JP2000075432A - Silver halide photographic emulsion and silver halide photographic sensitive material containing same and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide color printing material capable of obtaining an always sufficient maximum density and proper gradation in the wide exposure time range of 106-100 sec and preventing impairment of quality even in the case of storing the color printing material for a long period at room temperature. SOLUTION: The silver halide photographic emulsion is characterized that it is prepared including a process for adding the minute grain emulsion high in silver chloride content containing a photographic useful compound and an average grain diameter of the minute grain emulsion high in silver chloride content is <=1/2 of that of the emulsion high in silver chloride (a host emulsion) into which a minute grain emulsion is to be added and >=0.01 μm and the average silver chloride content of the minute grain emulsion high in silver chloride is >=80 mol%, and a kind of the photographic useful compound contained in the minute grain emulsion high in silver chloride content is an iridium compound, and the above-mentioned features are the character of this invention.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photograph capable of always obtaining a stable and high-quality print regardless of a conventional analog exposure system and a recent digital exposure system, or a surface exposure system and a scanning exposure system. Regarding the photosensitive material, in detail, a halogen that can always obtain a sufficient maximum density and an appropriate gradation in a wide exposure range of about 10 ^{-6 to} 100 seconds and that does not impair the quality even when stored at room temperature for a long time. It relates to a silver halide color print material.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials (hereinafter, also referred to as "photographic light-sensitive materials" or simply as "light-sensitive materials") are other light-sensitive materials having high sensitivity and excellent gradation. It has very excellent characteristics as compared with, and is widely used today. In recent years, printers, automatic processors and other equipment have been improved, developing solutions have been improved, and the performance of photographic photosensitive materials has been improved. With the spread of so-called mini-labs that can process images, photography has become more familiar. On the other hand, there is an increasing demand for a high quality print image to be provided easily and stably in a short period of time, even without a skilled technician.

[0003] In recent years, with the rapid trend toward digitization, the opportunities for digital exposure using a laser beam or the like to photographic photosensitive materials have been increasing. Along with this, the suitability for exposure to light with high illuminance in a very short time of about millisecond to nanosecond and the suitability for scanning exposure have been required. At the same time, in response to the rapid progress of other non-silver salt output media such as the inkjet system,
There is a strong demand for further evolution of photographic light-sensitive materials that are advantageous in image quality, cost, and mass productivity.

Conventionally, color paper, which is a photographic light-sensitive material for color printing, has been strongly demanded for faster processing performance.
By using a silver chloride emulsion or a silver halide emulsion having a high silver chloride content as the silver halide emulsion to be used, rapid color development has been achieved. For example, US Pat.
Nos. 3,756, 4,225,666;
No. 26589, No. 58-91444, No. 58-953
No. 39, No. 58-94340, No. 58-95736
No. 58-106538, No. 58-107531
No. 58-107532, No. 58-107533
Nos. 58-108533, 58-125612, and the like, describe the technology. With the introduction of these technologies, current color papers have been devised so that high-quality images can be obtained by development processing for only several tens of seconds.

On the other hand, it is generally known that doping with an iridium compound is effective for improving reciprocity failure characteristics, which is one of the problems of silver halide emulsions. For example, JP-A-51-139323, JP-A-59-1
No. 71947 discloses that inclusion of a Group 8 metal compound in the periodic table can improve reciprocity failure and increase sensitivity. Also, JP-B-49-3378
No. 1, JP-A-50-23618, JP-A-52-18310
No. 58-15952, No. 59-214028,
No. 61-67845 discloses that by containing a rhodium compound or an iridium compound, reciprocity failure can be improved and a high contrast can be achieved.

[0006] However, in the improvement of reciprocity failure characteristics of a silver chloride emulsion or a silver halide emulsion having a high silver chloride content imparted with rapid processing suitability, the above-mentioned means involves deterioration of latent image stability. Was inadequate.

To solve this, for example, Japanese Patent Laid-Open No.
Japanese Patent No. 105940 discloses a technique of doping a specific region with an iridium compound.
A technique has been disclosed in which an iridium compound and an iron compound are contained on the surface side in an amount of 50% or more of the particle volume to reduce reciprocity failure and a change in development density in processing with time after exposure. On the other hand, Japanese Patent Application Laid-Open No. 5-283838 discloses a technique for containing a compound such as gallium, germanium, indium, and thallium which has a localized phase of silver bromide. A technique for containing a metal complex having a ligand in a silver halide grain, and a technique for containing two kinds of specific metal complexes in the grain are disclosed in JP-A-6-102609. And stability of latent image stability.

US Pat. No. 4,933,272 discloses a halogen having a face-centered cubic lattice containing a complex having a nitrosyl or thionitrosyl ligand, having a metal element of Group 5 to 10 of the periodic table as a central metal. It is disclosed that a silver halide photographic emulsion can improve reciprocity failure and obtain hard characteristics. Similar techniques are disclosed in JP-A-6-235994, JP-A-6-235993, JP-A-6-235592, and JP-A-6-25992.
No. 42539, and the like, which discloses that high contrast characteristics can be obtained. Further, JP-A-5-50
No. 8036 shows the reciprocity failure and the effect of improving latent image stability in a silver halide emulsion containing a complex having a nitrosyl ligand and containing an iridium compound in the outer 10% of the grain volume. Have been. Similar techniques are disclosed in JP-A-8-179454 and JP-A-8-212529.
And Japanese Patent Application Laid-Open No. 8-212530, which describe that high contrast can be obtained by hardening the leg gradation.

Various known methods are known for doping a silver halide grain with a target metal compound.
In particular, when silver bromide fine particles doped with a target metal in advance are added to the host emulsion, the target metal can be doped into a localized portion having a high silver bromide content, and other performance improvements including reciprocity failure are accompanied. It is stated in some patents and the like that it is advantageous. For example, the description is found in JP-A-64-26837 and JP-A-3-156439, and the above-mentioned JP-A-8-179454 and 8-21 are mentioned.
No. 1529 also describes an example in which silver bromide fine particles known as Lippmann particles are doped in advance with a target compound and added to a host emulsion.

Japanese Patent Application Laid-Open No. 8-248553 discloses a method for finishing silver halide grains, which comprises adding a silver halide fine grain emulsion having a photographically useful compound attached thereto to a high silver chloride emulsion. Have been. However, in the embodiment of the present invention, an antifoggant is adsorbed to silver bromide fine particles to form an epitaxy bonding to a high silver chloride host emulsion, and the fog increase during long-term storage of the photosensitive material is efficiently suppressed. Is the object of the invention, which is completely different from the object and idea of the present invention.

Japanese Patent Application Laid-Open No. 7-306488 discloses a halogen containing a higher concentration of iridium ions and having a guest portion having a halogen composition substantially equal to that of the host particle surface with respect to the iridium ion-containing host particles. Silver halide particles are claimed. However, the embodiment of the present invention is a tabular grain having a high silver bromide composition containing a small amount of silver iodide, and is mainly intended to improve reciprocity failure in a photographic light-sensitive material such as a color film. This is completely different from the present invention which proposes a method for improving the digital exposure suitability of a high silver chloride emulsion for producing color prints.

In US Pat. No. 5,627,020, the preparation of a silver halide emulsion in which silver bromide fine particles containing an iridium compound in advance are added to a high silver chloride emulsion, the silver bromide content and the iridium compound content are described. A technique has been disclosed in which the amount is defined in accordance with a certain correlation equation so as to provide suitability for exposure at high illuminance.

When exposing digital information to a photographic light-sensitive material, a method of performing high illuminance exposure in a very short time by using, for example, a laser beam is generally used. Therefore, when photographic performance conforming to the digital exposure method is intended, it is necessary to provide high illuminance exposure suitability in the millisecond to nanosecond range. Although the method described in the above-mentioned US Pat. No. 5,627,020 and the like can certainly improve the short-time exposure suitability under high illuminance, on the other hand, in the conventional analog-type exposure, the enlargement is particularly large. It has been clarified that the suitability is remarkably impaired at the time of long-time exposure.

Further, the technique described so far is characterized in that metal compounds such as iridium are concentrated in a localized phase of silver bromide near the surface of the grains, and thus the silver bromide during chemical sensitization or the like is characterized. In many cases, a device (for example, reaction temperature or the like) for preventing dispersion of the existing phase is required.

There are many problems that can be solved by forming a silver bromide localized phase in such high silver chloride grains and functionally controlling doping. Several performance degradations, presumed to be due to poor stability, were revealed in our studies. For example, it has been found that when the print material before exposure prepared by the above-described method is stored for a long period of time or stored under high-temperature conditions, fogging is significantly generated and the print material is not practical.

The present inventors have developed a print output material which is not easily affected by the length of the storage period and storage conditions, regardless of the exposure system such as the analog system or the digital system, and which can always obtain a stable print easily. The research has been repeated with the aim of providing the device at a lower cost, and the above disclosed technology is completely insufficient for that purpose.

Other techniques applicable to digital exposure methods include a chemical and color sensitization method suitable for forming a silver bromide localized phase described in US Pat.
There are methods using silver iodochloride emulsions described in JP-A Nos. 50,222 and 772,079 and the like, but they have been insufficient and have not been sufficient for realizing the above object of the present inventors.

On the other hand, using silver chloride emulsion grains as a host, silver halide fine grains having a high silver chloride content
There are few examples of adding a photographically useful compound such as a metal compound. For example, JP-A-7-225440 describes a method of doping mercury chloride into silver chloride fine particles in advance as a means for introducing a mercury compound into high silver chloride (100) tabular grains during the preparation of the grains. is there. However, in this case, silver chloride fine particles were merely used for the purpose of introducing a mercury compound into the tabular grains, and the purpose intended by the present invention is not described at all.

