N (R ₉₎ - represents a. R ₉ and R ₁₀ are each
Hydrogen atom, alkyl group, alkenyl group, alkynyl
Represents a group, an aryl group or a heterocyclic group. Also, R ₁ and R ₂ , R
₃ and R ₄ , R ₉ and R ₁₀ are bonded to each other to form a ring.
Good. ] 5. The silver chloride content is 98 to 99.9%.
The method according to any one of claims 1 to 4, characterized in that
Silver rogenide emulsion. 6. A dye containing a dye represented by the following general formula (SPS-I):
It has, It describes in any one of Claims 1-5 characterized by having.
The listed silver halide emulsion. [Chemical A] (In the formula, Z ₁₁ and Z ₁₂ are an oxazole nucleus and a thiazole, respectively.
Nucleus, selenazole nucleus, pyridine nucleus, benzoxazole
Nucleus, benzothiazole nucleus, benzoselenazole nucleus, Ben
Timidazole nucleus, naphthoxazole nucleus, naphthothia
Zole nucleus, naphthoselenazole nucleus, naphthimidazole
List the atomic groups required to form the nucleus or quinoline nucleus.
R ₁₁ and R ₁₂ are each an alkyl group, an alkenyl group, or
Represents an aryl group. X ^- represents an anion, m is 0 or
Or represents 1. )