JP2000105436A - Silver halide emulsion, its preparation, silver halide photographic sensitive material containing same, photosensitive material for heat development, photosensitive material for activator development and image forming method using those - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a silver halide emulsion having high sensitivity and excellent in rapid processing, to obtain silver halide photographic sensitive material containing the silver halide emulsion, photosensitive material for heat development and photosensitive material for activator development and to provide an image forming method using those materials. SOLUTION: In the silver halide emulsion containing a dispersive medium and silver halide grains, a silver chloride content of the silver halide grains based on the total amount of silver is >=50 mol %, flat platy grains having (100) faces as principal planes and an aspect ratio of >=2 account for >=50% of the total projection area. The silver halide emulsion is formed through at least (a) a step for forming core grains, (b) a step for forming anisotropic growth defects by adding halogen different from the core grains in composition and (c) a step for growing flat platy grains. The methionine content of a dispersive medium in the step (c) is <=70% of that in at least one of the steps (a) and (b).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion, a method for producing the silver halide emulsion, a silver halide photographic material containing the silver halide emulsion, a light-sensitive material for heat development, and a light-sensitive material for activator development. More specifically, the present invention relates to a silver halide emulsion having high sensitivity and excellent rapid processing, a method for producing the silver halide emulsion, and a silver halide photographic light-sensitive material containing the silver halide emulsion. The present invention relates to a material, a photosensitive material for thermal development, a photosensitive material for activator development, and an image forming method using the photosensitive material.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials are very popular today because they have very high characteristics, such as high sensitivity and excellent gradation, as compared with other light-sensitive materials. It is used for Among them, a light-sensitive material using silver halide grains having a high silver chloride content is preferred from the viewpoint of processing speed.
In such silver halide grains having a high silver chloride content, recently, higher sensitivity, higher sharpness, improved graininess,
Studies on tabular silver halide grains have been actively conducted with the aim of speeding up processing.

[0003] Such tabular silver halide grains having a high silver chloride content include grains having a (111) major plane (hereinafter also referred to as (111) tabular grains) and (10).
0) Grains having a main plane (hereinafter also referred to as (100) tabular grains) are known.

Among these, as a method for forming tabular grains having a (111) plane as a main plane, the grains are formed in the presence of a crystal habit controlling agent such as aminoazaindene, pyrimidine, aminoazine, thiourea, or xanthoidoid. Methods are known. However, in general, the (100) plane is stable in silver halide grains having a high silver chloride content, and these crystal habit controlling agents are desorbed when salts formed during the formation of silver halide grains are removed. The shape of the particles changes (1)
11) It has been difficult to stably obtain tabular grains having a plane as a main plane. Further, many of such crystal habit control agents are known as so-called inhibitors, and there has been a problem that chemical sensitization cannot be performed well in the presence of these compounds. On the other hand, tabular grains having a (100) plane as a main plane are described in JP-A-5-204073, U.S. Pat. Nos. 5,264,337 and 5,275,930.
JP-A-6-301131 and JP-A-6-308648
And JP-A-6-337489, JP-A-6-337490, and JP-A-6-337507. These (10
0) The tabular silver halide grains having a plane as a main plane include:
Compared with tabular silver halide grains having a (111) plane as a main plane, the silver halide grains are more stable in shape and have an advantage that spectral chemical sensitization is easily performed since no crystal habit controlling agent is particularly required.

[0005] As a method for introducing anisotropic growth into grains to grow them into (100) tabular grains, imidazole,
A method of adding a (100) plane formation accelerator such as 3,5-diaminotriazole and a method of forming a halogen composition gap by adding a halogen having a different composition from the core particles (hereinafter referred to as a different kind of halogen), There is a method in which a crystal plane is distorted depending on conditions such as pressure and high pressure.
The former method of forming with the (100) plane formation promoter is described in (1)
11) Like the plane formation accelerator, there is a problem that chemical sensitization cannot be performed well in the presence of these compounds, and the influence on photographic performance cannot be ignored. A method utilizing a gap surface of a halogen composition is preferably used. As a typical example of the method using the gap of the halogen composition, many methods have been reported in which silver iodide and silver bromide are present to cause nuclei to be distorted due to the difference in crystal lattice size from silver chloride. . However, in any of the methods, many non-tabular grains including irregular grains were formed, and it was difficult to obtain an emulsion having a high tabular grain ratio.

As a dispersion medium for forming silver halide grains, JP-A-5-204073 and JP-A-7-270951 are used.
No. 4 describes that the methionine content of the dispersion medium is specified, and it is preferable to use a dispersion medium containing a small amount of methionine. However, an emulsion having a sufficient tabular grain ratio could not be obtained. Furthermore, Japanese Patent Application Laid-Open No. Hei 9-15773 states that the protective colloids at the time of seed particle formation and at the time of complete particle growth are different.
The effect of improving the tabular grain ratio has not been obtained.

[0007]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a silver halide emulsion having high sensitivity and excellent rapid processing, a method for producing the silver halide emulsion, and a silver halide containing the silver halide emulsion. It is an object of the present invention to provide a photographic material, a photosensitive material for thermal development, a photosensitive material for activator development, and an image forming method using the photosensitive material.

[0008]

The above objects of the present invention have been attained by the following constitutions.

1. In a silver halide emulsion containing a dispersion medium and silver halide grains, the silver halide grains have a silver chloride content of 50 mol% or more of the total silver, and (10
0) tabular grains having a plane in the main plane and an aspect ratio of 2 or more account for 50% or more of the total projected area, and the silver halide emulsion has at least a) a nucleus grain formation process; Are formed through an anisotropic growth defect forming process by adding halogens having different compositions, c) a tabular grain growing process,
A method for producing a silver halide emulsion, wherein the content of methionine in the dispersion medium in step c) is at least 70% or less selected from steps a) and b).

[0010] 2. Wherein at least one of the a) core particle forming step and b) anisotropic growth defect forming step by addition of halogen having a different composition from the core particle has a dispersion medium concentration of 1 w% or more. A method for producing a silver halide emulsion as described above.

3. 3. A silver halide emulsion produced by the method for producing a silver halide emulsion according to any one of 1 to 2 above.

4. 4. A silver halide photographic light-sensitive material, wherein at least one layer contains the silver halide emulsion described in the above item 3.

5. 5. An image forming method, wherein the silver halide photographic light-sensitive material according to the above item 4 is imagewise exposed and then developed.

6. 4. A photothermographic material comprising at least one layer containing the silver halide emulsion described in the above item 3.

[0015] 7. 7. An image forming method, wherein the heat-developable photosensitive material according to the above item 6 is subjected to heat development after imagewise exposure.

8. 4. A light-sensitive material for activator development, wherein at least one layer contains the silver halide emulsion described in 3 above.

9. 9. An image forming method, comprising subjecting the activator development photosensitive material according to the above item 8 to imagewise exposure and then subjecting it to a heat development treatment.

Hereinafter, the present invention will be described in detail.