As described above, most of the prior art has always been about doping epitaxy junctions having different lattice constants. By doping non-epitaxy junctions or controlling local compound-containing sites, It was completely unexpected that an excellent improvement effect as in the present invention could be obtained.

[0020]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide emulsion containing silver chloride or a silver halide emulsion having a high average silver chloride content and having a stable exposure time in a wide exposure range of about 10 ^{-6 to} 100 seconds. An object of the present invention is to provide a silver halide emulsion which can provide a sufficient maximum density and an appropriate gradation, and suppress generation of fog even when stored at room temperature for a long time. An object of the present invention is to provide a photosensitive material and an image forming method for scanning and exposing the photographic material.

[0021]

DISCLOSURE OF THE INVENTION The present inventors have developed a color photographic method capable of obtaining a stable, high-quality print in a very short time regardless of the conventional analog surface exposure method or the latest digital scanning exposure method. While studying materials,
It has been found that the above object of the present invention is achieved by the following constitutions.

(1) A silver halide photographic emulsion prepared by adding a high silver chloride fine grain emulsion containing a photographically useful compound to a high silver chloride emulsion.

(2) The average grain size of the high silver chloride fine grain emulsion is
The average grain size of a high silver chloride emulsion (hereinafter, referred to as a host emulsion) to which the fine grain emulsion is added is 以下 or less,
The silver halide photographic emulsion according to (1), which is not less than 01 μm.

(3) The silver halide photographic emulsion according to (1) or (2), wherein the high silver chloride fine grain emulsion has an average silver chloride content of 80 mol% or more.

(4) The silver halide photographic emulsion according to (1), (2) or (3), wherein both the host emulsion and the high silver chloride fine grain emulsion have an average silver chloride content of 95 mol% or more.

(5) The silver halide photographic emulsion according to any one of (1) to (4), wherein the high silver chloride fine grain emulsion is added to the host emulsion after completion of the grain formation process of the host emulsion. .

(6) The compound according to any one of (1) to (5), wherein the photographically useful compound contained in the high silver chloride fine grain emulsion is a compound containing a Group 8 metal of the periodic table. Silver halide photographic emulsion.

(7) The silver halide photograph according to any one of (1) to (6), wherein at least one of the photographically useful compounds contained in the high silver chloride fine grain emulsion is an iridium compound. emulsion.

(8) The silver halide photographic emulsion according to (7), wherein the iridium compound is a compound having a bromine atom in at least one of the ligands.

(9) The silver halide photographic emulsion according to (7), wherein the host emulsion contains a metal compound satisfying the following condition A:

Condition A: The metal compound was uniformly added at 1 × 10 ⁻⁸ mol per mol of silver halide, and the average side length was 0.4.
The decay time of the photoconductivity signal in the induced absorption of the microwave photoconductivity measurement of a silver halide emulsion composed of a silver chloride cubic crystal having a thickness of .mu.m was determined by replacing the metal compound with an equimolar amount of potassium hexachloroiridate (IV). It is shorter than the decay time of the photoconductivity signal of the silver emulsion.

(10) The silver halide photographic emulsion according to (7), wherein the high silver chloride fine grain emulsion is added to the host emulsion before the chemical sensitizer.

[0033] (11) the average content of silver 95 mol% or more of high silver chloride emulsion chloride, halide per mole ^10-9 inside the particles between up to 50% from the center in the emulsion grain volume
^A silver halide photographic emulsion containing ^-7 moles of an iridium compound and containing an iridium compound in an amount of 10 to 1000 times the amount of iridium inside the grains in the vicinity of the grain surface at a grain volume of 90 to 100% from the center.

(12) A silver halide photographic material containing at least one of the emulsions described in any one of (1) to (11).

(13) An image forming method for scanning and exposing the silver halide photographic material as described in (12).

Hereinafter, the present invention will be described in more detail.

The silver halide photographic emulsion according to the present invention (hereinafter also referred to as the emulsion of the present invention) has a high silver chloride content.
It is a so-called high silver chloride emulsion. In particular, a high silver chloride emulsion in which 95 mol% or more is silver chloride is preferable. In this case, a silver halide emulsion having any halogen composition such as silver chloride, silver chlorobromide, silver chloroiodobromide, silver chloroiodide, etc. However, silver chlorobromide and silver chloroiodide containing 97 mol% or more of silver chloride are particularly preferable. From the rapid processing and processing stability,
More preferably, it is a silver halide emulsion containing 98 to 99.9 mol% of silver chloride.

One preferred embodiment of the emulsion according to the present invention is a method of preparing a photographically useful compound separately prepared in a so-called host emulsion having a relatively large grain size during grain growth or after grain growth. Is a silver halide emulsion prepared by including a step of adding a silver halide fine grain emulsion as a so-called guest, and comprising a silver halide grain having a guest portion deposited on a host grain or in a grain.

In this case, the temperature at which the silver halide fine grain emulsion serving as the guest is added and deposited on the host emulsion is:
It may be arbitrarily selected within a range in which the fine grain emulsion can be dissolved and deposited on the host emulsion, but the temperature is preferably from 30 to 80C.

The fine grain emulsion can be added at any time during the formation of silver halide host grains, during physical ripening after formation of silver halide host grains, or during chemical sensitization. For example, it may be carried out successively after grain formation, after the desalting step, or after chemical sensitization,
In order to further bring out the effects of the present invention, it is preferable after the completion of host particle formation.

In a preferred embodiment of the present invention, the fine grain emulsion is added to the surface of the host grain after the formation of the grains of the host and before the so-called chemical sensitizer for chemical sensitization is added. It is particularly preferred to have the guest part deposited on top. In the present invention, all compounds added for the purpose of performing chemical sensitization are referred to as chemical sensitizers.

Various methods known in the art can be used for preparing silver halide fine grain emulsions. When the reaction mother liquor is concentrated after the preparation of the fine particle emulsion, concentration by ultrafiltration is preferably used.

The average grain size of the silver halide fine grain emulsion used in the present invention is not more than 1/2 of the average grain size of the silver halide emulsion used as a host and 0.01 μm or more. Is preferably 1/3 or less, particularly preferably 1/4 or less. The average particle size of the host emulsion is not particularly limited, but is preferably 0.1 to
The average particle diameter of the silver halide fine grain emulsion used as a guest is preferably from 0.01 to 0.5 μm, more preferably from 0.2 to 1.0 μm, and more preferably from 0.2 to 1.0 μm. It is 0.01 to 0.1 μm.

If the silver halide fine grain emulsion is a so-called high silver chloride emulsion having a high silver chloride content, an arbitrary halogen composition such as silver chloride, silver chlorobromide, silver chloroiodobromide and silver chloroiodide is used. However, silver chlorobromide containing 80 mol% or more of silver chloride and containing substantially no silver iodide is preferred. In particular, it is preferable that the fine grain emulsion has a silver chloride content of 95 mol% or more together with the host emulsion.
More preferably, a fine grain emulsion having the same halogen composition as the host emulsion is used, and a fine grain emulsion substantially consisting of silver chloride is used.

In these embodiments, the amount of the silver halide fine grain emulsion added as a guest can be any amount according to the purpose as long as the effects of the present invention are not impaired.
It is preferably at most 10 mol%, more preferably at most 5 mol%, of the silver halide emulsion serving as a host.

The present invention is characterized in that a silver halide fine grain emulsion serving as a guest contains a photographically useful compound in advance.

The photographically useful compounds in the present invention mean all compounds used for the purpose of improving the photographic performance of the prepared silver halide emulsion. For example, compounds such as dopant agents, antifoggants, chemical sensitizers, gold sensitizers, and color sensitizing dyes all correspond to this.

The amount of these compounds to be added to the silver halide fine grain emulsion can be arbitrarily set according to the type and purpose of the compounds, but is preferably from 10 ^-8 to 10 ^-1 mol per mol of silver halide.

In one preferred embodiment of the present invention, the high silver chloride fine grain emulsion contains a compound containing a metal belonging to Group 8 of the periodic table as a dopant in advance. As the metal compound that can be used for this purpose, a compound represented by the following general formula [II] is preferable.

Formula [II] R _n [MX _m Y _6-m ] In the formula, M represents a metal selected from Group 8 elements of the periodic table, and is preferably iron, cobalt, ruthenium, rhodium,
Osmium, nickel, palladium and iridium. R represents an alkali metal atom, preferably sodium or potassium. m represents an integer of 0 to 6, and n represents an integer of 2 or 3.

X and Y each represent a ligand of the above metal complex;
Groups such as nitrosyl, thionitrosyl and carbonyl are preferred, and compounds in which some or all of the ligands are halide ions can also be preferably used.

In particular, iridium compounds have a large effect and are preferably used. Among them, an iridium compound containing a bromine atom in at least one of the ligands is particularly preferable.
The following are representative examples of preferred iridium compounds,
The present invention is not limited to this.

II-1: K ₂ [IrCl ₆ ], II-2: K ₃
[IrCl ₆ ], II-3: K ₂ [Ir (CN) ₆ ], II-4: K ₃ [Ir (C
N) ₆ ], II-5: K ₂ [Ir (NO) Cl ₅ ], II-6: K ₃ [Ir
(NO) Cl ₅ ], II-7: K ₂ [IrBr ₆ ], II-8: K ₃ [IrBr ₆ ], II-9: Na ₂ [IrBr ₆ ], II-10: Na ₃ [Ir
Br ₆ ], II-11: K ₂ [IrBr ₄ Cl ₂ ], II-12: K ₃ [I
rBr ₄ Cl ₂ ], II-13: K ₂ [IrBr ₃ Cl ₃ ], II-14: K ₃ [I
rBr ₃ Cl ₃ ], II-15: K ₂ [IrBr ₅ Cl], II-16: K ₃ [Ir
Br ₅ Cl], II-17: K ₂ [IrBr ₅ I], II-18: K ₃ [IrB
r ₅ I], II-19: K ₂ [IrBr ₅ (H ₂ O)], II-20: K ₃
[IrBr ₅ (H ₂ O)] These iridium compounds may be used in combination of a plurality of compounds, or other metal compounds or photographically useful compounds will not impair the effects of the present invention. Any combination may be used within the range. The addition amount of the iridium compound to the silver halide fine grains is preferably from 10 ^-7 to 10 ^-2 mol, more preferably from 10 ^-5 to 10 ^-3 mol, per mol of silver halide.