The cubic particles are made to have anisotropic growth, and (10
0) In the formation process of growing tabular grains, tabular grains are formed by causing different types of halogens to be present at the time of nucleation or immediately after nucleation and causing strain in the nuclei due to the difference in the size of the crystal lattice with silver chloride. Many methods have been reported.
However, the tabular grain ratio of (100) tabular grains is very low for use as a photographic emulsion, and it is important how to increase the tabular grain ratio. Since the anisotropic growth of (100) tabular grains depends on the step of the surface structure, it is expected that the anisotropic growth will be reduced if other compounds are adsorbed on the grain surface. In order to promote the growth of tabular grains, a method described in JP-A-5-204073, in which the concentration of the dispersing medium during grain formation and the methionine content in the dispersing medium were reduced, was attempted. The tabular grain ratio could not be increased. However, when formed by the method of the present invention, the flat plate ratio is sufficiently high (10
0) It was surprising that tabular grain emulsions could be obtained.

Therefore, according to the present invention, a silver halide emulsion having a higher aspect ratio tabular ratio can be produced, and a silver halide photographic light-sensitive material which can be processed with high sensitivity and can be processed quickly can be obtained.

<Halogenation is a tabular grain in which 50% or more of the total projected area has a silver chloride content of 50 mol% or more of the total silver, has a (100) plane as a main plane, and an aspect ratio of 2 or more. Silver particle> The aspect ratio as used herein means the diameter of a circle having the same area as the projected area of a tabular grain and the diameter of 2%.
It represents the ratio of the distance between two parallel planes. In the present invention, the aspect ratio is 2 or more, preferably 3 or more and less than 25, and particularly preferably 4 or more and less than 20.

The tabular grains of the present invention preferably have a thickness (distance between main planes) of 0.3 μm or less. Also,
The distribution of tabular grains can be calculated by using the coefficient of variation (the standard deviation S of the diameter distribution of a circle when the projected area is approximated by a circle).
Is 100% of the value S / D obtained by dividing by the average diameter D) is preferably 30% or less.

In the tabular silver halide grains according to the present invention, it is preferable that the parallel main plane is the (100) plane. The principal plane referred to here is a set of parallel planes having the largest area among the crystal surfaces forming substantially rectangular parallelepiped emulsion grains. The average particle diameter of the main plane can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times and measuring the projected area of the particles on the print (the number of measured particles is zero). Discrimination is assumed to be 1000 or more). The particle thickness can also be obtained by actually measuring an electron micrograph.

The fact that the main plane is the (100) plane can be determined by an electron diffraction method or an X-ray diffraction method. According to electron micrograph observation, particles having a (100) principal plane have an orthogonal square (square or rectangular).
It can be checked because it is a surface.

The composition of the tabular silver halide grains is Ag
Any of Cl, AgClBr, AgClI, AgClBrI and the like can be used arbitrarily, but it is preferable that AgCl is a high silver chloride grain containing 90 mol% or more. More preferably, AgC of AgCl 95 mol% or more and AgI 1 mol% or less.
1, AgClBr, AgClI or AgClBrI. From the viewpoint of rapid processing property and processing stability, a silver halide emulsion containing 97 mol% or more of AgCl is more preferable.
AgC with gCl of 98 mol% or more and AgI of 1 mol% or less
1, AgClBr, AgClI or AgClBrI is particularly preferred.

In the tabular grains, silver halides having different compositions can be epitaxially grown or shelled on specific surface portions. In order to control the photosensitive nucleus, dislocation lines may be provided on the surface or inside of the tabular grains.

<Silver halide grain nuclei> It is preferred that the nuclei of the silver halide grains of the present invention are substantially free of iodine, and are normal crystals having neither twinning nor dislocation lines. The particle size of the core particles is preferably 0.2 μm or less for 70% or more of the total number of core particles, and more preferably 0.1% or more for 70% or more of the total number of core particles.
Most preferably, it is within a range of 1 μm or less and 0.005 μm or more. The coefficient of variation of the core particle size is preferably 30% or less, and most preferably 15% or less.

<Different Halogen> The different halogen ion used in the production method of the present invention is preferably a halide ion which forms a silver halide which is more insoluble than the host grains. Here, to give an example of the solubility of silver halide,
AgCl>AgBr> AgI. When the composition is two or more, the solubility decreases as the composition having a low solubility alone is contained. For example, in AgClBr, as the Br content increases,
In the case of containing I, the solubility increases as the I content increases.

<Production Method> The nucleation and / or the introduction of different types of halogens are carried out at a dispersion medium concentration of 1% by weight or more, preferably 1.5% by weight to 10% by weight.
The methionine content of the dispersion medium at the time of tabular grain growth is preferably 70% or less, more preferably 50% or less, and most preferably 30% or less at the time of the nucleation and / or introduction of a different type of halogen.
% Or less is good. The methionine content of the dispersion medium can be relatively compared by quantitative analysis of amino acids and the like. As a means for reducing the methionine content, a method for reducing the methionine in the dispersion medium in the reaction vessel by, for example, oxidizing the methionine after the nucleation and / or the introduction of a different type of halogen, or the nucleation and / or the introduction of a different type of halogen. For example, a method in which the dispersion medium is removed and a dispersion medium having a low methionine content is newly added can be selected for convenience. As a method for producing a dispersion medium having a low methionine content, US Pat.
No. 323, No. 4,942,120 and the like.

The physical ripening is performed following the heterogeneous halogen mixing process. The aging temperature is preferably 50 to 90 ° C,
~ 80 ° C is preferred. The aging time is preferably determined experimentally because the aging speed varies depending on conditions such as pCl.

In order to control grain growth during the formation of tabular grains, for example, ammonia, a thioether compound, a thione compound or the like can be used as a silver halide solvent. In addition, metal salts such as zinc, lead, thallium, iridium, and rhodium can coexist during physical ripening or chemical ripening.

The grain growth process is preferably carried out by a double jet method. One type of the double jet method is to maintain a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double method. The jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the tabular silver halide grains of the present invention, some or all of the steps during grain formation may be grain forming steps by supplying fine silver halide grains. Since the particle size of the fine particles supports the supply rate of halide ions, the preferred particle size varies depending on the size and the halogen composition of the silver halide grains of the host, but those having an average equivalent spherical diameter of 0.3 μm or less are preferably used. . More preferably, it is 0.1 μm or less. In order for the fine particles to be deposited on the host particles by recrystallization, the size of the fine particles is desirably smaller than the equivalent sphere diameter of the host particles, and more preferably 1/5 of the equivalent sphere diameter.
It is as follows.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention can be prepared by removing soluble salts after the completion of the growth of the silver halide grains to remove pAg suitable for chemical sensitization.
To obtain an ion concentration, a Nudel washing method, a flocculation sedimentation method, or the like may be used. As a preferred washing method, for example, an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086 is used. Method,
Alternatively, a desalting method using exemplified G-3, G-8, etc. which are polymer flocculants described in JP-A-2-7037 can be mentioned. Also, Research Disclosure (RD) V
ol. 102, 1972, October issue, Item 102
08 and Vol. 131, 1975, March, Item
Desalting may be performed using the ultrafiltration method described in JP13122.

<Silver halide photographic light-sensitive material> At least one photosensitive silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention contains tabular silver halide grains. Tabular grains having an aspect ratio of 2 or more account for 50% or more of the total projected area of all silver halide grains in the emulsion layer.
Particularly, as the proportion of tabular grains increases to 70% and further to 80%, more favorable results are obtained.

In the silver halide photographic light-sensitive material according to the present invention, non-tabular silver halide grains can be used in combination. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat.
Nos. 3,756, 4,225,666;
No. 26589, JP-B-55-42737, and The Journal of Photographic Science (J.
Photogr. Sci. ), Octahedron, tetrahedron, etc. by methods described in documents such as 21, 39 (1973).
Particles having a shape such as a dodecahedron can be produced and used. Further, particles having a twin plane may be used.

The composition of the silver halide grains other than the tabular grains is not particularly limited, and the preferred range is the same as that of the above-mentioned tabular grains. The particle size is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.1 to 1.2 μm, in consideration of other photographic properties such as rapid processing property and sensitivity.
It is in the range of 2 to 1.0 μm. Here, the particle size is represented by the length of one side of a cube when the silver halide grains are converted into a cube having the same volume.

The particle size distribution of the non-tabular silver halide grains is preferably a monodispersed silver halide grain having a coefficient of variation of 22% or less, more preferably 15% or less.

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

The non-tabular 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 one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Further, JP-A-57-92523 and JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble solution described in German Patent No. 2,921,164. Apparatus for continuously changing the concentration of silver salt and water-soluble halide salt aqueous solution, Japanese Patent Publication No. Sho 56
For example, an apparatus described in JP-A-501776, which takes out a reaction mother liquor out of a reactor and concentrates the solution by ultrafiltration to form grains while keeping the distance between silver halide grains constant, may be used.

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.

In the present invention, regardless of whether the silver halide grains are tabular or not, when AgBrCl or AgBrClI grains of high silver chloride are used, the silver halide grains having a portion containing silver bromide at a high concentration are used. Silver particles are particularly preferably used. In this case, the portion containing a high concentration of silver bromide may be epitaxy-bonded to silver halide emulsion grains, a so-called core-shell emulsion, or may be formed only partially without forming a complete layer. May simply have regions with different compositions. Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

It is advantageous that silver halide grains contain heavy metal ions. Heavy metal ions that can be used for such purposes include iron, iridium, platinum,
Group 8-10 metals such as palladium, nickel, rhodium, osmium, ruthenium, cobalt and cadmium,
Group 12 transition metals such as zinc and mercury, lead, rhenium,
Examples include molybdenum, tungsten, gallium, and chromium ions. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

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

When the heavy metal ion forms a complex, its ligand may be cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl, ammonia And the like. Among them, cyanide ion, thiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to allow the silver halide grains to contain heavy metal ions, the heavy metal compound is added to the silver halide grains during physical ripening before formation, during formation of silver halide grains, and during physical ripening after formation of silver halide grains. It may be added at any place in the process. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The amount of the heavy metal ion to be added is at least 1 × 10 ⁻⁹ mol per mol of silver halide and 1 × 10 ⁻² mol or more.
Mol or less, more preferably 1 × 10 ⁻⁸ mol or more and 5 × or less.
It is preferably at most 10 ^-5 mol.

In the silver halide emulsion layer of the silver halide color photographic light-sensitive material according to the present invention, a silver halide emulsion composed of single-shaped grains is preferably used, and two types of monodispersed silver halide emulsions are used. These may be added to the same layer.

The silver halide emulsion according to the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

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

The addition amount of the sulfur sensitizer according to the present invention is preferably changed depending on the kind of the silver halide emulsion to be applied and the size of the expected effect. ^In the range of ^{-10 to} 5 × 10 ^-5 mol,
Preferably it is in the range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

As the gold sensitizer according to the present invention, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ per mol of silver halide.
Preferably it is molar. More preferably, 1 × 10 ⁻⁵
Mol to 1 × 10 ⁻⁸ mol.

The chemical sensitization of the silver halide emulsion according to the present invention may be a reduction sensitization.

The silver halide emulsion according to the present invention is intended to prevent fogging during the preparation process of the silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fogging during development. And known antifoggants and stabilizers can be used. Examples of preferred compounds that can be used for such purposes include JP-A-2-146.
The compound represented by the general formula (II) described in the lower column of page 7 of the specification of JP-A No. 036 can be mentioned, and a more preferred specific compound is (IIa-1) described on page 8 of the same publication. ) To (IIa-8), (IIb-1) to (IIb)
-7) or 1- (3-methoxyphenyl) -5
Compounds such as -mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned. These compounds, depending on their purpose,
It is added in steps such as a step of preparing silver halide emulsion grains, a step of chemical sensitization, and a step of preparing a coating solution at the end of the step of chemical sensitization. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 × 10 ⁵ mol / mol of silver halide is used.
It is preferably used in an amount of about ^-4 mol. When added at the end of chemical sensitization, 1 × 10
^-6 mol to 1 × 10 ^-2 mol is preferable, and 1 × 10
^-5 mol to 5 × 10 ^-3 mol is more preferred. In the coating solution preparation step, when adding to the silver halide emulsion layer,
The amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide, more preferably 1 × 10 ^-5 mol to 1 × 10 ^-2 mol. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 × / m ^2.
An amount of about 10 ⁻⁹ mol to 1 × 10 ⁻³ mol is preferable.

In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, dyes having absorption in the visible region include AI described in JP-A-3-251840, page 308.
Dyes described in JP-A-6-3770 and dyes described in JP-A-6-3770 are preferably used. Examples of the infrared absorbing dye include general formula (I) described in the lower left column of page 2 of JP-A-1-280750. , (II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and are preferable because there is no contamination by residual color. Specific examples of preferred compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column of the same publication.

In order to improve the sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is more preferably 0.7 or more, and even more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the silver halide photographic light-sensitive material using the reflective support according to the present invention since the whiteness can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

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

As the spectral sensitizing dye for use in the silver halide emulsion according to the present invention, any known compounds can be used.
BS-1 to 8 described in page 28 of JP 51840 can be preferably used alone or in combination. Examples of the green photosensitive sensitizing dye include G
S-1 to S-5 are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. Issue 1
It is preferable to use the compounds S-1 to S-17 described on pages 5 to 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 silver halide photographic light-sensitive material according to the present invention, a coupling reaction with an oxidized form of a color developing agent is performed to form a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm. Any compound that can be used can be used, and particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500.
Typical examples are magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of -600 nm and cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

When an oil-in-water emulsion dispersion method is used to add the couplers and other organic compounds used in the silver halide photographic light-sensitive material according to the present invention, the water-insoluble emulsion usually has a boiling point of 150 ° C. or higher. In the boiling point organic solvent, if necessary, dissolve in combination with a low boiling point and / or water-soluble organic solvent,
It is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high-boiling organic solvents that can be used to dissolve and disperse the coupler include dioctyl phthalate, diisodecyl phthalate, phthalic acid esters such as dibutyl phthalate, tricresyl phosphate, and phosphoric acid esters such as trioctyl phthalate. It is preferably used. The dielectric constant of the high-boiling organic solvent is 3.
It is preferably from 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).