[0054] Also, as a result of the deposited host grains as a guest by fine particles, the amount of iridium compound to be contained in a silver halide emulsion that is eventually prepared, per mol of silver halide ^{10-8 - It} is preferably ⁴ mol, more preferably 10 ^-8 to 10 ^-6 mol.

In order to make the silver halide fine grain emulsion contain a photographically useful compound in advance, the compound may be added during grain formation of the fine grain emulsion. As a preferable method, the compound may be dissolved together with the halide salt and added continuously over the whole or a part of the grain forming step, and particularly, the compound is added over the entire grain forming step. Is preferred.

It is advantageous that the emulsion of the present invention contains a metal ion. In particular, it is preferable to add a metal ion to a host emulsion to which a high silver chloride fine grain emulsion containing the above photographically useful compound is added as a guest.

Examples of such a metal ion include metals belonging to Groups 8 to 10 of the periodic rule such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium and cobalt; and Group 12 metals such as cadmium, zinc and mercury. Examples include transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, chromium and the like. Among them, metal ions such as 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 metal ion forms a complex, cyanide, thiocyanic acid,
Examples include ions of isothiocyanic acid, cyanic acid, chloride, bromide, iodide, nitric acid, carbonyl, ammonia and the like. Among them, cyanide, thiocyanic acid,
Isothiocyanic acid, chloride and bromide ions are preferred.

In order for the emulsion of the present invention and the above-mentioned host emulsion to contain metal ions, the metal compound is physically added before, during, or after silver halide grains are formed. It may be added at any place in each step during ripening, but it is preferable to dissolve the metal compound together with the halide salt and to continuously add it over the whole or a part of the grain forming step.

The amount of the metal ion added to the host emulsion is from 1 × 10 ^-9 to 1 × per mol of silver halide.
It is preferably 10 ^-2 mol, particularly preferably 1 × 10 ^{-9 to} 5 × 10 ^-6 mol.

One of the preferred embodiments of the emulsion of the present invention contains 10 ^-9 to 10 ^-7 mol of an iridium compound per mol of silver halide in the interior of the grain up to 50% from the center of the grain volume. 90 to 100 from the center in terms of particle volume
% Of the iridium content inside the particle near the particle surface of 10%.
A silver halide emulsion containing an iridium compound in an amount of up to 1000 times.

As a method for preparing such silver halide grains, for example, a plurality of types of halide solutions obtained by dissolving a target iridium compound together with a halide salt are prepared with different concentrations of the iridium compound. In addition, the silver halide grains may be switched at an arbitrary stage to precipitate the silver halide grains. At this time, the iridium compound which is added until the formation of the target silver halide grains is completed by 50% by volume, and which is considered to be contained in the grains, is 10 ^-9 to 1 mol per mol of silver halide. It may be in the range of 10 ^-7 mol. Then, grain formation is continued, and after the formation of the target silver halide grains is completed by 90% by volume, 100 grains are formed.
% Of the iridium compound added until the completion of the iridium compound and considered to be contained in the particles is adjusted to be 10 to 1000 times the number of moles of the iridium compound at the time of the 50% completion. do it.

Specifically, 10 ^-9 to 10 ^-7 mol of an iridium compound is contained per mol of silver halide within 50% of the grain volume, and 90 to 100% of the grain volume near the grain surface is contained. Between 10 and 10 per mole of silver halide
^It is preferable to contain ^-8 to 10 ^-5 mol of the iridium compound, and it is more preferable that the iridium compound be contained between 95 and 100% even in the vicinity of the particle surface.

The iridium compound contained in the particle and in the vicinity of the particle surface includes, for example, the above-mentioned exemplified compound II-
1 to II-20 can be preferably used.

The iridium compound may contain the same compound inside the particle and near the particle surface, or may be different. Further, a plurality of compounds may be contained in combination. It is also preferable to use other metal compounds in an optional combination as long as the effects of the present invention are not impaired.

In one preferred embodiment of the emulsion of the present invention, the host emulsion to which the above-mentioned photographically useful compound, particularly a high silver chloride fine grain emulsion containing an iridium compound is added as a guest, satisfies the condition A. It is to contain a metal compound.

Here, the condition A is defined as a micro-size of a silver halide emulsion comprising a silver chloride cubic crystal having an average side length of 0.4 μm and uniformly adding 1 × 10 ^-8 mol of the metal compound per mol of silver halide. The decay time of the photoconductivity signal in the induced absorption of the wave photoconductivity measurement is less than or equal to the decay time of the photoconductivity signal of a silver halide emulsion in which the metal compound is replaced with potassium hexachloroiridate (IV) in an equimolar amount. It is.

A silver halide emulsion composed of cubic silver chloride having an average side length of 0.4 μm and uniformly added with a metal compound satisfying the condition A can be prepared by a known method. For example, it can be easily prepared by a double jet method.
What is necessary is just to add and prepare an amount equivalent to containing 1 × 10 ⁻⁸ mol per mol, and mix this with an aqueous silver salt solution.

Microwave photoconductivity measurement characterizing the metal compound according to the present invention is a well-known method in the art for evaluating the physical properties of silver salt photographic emulsions.
L. M. Kellog, Photographic Science and Engineering, 18, 378 (1
974) can be measured with reference to the method described therein. The measurement of microwave photoconductivity in the present invention was performed according to the description in JP-A-5-45758. Further, the decay time of the photoconductivity in the microwave photoconductivity measurement of the present invention is defined by the time required to decay to half the peak intensity.

The decay time of the photoconductivity signal in the induced absorption of the microwave photoconductivity measurement was determined by adding potassium hexachloroiridate (IV) to 1 × per mole of silver halide.
The metal compound for obtaining an emulsion which is not more than a silver halide emulsion composed of silver chloride cubic crystals having an average side length of 0.4 μm and uniformly added at 10 ⁻⁸ mol (hereinafter referred to as a comparative emulsion under condition A) includes: Certain metal complexes can be preferably used. As the metal complex that can be used for this purpose, a metal complex represented by the following general formula [I] is preferable.

[0071] In the general formula (I) _{^{R 1 n1 [M 1 X 1}} m1 Y 1 6-m1] formula, M ¹ is a metal selected from Group 8 elements of the periodic table, preferably iron, cobalt, Ruthenium, rhodium, osmium, nickel, palladium and iridium. R ¹ represents an alkali metal atom, preferably sodium or potassium. m ₁ is Less than six, n ₁ is 2
Represents an integer of 5.

X ¹ and Y ¹ each represent a ligand of the above metal complex, preferably a group such as nitrosyl, thionitrosyl, carbonyl and the like, and a compound in which some or all of the ligands are halide ions is also preferably used. Can be

The amount of the metal compound according to the present invention is preferably from 10 ^-9 to 10 ^-5 mol per mol of silver halide. It is preferable that these metal compounds be present in the inside of the particles of 50% or less of the particle volume.

The following compounds can be mentioned as typical examples of preferably used metal compounds.

I-1: K ₂ [RuCl ₆ ], I-2: K ₂
[PtCl ₆ ], I-3: K ₂ [Pt (SCN) ₄ ], I-4: K ₂ [Ni
Cl ₄ ], I-5: K ₂ [PdCl ₆ ], I-6: K ₃ [RhC
l ₆ ], I-7: K ₂ [OsCl ₆ ], I-8: K ₂ [ReC
l ₆ ], I-9: K ₃ [RhBr ₆ ], I-10: K ₃ [Mo (O
CN) ₆ ], I-11: K ₃ [Re (CNO) ₆ ], I-12: K
₄ [Ru (CNO) ₆ ], I-13: K ₄ [Fe (CNO) ₆ ], I-14: K
₂ [Pt (CNO) ₄ ], I-15: K ₃ [Co (NH ₃ ) ₆ ], I-16: K ₅ [C
o ₂ (CNO) ₁₁ ], I-17: K ₃ [Re (CNO) ₆ ], I-18: K
_{4 [Os (CNO) 6]} , I-19: Cs 2 [Os (NO) Cl 5], I-20: K 2 [Ru (NO) Cl 5], I-21: K 2
_{[Ru (CO) Cl 5]} , I-22: Cs 2 [Os (CO) Cl 5], I-23: K 2 [Fe (NO) (CN) 5], I-24: K 2 [Ru ( _{NO) Br 5], I-} 25: K 2
_{[Ru (NO) I 5]} , I-26: K 2 [Re (NO) (CN) 5], I-27: K 2 [Re (NO) Cl 5], I-28: K 2
_{[Ir (NO) Cl 5]} I-29: K 2 [Ru (NS) Cl 5], I-30: K 2
_{[Os (NS) Br 5]} I-31: K 2 [Ru (NS) (CN) 5] I-32: the shape of _{K 2 [Ru (NS) (} SCN) 5] Silver halide grains according to the present invention Can be used as long as it has a high silver chloride composition. One preferable example is a cube having a (100) plane as a crystal surface. No. 4,183,75.
No. 6,225,666, JP-A-55-2658.
9, No. 55-42737, and The Journal
Of Photographic Science (J. Photo
ogr. Sci. ) Particles having shapes such as octahedron, tetradecahedron, and dodecahedron can be produced by a method described in a document such as Vol. 21, p. 39 (1973) and used. Further, particles having a twin plane may be used.

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

The grain size of the silver halide grains is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.2 to 1.2 μm, in consideration of other photographic properties such as rapid processing and sensitivity. The range is 1.0 μm. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The distribution of the grain size of the silver halide grains is preferably a monodispersed silver halide grain having a coefficient of variation of 0.05 to 0.22, more preferably 0.05 to 0.15.
Particularly preferably, two or more monodispersed emulsions of 0.05 to 0.15 are added to the same layer. Where the coefficient of variation is
This is a coefficient indicating the width of the particle size distribution, and is defined by the following equation.

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

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

The silver halide emulsion may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at a time, or may be grown after seed particles have been produced. The method for producing the seed particles and the method for growing the seed particles may be the same or different.

The form of reacting the soluble silver salt with the soluble halide may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but the method obtained by the simultaneous mixing method is preferable. . Further, as one form of the simultaneous mixing method, pA described in JP-A-54-48521 and the like are described.
g The controlled double jet method can also be used.

Further, JP-A-57-92523 and JP-A-57-92523.
No. 92524, etc., a device for supplying a water-soluble silver salt and a water-soluble halide aqueous solution from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt described in DE 2,921,164. And an apparatus for continuously adding an aqueous solution of a water-soluble halide while changing its concentration, Japanese Patent Publication No. 56-5017.
No. 76, etc., a reaction mother liquor may be taken out of the reactor and concentrated by an ultrafiltration method to form grains 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 silver halide emulsion can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As a chalcogen sensitizer applied to the silver halide emulsion, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, and a sulfur sensitizer is preferable.

Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.

The amount of the sulfur sensitizer to be added is preferably changed depending on the kind of the silver halide emulsion to be applied, the size of the expected effect, and the like.
10 ^{-10 to} 5 × 10 ^-5 mol, preferably 5 × 10 ^{-8 to} 3
A range of ^10-5 mol is desirable.

As a gold sensitizer, 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, mercaptotriazole and the like. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc., but usually 1 × 10 ^-4 to 1 × 10 ^-8 mol per mol of silver halide. Is preferably
More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

The chemical sensitization of a silver halide emulsion includes:
A reduction sensitization method may be used.

The silver halide emulsion may contain a known antifoggant for the purpose of preventing fogging during the preparation of the light-sensitive material, reducing performance fluctuation during storage, and preventing fogging during development. Agents can be used. Preferred examples of the compound used for such purpose include a compound represented by the general formula [II] described in the lower column on page 7 of JP-A-2-14636, and more preferred specific compounds include II described on page 8 of the publication
a-1 to IIa-8, IIb-1 to IIb-7, 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, a step of finishing a chemical sensitization step, a step of preparing a coating solution and the like according to the purpose. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ per mol of silver halide is used.
It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 × 10
^-6 to 1 × 10 ⁻² mol is preferable, and 1 × 10 ^-5 to
5 × 10 ⁻³ mol is more preferred. When added to the silver halide emulsion layer in the coating solution preparation step, the amount of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide is preferred, 1 × 10 ^-5 ~ × 10 ^{- Two} moles are more preferred.
Further, when added to a layer other than the silver halide emulsion layer,
The amount in the coating film is 1 × 10 ⁻⁹ to 1 × 10 ⁻³ per m ^2.
Molar amounts are preferred.

For the light-sensitive material, 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. In particular, as dyes having absorption in the visible region, dyes of AI-1 to 11 described in JP-A-3-251840, p. The dyes described in JP-A-3770 are preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 are preferable. It is preferable because it has spectral characteristics, does not affect the photographic characteristics of the photographic emulsion, and does not stain due to residual color. 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. 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 to 3.0, and more preferably 0.8 to 3.0. More preferably, it is 3.0.

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 [I] described in JP-A-2-232652.
I].

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

As the spectral sensitizing dye used in the present invention, any of the known compounds can be used. Examples of the blue-sensitive sensitizing dye include BS-1 to BS-1 described on page 28 of JP-A-3-251840. BS-8 can be preferably used alone or in combination. Green photosensitive sensitizing dyes include:
GS-1 to GS-5 described on page 28 of the publication are preferable,
Further, as the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. When performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye,
Examples of the infrared-sensitive sensitizing dye include JP-A-4-285950.
And the dyes IRS-1 to IRS-11 described on pages 6 to 8 are preferably used. These infrared, red, green, and blue sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-6-6.
No. 6515, pages 15 to 17, compounds S-1 to S-
It is preferable to use 17 in combination.

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

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

As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by coupling reaction with an oxidized form of a color developing agent is used. Although it is also possible to use, particularly typical couplers include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm,
Examples include those known as cyan dye-forming couplers having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

Preferable examples of the cyan coupler which can be preferably used include couplers represented by general formulas [CI] and [C-II] described in the lower left column on page 5 of JP-A-4-114154. As a specific compound, the publication 5
There can be mentioned those described as CC-1 to CC-9 in the lower right column of page 6 to the lower left column of page 6.

Examples of the magenta coupler that can be preferably used include couplers represented by general formulas [MI] and [M-II] described in the upper right column of page 4 of JP-A-4-114154. Specific compounds include those described as MC-1 to MC-11 in the lower left column of page 4 to the upper right column of page 5 of the publication. Among the above magenta couplers, more preferred are those represented by the general formula [MI]
A coupler represented by the general formula [M-
The coupler of the formula (I) wherein R _M is a tertiary alkyl group is particularly preferred because of its excellent light resistance. M described in the upper column on page 5 of the publication
C-8 to MC-11 are preferable because they are excellent in reproduction of colors ranging from blue to purple and red, and are also excellent in detail description.

As the yellow coupler which can be preferably used, a coupler represented by the general formula [YI] described in the upper right column on page 3 of JP-A-4-114154 can be mentioned. YC on the lower left column of page 3
-1 to YC-9. Among them, a coupler of the formula [Y-I] in which R _Y1 is an alkoxy group or a coupler represented by the formula [I] described in JP-A-6-67388 is preferable because it can reproduce yellow having a preferable color tone. Of these, YC-8 and YC-9 and JP-A-6-673881 described in the upper left column of page 4 of JP-A-4-114154 are particularly preferred.
Compounds represented by Nos. (1) to (47) on pages 3 to 14 can be exemplified. The most preferred compound is a compound represented by the general formula [Y-1] described in JP-A-4-81847, pages 1 and 11-17.

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 more, 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 included.

Examples of the high boiling point organic solvent which can be used for dissolving and dispersing the coupler include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate and dibutyl phthalate, tricresyl phosphate, and trioctyl phosphate. And the like are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

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-1 described in JP-A-64-26854.
1 is mentioned. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are
Usually, it is added to a coating solution containing a silver halide emulsion, but it is better that the time until the addition to the coating solution after dispersion and the time from the addition to the coating solution to the coating are shorter, each being preferably within 10 hours. More preferably, within 3 hours and 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 include phenyl ether compounds represented by general formulas [I] and [II] described in JP-A-2-66541, page 3, and phenols represented by general formula [IIIB] described in JP-A-3-174150. Amine compounds represented by the general formula [A] described in JP-A-64-90445;
General formulas (XII), (XIII) and (XI) described in No. 182741
V] and metal complexes represented by [XV] are particularly preferred for magenta dyes. Also, a compound represented by the general formula [I] described in JP-A-1-19649 and JP-A-5-1141.
The compound represented by the general formula [II] described in No. 7 is particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, compounds such as compound d-11 described in the lower left column of page 9 of JP-A-4-114154 and compound A'-1 described in the upper left column of page 10 are used. be able to. In addition, the fluorescent dye releasing compounds 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 prevent fog or the like. Is preferably improved. As the compound for this, a hydroquinone derivative is preferred, and more preferably
Dialkylhydroquinones such as 5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula [II] described in JP-A-4-133056, and the compounds II-1 to II-14 described on pages 13 to 14 of the same publication.
Compounds-1 described on pages II-14 and 17 are mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or to improve the light fastness of the dye image. Preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are those represented by the general formula [III-] described in JP-A-1-250944.
3], a compound represented by the general formula [III] described in JP-A-64-66646, and a compound represented by JP-A-63-18
No. 7240, UV-1L to UV-27L;
Compounds represented by the general formula [I] described in JP-A-1633 and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

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

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener, a chlorotriazine hardener, and a carboxyl group-active hardener alone or in combination. JP-A-61-249054, 61-
It is preferable to use the compounds described in US Pat. Further, in order to prevent the growth of molds and bacteria which adversely affect the photographic performance and image storability, JP-A-3-15764 is incorporated in the colloid layer.
It is preferable to add a preservative and an antifungal agent as described in No. 6. In order to improve the physical properties of the surface of the light-sensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.

As the support used for the light-sensitive material, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, a vinyl chloride sheet, and a 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 preferred.

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, sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, silicas such as fine silica powder, synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, oxide Zinc, talc, clay and the like can be mentioned. 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 sharpness.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support 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 variation coefficient described in the publication.

Further, it is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, more preferably 0.12 μm or less, because the effect of good gloss is obtained.
Also, in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer, to improve the whiteness by adjusting the spectral reflection density balance of the white background after treatment, ultramarine blue, oil-soluble dyes, etc. It is preferable to add a small amount of a bluing agent or a reddish agent.

The photosensitive material may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or to an undercoat layer (adhesion, antistatic property, dimensional stability on the support surface). , One or more undercoating layers for improving friction resistance, hardness, antihalation property, frictional properties and / or other properties).

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

In order to form a photographic image using the photosensitive material of the present invention, the image recorded on the negative may be optically focused on the photosensitive material to be printed and printed. May be once converted into digital information, the image may be formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed, for example, based on digital information. It is preferable to print by scanning while changing the intensity of the laser beam.