Preferred examples of the compound used as a surfactant for dispersing a photographic additive or adjusting the surface tension during coating include a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. Containing. Specifically, A-1 described in JP-A-64-26854 is described.
To A-11. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after dispersion and the time from the addition to the coating solution after the addition are preferably shorter.
The time is preferably within 3 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 on page 3 of JP-A-2-66541,
A phenolic compound represented by the general formula IIIB described in JP-A-3-174150, an amine-based compound represented by the general formula A described in JP-A-64-90445, and a phenolic compound described in JP-A-6-182741. Formulas XII, XIII, XI
Metal complexes represented by V and XV are particularly preferred for magenta dyes. Further, compounds represented by the general formula I described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and the compound described in the lower left column of page 10 of the same specification are disclosed. Compounds such as (A'-1) can be used. In addition, U.S. Pat.
No. 74,187 can also be used.

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

It is preferable to add an ultraviolet absorber to the light-sensitive material according to the present invention to prevent static fog or to improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by the formula III-3 described in JP-A-1-250944, and JP-A-64-6664.
6, a compound represented by the general formula III,
UV-1L to UV-27 described in 3-187240
L, compounds represented by the general formula I described in JP-A-4-1633, 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 silver halide photographic light-sensitive material according to the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other high polymers, gelatin Other than these, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers and copolymers can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-249
It is preferable to use the compounds described in JP-A Nos. 054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability. Further, in order to improve the physical properties of the surface of the light-sensitive material or the processed sample, a protective layer is disclosed in
It is preferable to add a slipping agent or matting agent described in JP-A-118543 or JP-A-2-73250.

As the reflective support used in the silver halide photographic light-sensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, or a paper support made of natural pulp or synthetic pulp. ,
A vinyl chloride sheet, polypropylene which may contain a white pigment, a polyethylene terephthalate support, baryta paper, and the like can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the reflective support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina,
Examples include alumina hydrate, titanium oxide, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the reflective support is preferably at least 13% by weight, more preferably at least 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 according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the coefficient of variation described in the above publication.

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

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the reflective support, if necessary, and then directly or undercoating (adhesion of the support surface). , One or more subbing layers to improve antistatic properties, dimensional stability, rub resistance, hardness, antihalation properties, friction properties and / or other properties) Is also good.

In the present invention, various kinds of transparent supports can be used. Examples of the support that can be used include polyester films such as polyethylene terephthalate and polyethylene naphthalate, cellulose triacetate films, cellulose diacetate films, polycarbonate films, polystyrene films, and polyolefin films.

The polyester support is not particularly restricted but includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid and ethylene glycol, 1,3-propanediol, 1,4-butanediol and the like. Condensation polymers with alkylene glycols such as, for example, polyethylene terephthalate, polyethylene-2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate and the like, and copolymers thereof.

In particular, JP-A-1-244446, JP-A-1-291248, JP-A-1-298350, JP-A-2-89045, JP-A-2-93641, and JP-A-1-244446, JP-A-1-291248, JP-A-2-93645, JP-A-2-181749, JP-A-2-214852 and JP-A-2-2911
It is preferable to use a polyester having a high water content as described in JP-A-35-35 and the like.

These polyesters may have a polar group and other substituents. In the present invention, the support is preferably polyethylene terephthalate or polyethylene naphthalate.

The polyester is preferably stretched at an area ratio of 4 to 16 times in order to satisfy the mechanical strength and dimensional stability of the film support. Further, it is preferable to perform a heat treatment (annealing treatment) as described in JP-A-51-16358 after film formation.

On the transparent support, there are provided a matting agent, an antistatic agent, a lubricant, a surfactant, a stabilizer, a dispersant, a plasticizer, an ultraviolet absorber, a conductive substance, a tackifier, a softener, and a fluidity-providing agent. , A thickener, an antioxidant, and the like.

The purpose of the transparent support is to neutralize the tint of the minimum density portion, prevent a light piping phenomenon (edge fogging) that occurs when light enters a film coated with a photographic constituent layer from an edge, and prevent halation. Can contain a dye.

The type of the dye is not particularly limited, but when a polyester film is used as the transparent support, those having excellent heat resistance in the film-forming step are preferable, and examples include anthraquinone-based chemical dyes. As for the color tone, when the purpose is to prevent light piping, gray dyeing is preferable as seen in general photosensitive materials. The dyes may be used alone or in combination of two or more. Diaresin, Bayer manufactured by Mitsubishi Chemical Corporation
The target can be achieved by using a dye such as MACROLEX manufactured by the company alone or in a suitable mixture.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be 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 formed on the photosensitive material to be printed and printed. Digital scanning exposure using monochromatic high-density light such as laser, light emitting diode, semiconductor laser, second harmonic generation light source (SHG) combining a solid-state laser using a semiconductor laser or a semiconductor laser as an excitation light source and a nonlinear optical crystal, etc. preferable. In particular, in order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) combining a semiconductor laser or a solid-state laser with a nonlinear optical crystal. Exposure time in such scanning exposure,
If the pixel size is defined as the exposure time when the pixel density is 400 dpi, the preferable exposure time is 10 ^-4 seconds or less, and more preferably 10 ^-6 seconds or less. As a specific method, a method using a light emitting diode as a light source described in JP-B-62-1305 or JP-A-63-18346.
The method uses a second harmonic obtained by using the semiconductor laser described in the above publication and the SHG element as a light source.

The present invention relates to a compound which forms a dye by a coupling reaction with a developing agent and an oxidized form of the developing agent, such as sulfonamidophenols, carbamoylhydrazines and carbamoylhydrazones described in Japanese Patent Application No. 10-44518. Or sulfonyl hydrazines can be used for a light-sensitive material having the light-sensitive material incorporated therein.

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

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β
-Hydroxyethyl) amino) aniline CD-6) 4-Amino-3-methyl-N-ethyl-N
-([Beta]-(methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9 ) 4-Amino-3-methyl-N-ethyl-N
-Methoxyethylaniline CD-10) 4-Amino-3-methyl-N-ethyl-
N- (β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-
N- (γ-hydroxypropyl) aniline In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

The processing temperature of color development according to the present invention is 35
The temperature is preferably from 70 ° C to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.

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

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

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a water washing process is performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed.

The developing apparatus used for developing the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is conveyed between rollers arranged in a processing tank, or a belt. An endless belt system that fixes and transports the photosensitive material may be used,
A processing tank is formed in a slit shape, and a processing liquid is supplied to this processing tank and a photosensitive material is transported. A spray method is used to spray the processing liquid. A web method is used to contact a carrier impregnated with the processing liquid. Alternatively, a method using a viscous treatment liquid may 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. In the form of adding a treating agent.
The method described in 5 is most preferred.

The image forming method according to the present invention can be preferably applied to a heat development system.

In the present invention, the heat development means that the exposed photosensitive material is heated to 50 ° C. to 250 ° C., preferably 60 ° C. to 150 ° C.
It refers to a method of performing development by heating to ° C. The heat treatment may be performed, for example, by a method of heating and conveying a photosensitive material between a heat drum and a drum belt as described in JP-A-63-71850, or by exposing a photosensitive material between a heater and a support base. A so-called direct heating method in which a material is set and heating is performed simultaneously with pressurization,
No. 2,640,42, etc., a method of passing a photosensitive material between far-infrared heaters, or heating by irradiating microwaves, a so-called indirect heating method, or a method combining a direct heating method and an indirect heating method. Can be used.

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 exposure and heat development are performed to obtain a final image by using one photosensitive material, and Examples 1 and 7 of JP-A-6-95321. As described in Example 1 of JP-A-225461, a final image is obtained by using a photosensitive material and a dye receiving material and diffusing and transferring the image dye formed or released by thermal development from the photosensitive material to the dye receiving material. Any of the so-called two-sheet systems obtained 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, Japanese Patent Application Laid-Open No.
As described in Example 1 of JP-A-20739, a method of performing development only by heating without supplying a reaction auxiliary from the outside, and described in Example 1 of JP-A-9-5968 and the like. As described above, any method may be used in which a small amount of a reaction aid (for example, water or the like) is supplied to a photosensitive material as necessary during thermal development and then thermal 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 is contained in the photosensitive material in advance is preferable, and examples of the thermal solvent include: For example, Japanese Patent Application Laid-Open No. 1-227150, page 4, upper left column-9
In the upper right column of the page, “0015” to “0” of JP-A-289856
018 "column and the like can be preferably used.

In the heat development, it is preferable to use a base generator from the viewpoint of improving the silver developing speed and the diffusion speed of the image dye.
No. 157637, page 3, lower right to page 6, ibid. 59-1805
No. 37, a method using a compound that generates a base by thermal decomposition, as described in the upper left column on page 4 to the lower left column on page 7, JP-A-8-87097, European Patent Publication 210,
No. 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 a metal ion constituting the basic metal compound. A method of generating a base with a combination of compounds capable of forming a complex using water as a medium can be used.

In the heat development, from the viewpoint of accelerating the silver development, an embodiment in which an organic silver salt is optionally contained in the light-sensitive material is also useful. Examples of the organic silver salt include long-chain aliphatic carboxylic acid silver salts and heterocyclic carboxylic acid silver salts described in JP-A-49-52626 and JP-A-53-36224. -137321,
A silver salt of a compound having an imino group described in JP-A-58-11838 or the like, or a silver salt of an acetylene compound described in JP-A-61-249044 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 preferably used. For example, compounds described in JP-A-9-5968, "0057" to "0060", can be preferably used.

When the light-sensitive material according to the present invention is used for thermal development, the compound capable of forming or releasing image dyes (dye-donating substance) is described in, for example, JP-A-61-611.
No. 57, No. 61-61158, No. 62-4438
Nos. 62-129850 and 62-129851
No. 62-169158, couplers forming a diffusible dye described in JP-A-3-73949 and the like;
Leuco dyes described in JP-A-61-88254, azo dyes described in U.S. Pat. No. 4,235,957, or JP-A-59-60434 and JP-A-59-6.
No. 5839, No. 59-71046, No. 59-8745
Compounds described in JP-A Nos. 59-155,055 and 59-165505, and JP-A-59-55430, JP-A-59-165054, and JP-A-59-165054.
Nos. 9-154445, 59-116655, 59
-124327, 59-152440, 64-
Compounds capable of forming image dyes in a manner opposite to silver development described in JP-A-13546 and JP-A-6-51474 can be preferably used.

Further, for example, JP-A-2-293753,
A photosensitive material using a microcapsule containing the polymerizable compound described in JP-A-2-308162 and the above-described dye-providing substance is subjected to a polymerization reaction in an image-like or reverse-image-like manner by heat development to produce a microcapsule. Cures and changes the diffusion speed of the image dye and the physical strength of the binder,
A heat development method of forming an image can also be used.

The light-sensitive material according to the present invention may employ a mode in which a developing agent or a precursor thereof is incorporated. The developing agent incorporated in the photosensitive material is required to be stable during storage of the photosensitive material and not to unnecessarily reduce silver salts. As developing agents satisfying such requirements, paraphenylenediamine-based agents described in JP-A-62-288835 and the like, and JP-A-9-15
806 and the like,
JP-A Nos. 5-241282, 8-234388, 8-286340, 9-152700, 9-1
No. 52701, No. 9-152702, No. 9-1527
No. 03, No. 9-152704 and the like, hydrazine-based active compounds described in JP-A Nos. 7-202002 and 8-234390.
And the like.

When the light-sensitive material according to the present invention contains a developing agent, development by activator processing can be preferably used in addition to the above-mentioned heat development processing. Activator processing refers to a processing method in which development processing is performed using a processing liquid (activator liquid) not containing a color developing agent.
Compounds necessary for color development are incorporated in the photosensitive material in advance. In this case, the activator solution is characterized in that it does not contain the color developing agent contained in the ordinary color developing solution component, and may contain other components such as an alkali and an auxiliary developing agent. Activator treatment is described in European Patent Nos. 545,491A1 and 565,165.
This is exemplified in known literature such as A1.

[0109]

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

Example 1 <Preparation of Tabular Grain Emulsion Em-a> The following solutions were prepared.

Solution G1 Ossein gelatin 31.45 g NaCl 1.26 g Make up 1534.5 ml with distilled water Solution Ag1 1.18 N silver nitrate aqueous solution X1 1.21 N NaCl aqueous solution X2 0.06 N KI aqueous solution Solution Ag2 2.94 N silver nitrate Aqueous solution Solution X3 3.01 N NaCl aqueous solution.

The total amount of the solution G1 was placed in a reaction vessel at 40 ° C.
The pH was adjusted to 4.3. While sufficiently stirring, the solution Ag1
And the same amount of solution X1 as 17.98 ml was simultaneously added over 15 seconds. After stirring for 3 minutes, 65 ml of solution X2 was added into the reaction vessel at 186 ml / min. After stirring for 9 minutes, 53.95 ml of solution Ag1 and the same amount of solution X1 were simultaneously added over 45 seconds. The pH was adjusted to 6.5 and the mixture was further stirred for 30 minutes. Adjust pCl to 1.75, 7
The solution was heated to 0 ° C. and aged for 20 minutes.
The same amount of solution X3 as 1.22 ml was simultaneously added over 20 minutes. After further aging for 30 minutes, the temperature was lowered to 45 ° C., desalted with 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 form a plate. A grain emulsion Em-a was obtained.

<Preparation of Tabular Grain Emulsion Em-b> The whole amount of the solution G1 was placed in a reaction vessel and adjusted to 40 ° C. and pH 4.3. With sufficient stirring, 17.98 ml of solution Ag1 and the same amount of solution X1 were simultaneously added over 15 seconds. After stirring for 3 minutes, 65 ml of solution X2 was added into the reaction vessel at 186 ml / min. After stirring for 9 minutes, 53.95 ml of solution Ag1 and the same amount of solution X1 were simultaneously added over 45 seconds. After adding 12.6 ml of 1.9% hydrogen peroxide solution, the pH was adjusted to 6.5, and the mixture was further stirred for 30 minutes. pC
1 was adjusted to 1.75, the temperature was raised to 70 ° C., and the mixture was aged for 20 minutes.
Was added simultaneously over 20 minutes. After further aging for 30 minutes, the temperature was lowered to 45 ° C., desalted using a 5% aqueous solution of Demol N and 20% aqueous magnesium sulfate manufactured by Kao Atlas Co., Ltd., and then mixed with an aqueous gelatin solution to form a plate. A grain emulsion Em-b was obtained.