As an image forming method by the scanning exposure method,
For example, Japanese Patent Publication No. 62-21305 discloses a method in which a photographic photosensitive material is subjected to scanning exposure using a light emitting diode as a light source. JP-A-63-18346 discloses a scanning exposure method using a second harmonic obtained as a light source by using a semiconductor laser and an SHG element. In such print production, particularly by digital printing, it is preferable that high-quality images can be obtained by exerting the effects of the present invention.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and particularly preferably to a light-sensitive material 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. In particular,
It is preferably applied to a photosensitive material having a reflective support.

Known compounds can be used as an aromatic primary amine developing agent used for color development. 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-lauryl) aminotoluene CD-4: 4- (N-ethyl-N-β-hydroxyethyl) aminoaniline CD-5: 2-Methyl-4- (N-ethyl-N-β-hydroxyethyl) amino) aniline CD-6: 4 -Amino-3-methyl-N-ethyl-N-
(Β-methanesulfonamido) ethylaniline CD-7: 4-amino-3-β-methanesulfonamidoethyl-N, N-diethylaniline 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) ethylaniline In the present invention, the color developing solution containing the above-mentioned developing agent can be used in an arbitrary pH range.
It is preferably from 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 is preferably 35 to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, it is preferable that the temperature is not too high from the viewpoint of the stability of the processing solution, and the more preferable the processing is at 37 to 60 ° C.

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

To the color developing solution, a known developing solution component compound can be added in addition to the aforementioned color developing agent. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chloride ion and benzotriazole, a preservative, a chelating agent and the like are 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 washing process, a stabilizing process may be performed.

The developing apparatus used in the processing of the photosensitive material of the present invention may be a roller transport type in which the photosensitive material is conveyed with rollers interposed in a processing tank. An endless belt method may be used, in which the processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is transported, or a spray method in which the processing liquid is sprayed, A web system by contact with a carrier impregnated with a treatment liquid, a system using a viscous treatment liquid, and the like can also be used.
When 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. And the method described in JP-A-94-16935 is most preferable.

The photosensitive material of the present invention can be preferably applied to a heat development system. Thermal development refers to a method of developing by heating the exposed photosensitive material to 50 to 250 ° C, preferably 60 to 150 ° C.

The heat treatment is performed, for example, in JP-A-63-7185.
No. 0 etc., a method of heating and conveying while sandwiching a photosensitive material between a heat drum and a drum belt,
Alternatively, a photosensitive material is set between a heater and a support, and heating is performed simultaneously with pressurization. A so-called direct heating method, or a photosensitive material is placed between a far-infrared heater described in JP-A-4-240642 and the like. It is possible to use a so-called indirect heating method, in which heating is performed by irradiating a microwave, or a method combining a direct heating method and an indirect heating method.

In the heat development, for example, JP-A-63-1
As described in JP 08337 and the like, a so-called one-sheet system in which a single photosensitive material is exposed and thermally developed to obtain a final image, or a so-called one-sheet system,
As described in Example 1 of JP-A-7-225461, a photosensitive material and a dye receiving material are used, and the image dye formed or released by thermal development is diffused and transferred from the photosensitive material to the dye receiving material. So-called 2 to get the final image
Any of the sheet systems can be used. A method in which a photosensitive layer and a dye image-receiving layer are laminated on one support, and image dyes formed or released by thermal development are diffused and transferred from the photosensitive layer to the dye-image receiving layer, and then the photosensitive layer is peeled off. Can also be preferably used.

In the heat development, for example, JP-A No. 2-12
As described in Example 1 of Japanese Patent Application Laid-Open No. 0739/0739, a method of performing development only by heating without supplying a reaction auxiliary from the outside, or as described in Example 1 of Japanese Patent Application Laid-Open No. 9-5968. Any method may be used in which a small amount of a reaction aid (for example, water or the like) is supplied to the photosensitive material as necessary at the time of heat development, and then heat development is performed. When there is no supply of a reaction aid from the outside, a mode in which a so-called thermal solvent that is solid at room temperature but liquefies at the heat development temperature, that is, a so-called thermal solvent is preferably contained in the photosensitive material in advance is preferable. For example, JP-A-1-227150, page 4, upper left column to page 9, upper right column,
The compounds described in columns “0015” to “0018” of JP-A-289856 can be preferably used.

It is preferable to use a base generator from the viewpoint of improving the silver developing speed and the image dye diffusion speed.
As a method for generating a base, for example, JP-A-59-157637
Nos. 3, pp. 3 to 6 of JP-A No. 59-180537, and from the upper left of page 4 to the lower left of page 7 of JP-A No. 59-180537.
No. 7097, EP 210,660, U.S. Pat. No. 4,740,445, etc., in the presence of a small amount of water, a basic metal compound which is hardly soluble in water, and the basic metal compound A method of generating a base with a combination of compounds capable of forming a complex using metal ion and water as a medium can be used.

In the heat development, from the viewpoint of accelerating silver development, an embodiment in which an organic silver salt is contained in the light-sensitive material as necessary is also useful.

As the organic silver salt, for example, JP-A-49-5
Nos. 2626 and 53-362224, silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocyclic ring, JP-A-52-137321 and JP-A-58-1186.
A silver salt of a compound having an imino group described in JP-A No. 38, etc., or a silver salt of an acetylene compound described in JP-A No. 61-249044 or the like can be preferably used.

In the heat development, it is preferable to use a dye mordant in combination from the viewpoint of reducing image bleeding and fading when the final image is stored. As the dye mordant, a polymer containing a tertiary amine or a quaternary ammonium salt is preferable. For example, JP-A-9-5968, “005”
The compounds described in "7" to "0060" can be preferably used.

When the light-sensitive material of the present invention is used for thermal development, compounds which form or release image dyes (dye-donating substances) are described in, for example, JP-A-61-61157.
Nos. 61-61158, 62-4438, 62
129850, 62-129851, 62-
Couplers forming diffusible dyes described in JP-A-169158 and JP-A-3-73949;
Leuco dyes described in US Pat.
Azo dyes described in US Pat.
Nos. 0434, 59-65839 and 59-7104
Nos. 6, 59-87450, 59-165055, JP-A-59-55430, and JP-A-59-55430.
-165054, 59-154445, 59-
No. 116655, No. 59-124327, No. 59-1
52440 and 64-13546, JP-A-6-51
Compounds capable of forming image dyes in a manner opposite to the silver development described in JP-A-474, etc. are preferred.

Further, for example, a photosensitive material using a microcapsule containing the polymerizable compound described in JP-A-2-293753 and JP-A-2-308162 and the above-described dye-providing substance is formed, and is imagewise or reversely developed by heat development. A thermal development method in which the microcapsules are cured by causing an imagewise polymerization reaction to change the diffusion speed of the image dye and the physical strength of the binder to form an image can also be used.

In the light-sensitive material of the present invention, a mode in which a developing agent or a precursor thereof is incorporated can be used.
The developing agent incorporated in the photosensitive material is required to be stable during storage of the photosensitive material and not to reduce silver salts unnecessarily. As developing agents satisfying such requirements, paraphenylenediamine-based agents described in JP-A-62-288835, sulfonamidophenol-based agents described in JP-A-9-15806, etc .;
No. 241282, No. 8-234388, No. 8-286
No. 340, No. 9-152700, No. 9-152701
Hydrazine-based agents described in JP-A Nos. 9-152702, 9-152703, and 9-152704, and hydrazone-based agents described in JP-A Nos. 7-200202 and 8-234390. Can be.

When the photosensitive material contains a developing agent,
Development by activator processing other than the above-mentioned heat development processing can also be preferably used. Activator processing is a processing solution that does not contain a color developing agent (activator solution)
The compounds necessary for color development are incorporated in the photosensitive material in advance. The activator solution in this case is characterized in that it does not contain the color developing agent contained in the usual components of the color developing solution, and may contain other components such as an alkali and an auxiliary developing agent. Regarding the activator treatment, see European Patent 54
Examples thereof are known documents such as 5,491A1 and 565,165A1.

[0143]

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

Example 1 A high-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare 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 the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon to prepare a silver halide photographic light-sensitive material. The coating solution was prepared as follows.

First layer coating solution 23.4 g of yellow coupler (Y-1), 3.34 g of dye image stabilizer (ST-1), 3.34 of (ST-2)
g, (ST-5) 3.34 g, a stain inhibitor (HQ-
1) 0.34 g, 5.0 g of image stabilizer A, 3.33 g of high-boiling organic solvent (DBP) and high-boiling organic solvent (DNP)
To 1.67 g, 60 ml of ethyl acetate was added and dissolved, and this solution was dissolved in 1 ml containing 7 ml of 20% surfactant (SU-1).
It was emulsified and dispersed in 220 ml of 0% gelatin aqueous solution using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

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

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

[0148]

[Table 1]

[0149]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) · sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2 5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl ] Hydroquinone Image Stabilizer A: pt-octylph Enol

[0151]

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[0152]

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[0153]

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[0154]

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(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
In a liter of a 2% aqueous gelatin solution kept warm in
Solution ₀ ) and (B ₀ solution) were added simultaneously over 15 minutes while controlling pAg = 7.3 and pH = 3.0.
Solution ₀ ) and (D ₀ solution) were simultaneously added over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pA
The g was controlled by the method described in JP-A-59-45437, and the pH was controlled by using sulfuric acid or an aqueous solution of sodium hydroxide.

(A ₀ solution) Sodium chloride 1.03 g Potassium bromide 0.01 g Water was added to 60 ml (B ₀ solution) Silver nitrate 3 g Water was added to 60 ml (C ₀ solution) Sodium chloride 102.7 g K ₂ IrCl ₆ 4 × 10 ⁻⁸ mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ⁻⁵ mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (D ₀ solution) Silver nitrate 300 g Add water 600 ml Addition is completed Thereafter, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle diameter of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion (EMP-1) was obtained.

Next, except that the addition time of (A ₀ solution) and (B ₀ solution) and the addition time of (C ₀ solution) and (D ₀ solution) were changed,
A monodisperse cubic emulsion (EMP-1B) having an average particle size of 0.64 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol% was obtained in the same manner as in MP-1.

The above-mentioned EMP-1 was optimally chemically sensitized at 60 ° C. using the following compounds. Also, EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver amount of 1: 1 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 stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole (Preparation of green-sensitive silver halide emulsion) ( _A0 solution) and (B
₀ solution) and the addition time of (C ₀ solution) and (D ₀ solution) were changed in the same manner as EMP-1 except that the addition time was changed.
55 μm, coefficient of variation 0.08, silver chloride content 99.5%
(EMP-2) was obtained.

Next, a monodisperse cubic emulsion (EMP-2B) having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

The above EMP-2 was optimally subjected to chemical sensitization at 65 ° C. using the following compounds. Also, EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G101).

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 stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (Preparation of silver halide host emulsion) 2 which kept warm
% Following aqueous gelatin solution in 1 liter (A ₁ liquid) and (B ₁ liquid) the pAg = 7.3, over 30 min while controlling the pH = 3.0 were simultaneously added, further the following (C ₁ solution) and (D ₁ solution) the pAg = 8.0, were simultaneously added over 120 minutes while controlling the pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(A ₁ solution) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (B ₁ solution) Silver nitrate 10 g Water was added to 200 ml (C ₁ solution) Sodium chloride 102.7 g Metal compound (II) -1) 2 × 10 ^-8 mol potassium bromide 1.0g water to make 600ml (D ₁ solution) after silver nitrate 300g water was added 600ml completion of addition, 20 of a 5% aqueous solution of magnesium sulfate Kao Atlas Co. Demol N % Desalted with an aqueous solution of gelatin and mixed with an aqueous solution of gelatin to obtain an average particle size of 0.40 μm.
m, a coefficient of variation of 0.08 and a monodispersed cubic emulsion (EMP-11) having a silver chloride content of 99.5%.

(Preparation of fine grain silver halide emulsion) 40 ° C.
2% aqueous solution of gelatin in 1 liter was kept in the following (A ₂ solution) and (B ₂ solution) the pAg = 7.3, pH = 2.
It was added simultaneously over 10 minutes while controlling to 0.

(A ₂ solution) 170 g of silver nitrate and 240 ml of water were added. (B ₂ solution) 58.5 g of sodium chloride was added and 240 ml of water was added. After the completion of the addition, the pH was adjusted to 5.5 with sodium hydroxide, and then added. After desalting was conducted by circulating a pump through a tube provided with a filtration membrane until the conductivity became 3 mS / cm or less, gelatin swelled with a small amount of water was added to adjust the gelatin concentration to 2.5%. As a result of observation with an electron microscope, a fine silver chloride emulsion (EMX-1) having an average particle size of about 0.07 μm was obtained.
0) was obtained.

[0166] In the preparation of silver chloride fine grain emulsion EMX-10, pre-metal compound (B ₂ solution) (II-1) a 1 × 1
A silver chloride fine grain emulsion (EMX-11) was obtained in the same manner except that ^0-4 mol was added.

Similarly, instead of the metal compound (II-1), 1 × 10 ⁻⁴ mol of each of STAB-1, chloroauric acid,
Using the metal compound (III-1) or (II-7), silver chloride fine grain emulsions (EMX-12) to (EMX-15) were obtained. Here, the metal compound (III-1) is K ₂ [Fe (CN)
₆ ].

[0168] In the preparation of silver chloride fine grain emulsion EMX-11, respectively 20 mole% of sodium chloride (B ₂ solution),
In the same manner as above, except that 50 mol% and all of them were replaced with potassium bromide of the corresponding mole number, silver chlorobromide fine grain emulsions (EMX-16), (EMX-17) and silver bromide fine grain emulsions (EMX) -18).

The above host emulsion EMP-11 was optimally subjected to chemical sensitization and color sensitization at 50 ° C. using the following compounds to obtain a red-sensitive silver halide emulsion (Em-R101).

Triethylthiourea 1.0 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 stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX sensitizing dye RS-2 1 × 10 ^-4 mol / mol AgX Supersensitizer SS- 12 × 10 ⁻³ mol / mol AgX The sensitizing dyes and supersensitizers used for color sensitization of each color-sensitive emulsion are as follows.

[0171]

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[0172]

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In the preparation of the above emulsion Em-R101,
Red-sensitive silver halide emulsion (Em-R102) was prepared in the same manner except that an aqueous solution of metal compound (II-1) was added at 50 ° C. in an amount of 1 × 10 ⁻⁶ mol per mol of silver halide.
I got

Next, with respect to the host emulsion EMP-11, 5
At 0 ° C., fine grain emulsions EMX-10 to EMX-18 were added and ripened in an amount corresponding to 1% of the silver halide in the host emulsion. Subsequently, using the above compound, Em
Performs optimal chemical sensitization at 50 ° C as in -R101.
Red-sensitive silver halide emulsions (Em-R103) to (Em-R103)
R111) was obtained.

In the preparation of the emulsion Em-R101,
After the chemical sensitization and the color sensitization are optimally completed, the silver chloride fine grain emulsion EMX-11 is added at 50 ° C. in an amount equivalent to 1% based on the amount of silver halide, followed by ripening.
A red-sensitive silver halide emulsion (Em-R112) was obtained.

[0176] Further, in the preparation of Emulsion Em-R101, in the preparation of the emulsion EMP-11 (C ₁ liquid) and (D
_When the addition of the _first solution) was completed at 80%, the addition was interrupted once, and the silver chloride fine grain emulsion EMX-11 was added at an amount corresponding to 1% based on the amount of silver halide and ripened. After aging, the remaining (C
₁ solution) and (D ₁ solution), and thereafter, a silver halide emulsion (EMP-12) was prepared in the same manner, and the same was used to perform optimal chemical and color sensitization in the same manner. A light-sensitive silver halide emulsion (Em-R113) was prepared.

In the preparation of Sample 101, the emulsion Em-R
In the same manner except that Em-R102 to Em-R113 were used instead of 101, samples 102 to
113 was obtained.

The samples 101 to 113 obtained as described above were evaluated for the illuminance change characteristics and the long-term storage stability of the samples by the following methods. Table 3 shows the results.

<< Irradiance change characteristic >> Under each exposure condition, wedge exposure was performed on a photosensitive material sample with a tungsten lamp using a tungsten lamp for an exposure time of 100 seconds and 1 second, while appropriately adjusting the illuminance so as to obtain a minimum density to a maximum density. did. Similarly,
Exposure time of 10 ^-3 seconds and 1 with xenon flash lamp
And wedge exposure at 0 ^-6 seconds. After subjecting each exposed sample to color development processing according to the following processing steps, a densitometer PDA-65 was used.
(Konica Corporation) was used to measure the R (red) concentration.

From the obtained characteristic curves, the maximum density (Dm) and gradation (γ) of the sample at each exposure time were calculated.
Here, Dm and γ are defined as follows.

Dm: Density at an exposure that is 2.0 LogE higher than the exposure that gives a density 0.1 higher than the fog density.

Γ: Density 0.7 higher than fog density and 1.
7 Average slope of characteristic curve during high concentration.

<< Long-term Sample Storage >> One of the unexposed samples was stored in a refrigerator for one month, and the other was stored in a high-temperature environment of 50 ° C. and 50% for one month. After leaving the both unexposed, color-developing according to the following processing steps, X-Rite
Using a 310TR densitometer (manufactured by X-Rite), the R density was measured under the reflection density measurement conditions.

The difference in minimum density between the sample stored in a high-temperature environment and the sample stored in a refrigerator was defined as ΔFog, and the fog increase during storage of the photosensitive material was evaluated.

The development process and the formulation of the processing solution are as follows. The amount of replenishment was represented by the amount per 1 m ² of the light-sensitive material. At this time, Konica Color QA paper type A7 was printed and run until the processing solution was replenished with a replenisher twice the tank volume of the color developing solution in advance.

Processing Step Processing Temperature Time Replenishment Color Development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 seconds 150 ml Drying 60- 80 ° C. 30 seconds (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 0.0g Diethylenetriaminepentaacetic acid sodium salt 2.0g 2.0g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make a total volume of 1 liter, and the tank solution was pH = 1.
Adjust the replenisher to pH = 10.60 to 0.10.

(Bleaching and Fixing Solution Tank Solution and Replenisher) Diethylenetriaminepentaacetic acid ammonium ferric 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 0 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopal 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 Polyvinylpyrrolidone 1.0 g Ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g Nitrilotriacetic acid / trisodium salt 1.5 g Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or ammonia water. I do.

[0189]

[Table 3]

A photosensitive material having a conventional structure such as the sample 101 has a low maximum density Dm at the time of exposure to high illuminance for a very short time and is very soft, so that it cannot be put to practical use. It was found that adding only the metal compound (II-1) or adding only the silver chloride fine grain emulsion had no effect.
It can be seen from 2,103.

On the other hand, when a silver chloride fine grain emulsion containing the metal compound (II-1) in advance is added as in the case of the sample 104 of the present invention, the exposure can be changed from short exposure at high illuminance to long exposure at low illuminance. Stable and sufficient Dm and gradation are obtained over the entire range.
Further, an effect of suppressing fog rise during long-term storage of the photosensitive material is also recognized.

From Samples 105 to 107, when the silver bromide content exceeds 20 mol% in the halogen composition of the fine grain emulsion, not only the effect of improving high-intensity exposure failure is reduced, but also
The fog rises significantly during long-term storage, indicating that it is not practical. In particular, when a fine grain emulsion having a high silver bromide content is used, the effects of the present invention cannot be obtained.