<Preparation of Tabular Grain Emulsion Em-c> The whole amount of the solution G1 was charged into a reaction vessel and adjusted to 40 ° C. and pH 4.3. With sufficient stirring, 17.98 ml of solution Ag1 and the same amount of solution X1 were simultaneously added over 15 seconds. After stirring for 3 minutes, 65 ml of solution X2 was added into the reaction vessel at 186 ml / min. After stirring for 9 minutes, 53.95 ml of solution Ag1 and the same amount of solution X1 were simultaneously added over 45 seconds. After adding 12.6 ml of 9.6% aqueous hydrogen peroxide, the pH was adjusted to 6.5, and the mixture was further stirred for 30 minutes. pC
1 was adjusted to 1.75, the temperature was raised to 70 ° C., and the mixture was aged for 20 minutes.
Was added simultaneously over 20 minutes. After further aging for 30 minutes, the temperature was lowered to 45 ° C., desalted using a 5% aqueous solution of Demol N and 20% aqueous magnesium sulfate manufactured by Kao Atlas Co., Ltd., and then mixed with an aqueous gelatin solution to form a plate. A grain emulsion Em-c was obtained.

<Preparation of Tabular Grain Emulsion Em-d> The following solutions were prepared.

Solution G2 Ossein gelatin 7.67 g NaCl 1.26 g Make up to 1534.5 ml with distilled water. In the preparation of Em-c, solution G2 was used instead of solution G1.
Was used in the same manner except that silver halide emulsion Em- was used.
d was obtained.

<Preparation of Tabular Grain Emulsion Em-e> The following solutions were prepared.

Solution G3 Ossein gelatin 18.41 g NaCl 1.26 g Make up to 1534.5 ml with distilled water. In the preparation of Em-c, solution G3 was used instead of solution G1.
Was used in the same manner except that silver halide emulsion Em- was used.
e was obtained.

Each of the obtained silver halide grains was all (1)
(00) on the main plane. Table 1 shows the measurement results. In Table 1, R1: ratio of tabular grains having an aspect ratio of 2 or more to the total projected area R2: average thickness [μm] R3: average aspect ratio R4: tabular halogenation having an aspect ratio of 3 or more and a thickness of 0.3 μm or less. Particle size distribution of silver particles (The particle size distribution is represented by a value obtained by dividing the standard deviation of the particle size distribution by the average particle size and multiplying by 100).

[0120]

[Table 1]

As is evident from Table 1, the method of the present invention can provide a high aspect ratio (100) flat plate having a higher flat plate ratio.

Example 2 (Preparation of Blue-Sensitive Silver Halide Emulsion (Em-B1)) 4
In 1 liter of a 2% aqueous gelatin solution kept at 0 ° C., the following (solution A1) and (solution B1) were pAg = 7.3, pH =
The solution was added simultaneously while controlling to 3.0, and the following (solution C1) and (solution D1) were simultaneously added while controlling to pAg = 8.0 and pH = 5.5. At this time, the control of pAg is described in
The control of pH was performed using sulfuric acid or an aqueous sodium hydroxide solution.

(Solution A1) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B1) 10 g of silver nitrate 200 ml with addition of water (Solution C1) 102.7 g of sodium chloride 102.7 g of potassium hexachloroiridium (IV) 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g Add water 600 ml (Solution D1) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas Demol After desalting was performed using a 5% aqueous solution of N and a 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size 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-1A was obtained. Next, in the preparation of EMP-1A, the average particle size was 0.64 μm and the particle size was the same except that the addition time of (A1 solution) and (B1 solution) and the addition time of (C1 solution) and (D1 solution) were changed. A monodisperse cubic emulsion EMP-1B having a distribution variation coefficient of 0.07 and a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-1A was optimally chemically sensitized at 60 ° C. using the following compounds. EMP-1
Similarly, after optimally chemical sensitizing B, the sensitized EMP-1A and EMP-1B were mixed at a silver amount of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B1). I got

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 (blue-sensitive tabular silver halide emulsion (Em-aB to eB)
Preparation of Em-a to e-
Optimum chemical sensitization was performed at 0 ° C to obtain blue-sensitive silver halide tabular emulsions Em-aB to eB.

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 (green-sensitive silver halide emulsion (Preparation of (Em-G1)) In the preparation of silver halide emulsion EMP-1A, (A1 solution)
The average particle size was 0.40 in the same manner except that the addition time of (B1 solution) and (C1 solution) and (D1 solution) were changed.
μm, monodisperse cubic emulsion EMP-11A having a silver chloride content of 99.5 mol%, and monodisperse cubic emulsion EMP-11B having an average particle size of 0.45 μm and a silver chloride content of 99.5 mol%.
I got

The above-mentioned EMP-11A was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also EMP-
Similarly, after optimally sensitizing EMP-11B, the sensitized EMP-11A and EMP-11B were mixed at a silver ratio of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G
1) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ^-4 mol / mol AgX Stabilizer STAB-3 3 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion (Em-R1)) The above-mentioned silver halide emulsion In preparing EMP-1A,
Except that the addition time of (A1 solution) and (B1 solution) and the addition time of (C1 solution) and (D1 solution) were changed, the average particle diameter was 0.43 μm and the silver chloride content was 99.5 mol%. Monodisperse cubic emulsion EMP-21A and average particle size 0.40μ
m, monodispersed cubic emulsion E having a silver chloride content of 99.5 mol%
MP-21B was obtained.

The above-mentioned EMP-21A was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also EMP-
Similarly, after optimally chemical sensitizing 21B, the sensitized EMP-21A and EMP-21B were mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R
1) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX SS-1 2.0 × 10 ⁻³ mol / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-3 3 × 10 ^-4 mol / mol AgX

[0131]

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(Preparation of Photosensitive Material (101)) Basis Weight 180
High-density polyethylene was laminated on both sides of g / m ² paper pulp to produce a paper support. However, on the side on which the emulsion layer was applied, a molten polyethylene containing anatase-type titanium oxide having a surface treatment dispersed therein at a content of 15% by weight was laminated. 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 material (101). In the preparation of the photosensitive material, each coating solution was prepared so as to have the following coating amount, and (H-
1) and (H-2) were added. Surfactants (SU-1), (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² . The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) 7th layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 6th layer (UV absorbing layer) Gelatin 0.40 AI-1 0.01 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Stain inhibitor (HQ-5) 0.04 PVP 0.03 Fifth layer (red-sensitive layer) Gelatin 1.30 Red-sensitive emulsion (Em-R1) 0.21 Cyan coupler (C-1) 0.33 Dye image stabilizer (ST-1) 0 .10 Anti-stain agent (HQ-1) 0.004 DBP 0.10 DOP 0.20 Fourth layer (ultraviolet absorbing layer) Gelatin 0.94 Ultraviolet absorbing agent (UV-1) 0.28 Ultraviolet absorbing agent (UV- 2) 0.09 UV absorption Agent (UV-3) 0.38 AI-1 0.02 Stain inhibitor (HQ-5) 0.10 Third layer (green-sensitive layer) Gelatin 1.30 AI-2 0.01 Green-sensitive emulsion ( Em-G1) 0.14 Magenta coupler (M-1) 0.20 Dye image stabilizer (ST-3) 0.20 Dye image stabilizer (ST-4) 0.17 DIDP 0.13 DBP 13 Second layer (intermediate layer) Gelatin 1.20 AI-3 0.01 Stain inhibitor (HQ-2) 0.03 Stain inhibitor (HQ-3) 0.03 Stain inhibitor (HQ-4) 05 Stain inhibitor (HQ-5) 0.23 DIDP 0.04 DBP 0.02 Optical brightener (W-1) 0.10 First layer (blue-sensitive layer) Gelatin 1.20 Blue-sensitive emulsion ( Em-B1) 0.26 Yellow coupler (Y-1) 0 70 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer (ST-2) 0.10 Dye image stabilizer (ST-5) 0.10 Stain inhibitor (HQ-1) 01 Image stabilizer A 0.15 DBP 0.10 DNP 0.05 Support Polyethylene laminated paper The amount of silver halide applied was shown in terms of silver.

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 H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium DBP: dibutyl phthalate DIDP: diisodecyl phthalate DOP : Dioctyl phthalate DNP: dinonyl phthalate PVP: polyvinylpyrrolidone 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) butylhydroquinone Image stabilizer A : Pt-octylpheno Rule

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The thus-prepared sample was designated as 101, exposed to a light wedge by a conventional method, and then subjected to a developing process in the following developing process.

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

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriamine Sodium pentaacetate 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make the total volume 1 liter. = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fix solution and replenisher Ferric ammonium diethylenetriaminepentaacetate dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 0.0g ammonium sulfite (40% aqueous solution) 27.5ml 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 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water.

In Sample 101, the used amount (addition amount) of Em-B1 was changed as shown in Table 2, or the amount of Em-B1 was changed.
Were changed to the emulsions shown in Table 2, except that samples 102 to 107 were prepared in the same manner as sample 101, and processed in the same manner as sample 101 to measure the following properties.

Using the obtained sample, the characteristic curve of blue density was measured using a PDA-65 densitometer (manufactured by Konica Corporation), and the maximum density, sensitivity and γ were measured. The sensitivity was defined based on the reciprocal of the exposure amount giving a density of 0.75, and was expressed as a relative value with the sensitivity of Sample 101 as a standard sample being 100.

Here, γ is defined as an exposure amount giving fog +0.3 and a slope connecting two points on a sensitometric curve at an exposure amount 100 times the exposure amount. Expressed as a relative value.

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[Table 2]

As can be seen from Table 2, the sample of the present invention has a high sensitivity, and can provide a photographic light-sensitive material having a high maximum sensitivity and a low fog even with a small amount of silver halide applied.

Example 3 The same processing as in Example 2 was performed as described below.

Processing Step Processing Temperature Time Replenishment Color Development 38.0 ± 0.3 ° C. 22 seconds 81 ml Bleaching and Fixing 35.0 ± 0.5 ° C. 22 seconds 54 ml Stabilization 30-34 ° C. 25 seconds 150 ml Drying 60-80 30 ° C. The composition of the developing solution is shown below.

Color developer tank liquid and replenisher tank liquid Replenisher Pure water 800 ml 800 ml diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.5 g 10.5 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxyamine 3. 5 g 6.0 g Triethanolamine 10.0 g 10.0 g Sodium salt of diethylenetriaminepentaacetic acid 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Add water to make the total volume 1 liter, Is pH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fix solution tank solution and replenisher tank solution Replenisher diethylenetriamine pentaacetate ammonium ferric dihydrate 100 g 50 g diethylenetriaminepentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml 2-amino-5-mercapto-1 2,3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml Add water to make the total volume 1 liter, use potassium carbonate or glacial acetic acid to adjust the tank solution to pH = 7.0, pH = 6.
Adjust to 5.

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 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g PVP 1.0 g Aqueous ammonia (25% aqueous ammonium hydroxide) 2.5 g Ethylenediaminetetraacetic acid 1 0.0 g Ammonium sulfite (40% aqueous solution) 10 ml Water is added to make the total volume 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

Evaluation was performed in the same manner as in Example 2, and it was confirmed that the effects of the present invention could be effectively obtained even when color paper was rapidly processed.

Example 4 In Example 2, Konica Corporation's N was used as an automatic developing machine.
PS-868J, ECOJET-P as processing chemical
And a running process was performed according to the process name CPK-2-J1. Evaluation was performed in the same manner as in Example 1, and it was confirmed that the effects of the present invention were obtained.

Example 5 The following composition was applied on a cellulose triacetate film support provided with an undercoat layer to prepare a sample 301 as a multilayer color photosensitive material.

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material is 1 m ² unless otherwise specified.
Indicates the number of grams per unit. Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed in moles per mole of silver halide.

First layer: Antihalation layer Black colloidal silver 0.18 Ultraviolet absorber (UV-11) 0.30 High boiling organic solvent (Oil-2) 0.17 Gelatin 1.59 Second layer: Intermediate layer High Boiling point organic solvent (Oil-2) 0.01 Gelatin 1.27 Third layer: Low-sensitivity red-sensitive layer Emulsion (Em-2) 0.80 Sensitizing dye (SD-1) 5.0 × 10 ^-5 sensitization Dye (SD-2) 9.0 × 10 ^-5 sensitizing dye (SD-3) 1.9 × 10 ^-5 sensitizing dye (SD-4) 2.0 × 10 ^-4 sensitizing dye (SD-5) ) 2.8 × 10 ^-4 cyan coupler (C-11) 0.42 Colored cyan coupler (CC-1) 0.02 High boiling solvent (Oil-1) 0.35 gelatin 1.02 Fourth layer: medium sensitivity red-sensitive layer emulsion (Em-1) 0.40 sensitizing dye (SD-3) 1.8 × 10 -5 sensitizing dye (SD 4) 2.4 × 10 ^-4 Sensitizing dye (SD-5) 4.5 × 10 -4 Cyan coupler (C-11) 0.26 Colored cyan coupler (CC-1) 0.05 DIR compound (D- 1) 0.01 High boiling solvent (Oil-1) 0.31 Gelatin 0.78.

Fifth layer: high-sensitivity red-sensitive layer Emulsion (Em-3) 1.51 Sensitizing dye (SD-3) 1.8 × 10 ^-5 Sensitizing dye (SD-4) 3.1 × 10 ^{− 4} Sensitizing dye (SD-5) 2.7 × 10 ^-4 Cyan coupler (C-12) 0.11 Colored cyan coupler (CC-1) 0.02 DIR compound (D-2) 0.04 High boiling solvent (Oil-1) 0.17 Gelatin 1.15 6th layer: Intermediate layer Gelatin 0.80 7th layer: Low sensitivity green-sensitive layer Emulsion (Em-2) 0.21 Sensitizing dye (SD-1) 9 × 10 ^-5 sensitizing dye (SD-6) 3.1 × 10 ^-4 sensitizing dye (SD-9) 1.8 × 10 ^-4 sensitizing dye (SD-11) 5.6 × 10 ^-5 Magenta coupler (M-11) 0.20 Colored magenta coupler (CM-1) 0.05 DIR compound (D-1) 0.02 High boiling organic Agent (Oil-2) 0.27 Gelatin 1.34.