As a photographically useful compound to be contained in the silver chloride fine grain emulsion in advance, a compound containing a metal belonging to Group 8 of the periodic table is advantageous. Particularly, in the case of an iridium compound, a compound having a high effect is particularly useful. Samples 104 and 108 to 111 that an iridium complex having a bromine atom is more preferable.
Can be understood from the results.

Samples 104, 112 to 1 are preferably prepared by adding the fine grain emulsion to the host emulsion after sensitization and more preferably before sensitization than during grain formation of the host emulsion.
I understand from 13.

As described above, it was confirmed that a remarkable illuminance failure improvement effect was recognized only in the embodiment of the present invention.

Example 2 A silver halide emulsion (EMP-E) prepared on a 120 μm-thick triacetyl cellulose film under the following conditions was prepared.
201) with an aqueous gelatin solution (gelatin / silver)
= 0.60 to prepare a coating solution. As a coating aid, a surfactant (SU-2) was added to adjust the surface tension. Using this coating liquid, the coating amount as silver was 1.2.
g / m ² was applied to prepare a sample 201 for measuring microwave photoconductivity.

[0197] The following 2% aqueous solution of gelatin in 1 liter was kept in (Preparation of Silver Halide Emulsion) 40 ° C. (A ₃ solution)
And (B ₃ solution) were simultaneously added while controlling pAg = 6.5 and pH = 3.0, and the following (C ₃ solution) and (D ₃ solution) were further added to pAg.
Ag was added simultaneously over 120 minutes while controlling to Ag = 7.3 and pH = 5.5. At this time, the control of pAg is described in
No. 45437, and the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

[0198] (A ₃ solution) Sodium chloride 3.45g metal compound (II-1) 5.88 × 10 -10 mol Water to make 200 ml (B ₃ solution) Silver nitrate 10.0g Water to make 200 ml (C ₃ Liquid) Sodium chloride 103.2 g Metal compound (II-1) 1.76 × 10 ⁻⁸ mol Add water 600 ml (D ₃ liquid) Silver nitrate 300 g Add water 600 ml After completion of addition, Kao Atlas Demol N After desalting using a 5% aqueous solution and a 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to obtain an average side length of 0.40 μm.
m, coefficient of variation = 0.07, monodispersed silver chloride cubic emulsion (E
MP-201) was obtained. This emulsion contains a metal compound (II-
1) potassium hexachloroiridate (IV) was uniformly added at 1 × 10 ⁻⁸ mol per mol of silver halide;
This is a silver halide emulsion composed of cubic silver chloride having an average side length of 0.4 μm.

Next, in the preparation of the emulsion EMP-201, the metal compound (II-1) of (A ₃ solution) and (C ₃ solution)
Were changed to the metal compounds shown in Table 4 in order to prepare emulsions (EMP-202) to (EMP-210), and in the preparation of sample 201, the emulsion EMP-201 was replaced with EMP-202 to 210. Samples 202-21
0 was produced.

Samples 201 to 210 were prepared as described in JP-A-5-457.
Microwave photoconductivity is measured by the method described in No. 58, pp. 2-3 (the light source is a UVD-33S filter manufactured by Toshiba Glass Co., Ltd., and excited by ultraviolet light), and the photoconductivity signal is attenuated by induced absorption. I asked for time.

Table 4 shows the measurement results. The decay time of the photoconductivity signal of each sample is 100 times the decay time of sample 201.
And expressed as relative values.

[0202]

[Table 4]

As shown in Table 4, the metal compounds (I-1) and (I-
7), (I-9), (I-19), (I-20), (I
Samples 202 to 210 coated with the emulsion to which -22) was added
The decay time of the photoconductivity signal is smaller than the decay time of the comparative sample 201, and thus it can be seen that the compound is a metal compound satisfying the condition A.

Example 3 In the preparation of the host emulsion EMP-11 in Example 1, the metal compound (II-1) was sequentially changed as described in the column of the host emulsion of Samples 301 to 308 shown in Table 5 to prepare the host emulsion. Emulsions (EMP-31) to (EMP-39) were prepared. To these host emulsions, similarly to the red-sensitive emulsion Em-R104, a silver chloride fine grain emulsion EMX-11 containing a metal compound (II-1) in advance is added to perform optimal chemical and color sensitization. Red-sensitive silver halide emulsion (Em-R301)
(Em-R308) was obtained.

At this time, a silver chloride fine grain emulsion E was used as a comparative example.
A red-sensitive emulsion to which MX-11 was not added (Em-R30
9), and in place of silver chloride fine grain emulsion EMX-11,
Red-sensitive emulsion (Em-R310) to which silver bromide fine grain emulsion EMX-18 containing metal compound (II-1) in advance is added
Was also prepared.

In the preparation of Sample 101, the red-sensitive emulsion E
Samples 301 to 310 were obtained in the same manner except that Em-R301 to R311 were used instead of m-R101.

With respect to the samples 301 to 310, the illuminance change characteristics and the long-term sample storability were evaluated in the same manner as in Example 1. The data of sample 104 are also shown again.

[0208]

[Table 5]

A metal compound to be contained in the host emulsion was
Samples 301 to 308 from (II-1) were replaced with compounds satisfying the condition A in Example 2. When the compound satisfying the condition A is contained in the host emulsion, in the embodiment of the present invention, from the short exposure of high illuminance to the long exposure of low illuminance, particularly, the gradation is stable while maintaining sufficient hardness. It is preferable. In addition, fog rise during long-term storage is further suppressed, and a remarkable effect is obtained.

It is clear from the results of Samples 309 and 310 that even if a compound satisfying the condition A is contained, there is no effect unless the embodiment of the present invention is taken.

Example 4 In the preparation of the red-sensitive emulsion Em-R104 of Example 1,
Triethylthiourea, sensitizing dye and silver chloride fine grain emulsion E
The red-sensitive emulsion (Em-R401) to the red-sensitive emulsion (Em-R401) were prepared in the same manner except that the order of adding MX-11 was sequentially changed as shown in Table 6.
(Em-R406) was prepared. At this time, it took at least 10 minutes between the addition of the triethylthiourea, the sensitizing dye, and the silver chloride fine grain emulsion. Chloroauric acid was added simultaneously with triethylthiourea. As shown in Table 6, no silver chloride fine grain emulsion was added during the preparation of the red-sensitive emulsion Em-R401.

Next, the red-sensitive emulsions Em-R401 to Em-R
In the preparation of R406, triethylthiourea was replaced with an equimolar amount of sodium thiosulfate and the heating temperature was reduced to 7
A red-sensitive emulsion (Em-R4
07) to (Em-R412).

In the preparation of Sample 101, the red-sensitive emulsion E
Em-R401 to Em-R41 instead of m-R101
Samples 401 to 412 were obtained in the same manner except that Sample No. 2 was used.

With respect to the samples 401 to 412, the illuminance change characteristics and the long-term sample storability were evaluated in the same manner as in Example 1. Table 6 shows the results.

[0215]

[Table 6]

A comparison of Samples 401 to 406 shows that the fine grain emulsion was added first to the chemical sensitizers triethylthiourea and chloroauric acid (Sample 40).
2 to 404), the effect of the present invention is particularly large.

Further, a similar sample was prepared by replacing the chemical sensitizer with sodium thiosulfate (samples 407 to 41).
In sample 2), the sample 40 to which the fine grain emulsion was previously added was also used.
The effect of 8-410 is clearly large.

From the above, it can be easily understood that it is more preferable to add the fine grain emulsion before the chemical sensitizer.

[0219] 2% aqueous solution of gelatin 1 liter kept at 40 ° C. (Preparation of host emulsion) Example 5, the following (A ₄ solution) and (B ₄ solution) p
Ag was added simultaneously over 30 minutes while controlling to Ag = 7.3 and pH = 3.0, and the following (C ₄ solution) and (D ₄ solution) were further pAg
= 8.0, pH = 5.5, and added simultaneously over 120 minutes. At this time, the pAg is controlled by the method described in JP-A-59-45.
No. 437, and the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(A ₄ solution) Sodium chloride 3.42 g Potassium bromide 0.03 g Metal compound (II-1) 5.88 × 10 ⁻¹⁰ mol Water was added thereto 200 ml (B ₄ solution) Silver nitrate 10 g Water was added 200 ml (C ₄ solution) Sodium chloride 102.7 g Potassium bromide 1.0 g Metal compound (II-1) 1.76 × 10 ⁻⁸ mol Add water 600 ml (D ₄ solution) Silver nitrate 300 g Add water 600 ml Add After completion, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average side length of 0.40 μm.
m, coefficient of variation = 0.07, monodisperse cubic emulsion (EMP-
51) was obtained. This emulsion was a silver halide emulsion in which the metal compound (II-1) was uniformly added from the center to the surface of the grains at 1 × 10 ⁻⁸ mol per mol of silver halide.

[0221] Next (A ₄ solution) - and variously changed the addition amount of the (D ₄ solution) and the amount of the metal compound (II-1), the distribution and amount of (II-1) in the particles Were as shown in Table 7 to prepare silver halide emulsions (EMP-52) to (EMP-64).

These emulsions were optimally subjected to chemical sensitization and color sensitization at 60 ° C. using the following compounds to obtain red-sensitive emulsions (Em-R501) to (Em-R514).

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 stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX sensitizing dye RS-2 1 × 10 ^-4 mol / mol AgX Supersensitizer SS- 12 × 10 ⁻⁹ mol / mol AgX In the preparation of sample 101 of Example 1, the red-sensitive emulsion Em
Em-R501 to Em-R514 instead of -R101
Samples 501 to 514 were obtained in the same manner except that was used.

With respect to the samples 501 to 514, the illuminance change characteristics and the long-term sample storability were evaluated in the same manner as in Example 1. Table 7 shows the results.

[0225]

[Table 7]

As is clear from the table, a remarkable improvement effect can be obtained only in the embodiment of the present invention. That is, the iridium compound is contained both in the interior of the grain at 50% by volume from the center and in the vicinity of the grain surface on the surface side of more than 90%, and the content of the iridium compound in the grain is 10 ^-9 mol per mol of silver under halogen. As described above, it can be understood that the content of the iridium compound near the surface needs to be 10 to 1000 times that of the inside. In particular, even near the surface,
It can be seen that more favorable effects can be obtained in the samples 513 and 514 in which the iridium compound is contained on the surface side from 95% of the particle volume.

Example 6 In the preparation of Sample 104 of Example 1, a green-sensitive emulsion and a blue-sensitive emulsion were prepared by applying the same embodiment of the present invention as in the preparation method of the red-sensitive emulsion.

The green and blue-sensitive emulsions thus obtained were used for the preparation of Sample 104 to prepare Sample 601 in which all the red, green, and blue color-sensitive emulsions were embodiments of the present invention.

Further, the sample 111 and the sample 30 of the third embodiment were used.
8. For the sample 410 of Example 4 and the sample 514 of Example 5, the same method as that for preparing each red-sensitive emulsion was applied, and the red-green-blue all-color emulsion was used in the practice of the present invention. Samples 602 to 605 to be forms were prepared.

With respect to Samples 601 to 605 and Sample 101, the illuminance change characteristics and the long-term storage stability of the samples B, G and R were evaluated in the same manner as in Example 1.

When the exposure time was changed, a sample 101 serving as a comparative example, especially when exposed at an ultra-high illuminance such as 10 ⁻³ or 10 ⁻⁶ seconds, had the highest density of the B, G, and R characteristic curves. Dm was low and extremely soft, so that it was not practical.

On the other hand, a sample 601 according to an embodiment of the present invention
With respect to ６０605, sufficient Dm and appropriately high tone were obtained regardless of the exposure time in any of the B, G, and R characteristic curves. That is, it is presumed that the change in the shape of the characteristic curve is small even in a wide exposure range of an exposure time of 100 seconds to 10 ^-6 seconds, so that a print of a stable tone can always be obtained regardless of the exposure method. In particular, samples 602 to 605
Is preferable because of less fluctuation.

Also, with respect to the rise in fog during long-term storage under high temperature conditions, Samples 601 to 605 were smaller than Comparative Sample 101, and the effects of the present invention were obtained.

Regarding the long-term storage property, one of the samples 601 to 605 and the sample 101 was placed in a refrigerator and the other was placed in a room at room temperature for evaluation in accordance with actual use conditions.
After storing for months, both samples were color-developed in the same manner as in Example 1, and the B, G, and R densities of the unexposed portions were measured using an X-RITE densitometer (described above). Also in this evaluation, the samples 601 to 605 of the present invention were superior to the comparative sample 101 with little increase in fog during storage at room temperature, similarly to the results described above.

From the above results, it can be seen that the improvement effect obtained by the practice of the present invention obtained in the red-sensitive emulsion can be similarly obtained in the green- and blue-sensitive emulsions, and that such an emulsion corresponding to the embodiment of the present invention can be obtained. It was confirmed that the sample prepared using the above-mentioned method exhibited excellent characteristics as a silver halide color photosensitive material.

Example 7 Samples 101 and 601-605 were actually exposed through a developed negative image of Konica Color JX400 by a general enlarger using a tungsten lamp.
Development processing was performed in the same manner as described above. At this time, by changing the enlargement ratio from the same negative image, prints of each size of the service size, the cabinet size, the quarter size, and the whole paper size were prepared using each sample. However, when producing prints of different sizes for each sample, filter conditions were employed that provided an optimal image in a print of a cabinet size.

The whole paper size print obtained from the comparative sample 101 was slightly reddish overall, the contrast of the picture was low, and it was difficult to obtain a print of the same quality as the cabinet or service size. On the other hand, samples 601 to
When 605 was used, there was little change in color balance or change in tone for each print size, and a print of stable image quality could be efficiently created.

As described above, in the conventional method of obtaining an actual color print by the analog surface exposure method,
It was confirmed that excellent color prints could be obtained with the photographic light-sensitive material of the present invention.

Example 8 Samples 601 to 605 and Sample 101 produced in Example 6
Was evaluated for digital exposure suitability as follows.

The developed negative image of Konica Color JX400 is converted into digital data using Konica Q Scan,
An environment that can be handled using Adobe software PHOTO SHOP was used.

[0241] Characters and fine lines of various sizes were added to the captured image to form one image data, and the image was operated so as to be exposed by the following digital scanning exposure apparatus.

Semiconductor laser GaAlAs as light source
(Oscillation wavelength of 808.5 nm) as an excitation light source using a YAG solid-state laser (oscillation wavelength of 946 nm) of SH of KNbO ₃
473 nm wavelength-converted and extracted by a G crystal, and a semiconductor laser GaAlAs (oscillation wavelength: 808.7 nm)
The YVO ₄ solid state laser as an excitation light source (oscillation wavelength 10
532 nm, which is obtained by converting the wavelength of a 64 nm) by using a KTP SHG crystal, and AlGaInP (having an oscillation wavelength of about 6 nm).
70 nm). An apparatus was manufactured in which laser light of each of the three colors was moved in a direction perpendicular to the scanning direction by a polygon mirror, and was sequentially scanned and exposed on color printing paper.
The amount of exposure was controlled by electrically controlling the light amount of the semiconductor laser. Scanning exposure was performed at 400 dpi, and the exposure time per pixel at this time was 5 × 10 ⁻⁸ seconds.

After variously adjusting the exposure amount so as to obtain an optimal print image for each sample, the substrate was subjected to scanning exposure and then developed in the same manner as in Example 1 to obtain a cabinet-size print image.

The print obtained from Comparative Sample 101 is
The density of each color was inadequate, there was no tightness of black, the whole was soft, and the tone of the shadow part was not reproduced at all.
In addition, characters blur and thin lines that should be black appear cyan,
No matter how the exposure conditions were adjusted, the print quality was completely unpractical.

On the other hand, the prints obtained from the samples 601 to 605 can be easily obtained in almost the same quality as the print image quality obtained by the analog surface exposure method of Example 7, which is of high quality without any practical problem. It was a print. No bleeding or color shift was observed in characters and fine lines, and prints obtained from samples 602 to 605 were particularly preferred because of high contrast.

Using the same image information and sample as above,
Konica Digital Minilab System QD-2
1 printer processor QDP-1500A.
The print obtained from was of a more favorable quality.

As described above, it was confirmed that an excellent color print can be obtained by the photographic light-sensitive material of the present invention also in the method of obtaining an actual color print by the digital scanning exposure method.

[0248]

According to the present invention, a color photographic light-sensitive material produced by using silver chloride or a silver halide emulsion containing silver chloride at a high concentration can be used in a wide exposure range of about 10 ^{-6 to} 100 seconds. A sufficient maximum density and appropriate gradation are always obtained, and the quality is not impaired even when stored at room temperature for a long time, that is, regardless of the exposure method and the storage condition of the photosensitive material,
It was an excellent silver halide color print material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/08 G03C 5/08

Claims (13)

[Claims] A silver halide photographic emulsion prepared by adding a high silver chloride fine grain emulsion containing a photographically useful compound to a high silver chloride emulsion. 2. The average grain size of the high silver chloride fine grain emulsion is 1/2 or less of the average grain size of the high silver chloride emulsion (hereinafter referred to as host emulsion) to which the fine grain emulsion is added. 01
2. The silver halide photographic emulsion according to claim 1, wherein said emulsion has a size of not less than μm. 3. The silver halide photographic emulsion according to claim 1, wherein the high silver chloride fine grain emulsion has an average silver chloride content of 80 mol% or more. 4. The silver halide photographic emulsion according to claim 1, wherein both the host emulsion and the high silver chloride fine grain emulsion have an average silver chloride content of 95 mol% or more. 5. The silver halide photograph according to claim 1, wherein the high silver chloride fine grain emulsion is added to the host emulsion after completion of the grain formation process of the host emulsion. emulsion. 6. The compound according to claim 1, wherein the photographically useful compound contained in the high silver chloride fine grain emulsion is a compound containing a Group 8 metal of the periodic table. Silver halide photographic emulsion. 7. The silver halide according to claim 1, wherein at least one of the photographically useful compounds contained in the high silver chloride fine grain emulsion is an iridium compound. Photographic emulsion. 8. The silver halide photographic emulsion according to claim 7, wherein the iridium compound is a compound having a bromine atom in at least one of the ligands. 9. The silver halide photographic emulsion according to claim 7, wherein the host emulsion contains a metal compound satisfying the following condition A. Condition A: 1 × 1 metal compound per mole of silver halide
The decay time of the photoconductivity signal in the induced absorption in the microwave photoconductivity measurement of a silver halide emulsion composed of silver chloride cubic crystals having an average side length of 0.4 μm and uniformly added in an amount of 0 to ⁸ moles is equal to that of the metal compound. It is shorter than the decay time of the photoconductivity signal of the silver halide emulsion substituted with molar potassium hexachloroiridate (IV). 10. The silver halide photographic emulsion according to claim 7, wherein the high silver chloride fine grain emulsion is added to the host emulsion before the chemical sensitizer. 11. A high silver chloride emulsion having an average silver chloride content of 95 mol% or more, wherein 10 ^-9 to 10 ^-7 mol per mol of silver halide is contained in the inside of the grain between 50% and 50% of the emulsion grain volume. A silver halide photographic emulsion containing an iridium compound and containing an iridium compound in an amount of 10 to 1000 times the amount of iridium inside the grains in the vicinity of the grain surface at 90 to 100% from the center by grain volume. 12. A silver halide photographic material comprising at least one of the emulsions according to claim 1. Description: 13. An image forming method, comprising scanning and exposing the silver halide photographic light-sensitive material according to claim 12.