Eighth layer: middle-sensitivity green-sensitive layer Emulsion (Em-2) 0.82 Sensitizing dye (SD-1) 5.0 × 10 ^-5 Sensitizing dye (SD-6) 2.7 × 10 ^{− 4} Sensitizing dye (SD-9) 1.7 × 10 ^-4 Sensitizing dye (SD-11) 4.8 × 10 ^-5 Magenta coupler (M-11) 0.21 Colored magenta coupler (CM-1) 0 0.05 DIR compound (D-4) 0.02 High boiling organic solvent (Oil-2) 0.33 Gelatin 0.89 Ninth layer: Highly sensitive green-sensitive layer Emulsion (Em-3) 0.99 Sensitizing dye ( SD-6) 3.6 × 10 ^-4 sensitizing dye (SD-7) 7.0 × 10 ^-5 sensitizing dye (SD-8) 4.8 × 10 ^-5 sensitizing dye (SD-11) 6 2 × 10 ^-5 Magenta coupler (M-11) 0.05 Magenta coupler (M-12) 0.06 Colored magenta coupler (CM-2) 0 0.03 High boiling organic solvent (Oil-2) 0.25 Gelatin 0.88 10th layer: Intermediate layer High boiling organic solvent (Oil-1) 0.25 Gelatin 0.50 11th layer: Yellow filter layer Yellow colloidal silver 0.11 color stain inhibitor (SC-1) 0.12 high boiling point solvent (Oil-2) 0.16 gelatin 1.00.

12th layer: Intermediate layer Gelatin 0.36 13th layer: Low-sensitivity blue-sensitive layer Emulsion (Em-2) 0.37 Sensitizing dye (SD-10) 5.6 × 10 ^-4 sensitizing dye ( SD-11) 2.0 × 10 ^-4 sensitizing dye (SD-13) 9.8 × 10 ^-5 Yellow coupler (Y-11) 0.39 Yellow coupler (Y-12) 0.14 DIR compound (D -5) 0.03 High boiling organic solvent (Oil-2) 0.11 Gelatin 1.02 Fourteenth layer: Medium-sensitivity blue-sensitive layer Emulsion (Em-2) 0.46 Emulsion (Em-1) 0.10 increase Sensitizing dye (SD-10) 5.3 × 10 ^-4 sensitizing dye (SD-11) 1.9 × 10 ^-4 sensitizing dye (SD-13) 1.1 × 10 ^-5 Yellow coupler (Y-11) ) 0.28 Yellow coupler (Y-12) 0.10 DIR compound (D-5) 0.05 High boiling organic solvent Agent (Oil-2) 0.08 Gelatin 1.12.

Fifteenth layer: high-sensitivity blue-sensitive layer Emulsion (Em-3) 0.04 Emulsion (Em-4) 0.28 Sensitizing dye (SD-11) 8.4 × 10 ^-5 sensitizing dye (SD -12) 2.3 × 10 ^-4 Yellow coupler (Y-11) 0.04 Yellow coupler (Y-12) 0.12 High boiling organic solvent (Oil-2) 0.03 Gelatin 0.85 16th layer: First protective layer Emulsion (Em-5) 0.30 UV absorber (UV-12) 0.03 UV absorber (UV-13) 0.015 UV absorber (UV-14) 0.015 UV absorber ( UV-15) 0.015 Ultraviolet absorber (UV-16) 0.10 High boiling organic solvent (Oil-1) 0.44 High boiling organic solvent (Oil-3) 0.07 Gelatin 1.35 17th layer: Second protective layer Alkali-soluble matting agent (PM- 0.15 Polymethyl methacrylate (average particle size 3 μm) 0.04 Slip agent (WAX-1) 0.02 Gelatin 0.54 In addition to the above-mentioned composition, compounds SU-11 and SU- 12,
SU-13, SU-14, viscosity modifier V-1, hardener H
-11, H-12, stabilizer ST-11, antifoggant A
F-1 and AF-2, two types of AF- having a weight average molecular weight of 10,000 and a weight average molecular weight of 1,100,000
3. Dyes AI-11, AI-12, AI-13, compounds FS-1, FS-2 and preservative DI-1 were appropriately added to each layer.

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The emulsions used in the above samples are as follows. The average particle size is shown as a particle size converted into a cube. Each emulsion was optimally subjected to gold, sulfur, and selenium sensitization.

Emulsion name Average AgCl Average AgBr Crystal habit Side length Content (mol%) Content (mol%) (μm) Em-1 99 1 cube 0.46 Em-299 1 cube 0.30 Em- 399 1 Cube 0.70 Em-4 991 Cube 0.85 Em-5 50 50 Cube 0.07 Next, in Sample 301, the emulsion Em-4 used for the 15th high-sensitivity blue-sensitive layer was replaced with Em-a Samples 302 to 306 were prepared by substituting the emulsions of Em.-Em-e with gold, sulfur, and selenium sensitized emulsions. The samples 301 to 306 thus obtained were exposed to white light wedge and subjected to the following development processing, and the fog (Dmin) was compared with a relative value of the sample 301 with the sensitivity of the blue-sensitive layer being 100.

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[Table 3]

However, the stabilization treatment was carried out in a three-tank counter current, in which the stabilizing solution was replenished to the last tank, and the overflow flowed into the preceding tank. Further, a part of the overflow of the stabilization tank following the fixing tank (275 ml / m ² )
Was poured into a fixing tank.

The compositions of the used color developing solution and its replenisher are as follows.

[Color developing solution] Potassium bromide 15 mg Potassium chloride 5.0 g Potassium sulfite 0.4 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylhydroxyl Amine 5.0 g Potassium carbonate 30 g Sodium diethylenetriamine pentaacetate 2.5 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Nitrilotri (methylenephosphonic acid) 2.0 g Hydrazinodiacetic acid 2.0 g Finished to 1 liter with water and hydroxylated The pH was adjusted to 10.05 with potassium or 50% sulfuric acid.

[Color Developing Replenisher] Potassium chloride 0.2 g Potassium sulfite 0.9 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 6.2 g Diethylhydroxylamine 7. 0 g Potassium carbonate 32 g Sodium diethylenetriamine pentaacetate 3.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.5 g Nitrilotri (methylenephosphonic acid) 2.5 g Hydrazinodiacetic acid 2.5 g Finished to 1 liter with water Potassium hydroxide or 50 The pH was adjusted to 10.40 with% sulfuric acid.

The composition of the bleaching solution used is as follows.

Ferric ammonium 1,3-diaminopropanetetraacetate 0.35 mol Disodium ethylenediaminetetraacetate 2 g Ammonium bromide 150 g Glacial acetic acid 40 ml Ammonium nitrate 40 g Add water to make 1 liter, and use ammonia water or glacial acetic acid. Adjust to pH 4.5.

The composition of the bleaching replenisher used was as follows.

Ferric ammonium 1,3-diaminopropanetetraacetate 0.40 mol Disodium ethylenediaminetetraacetate 2 g Ammonium bromide 170 g Ammonium nitrate 50 g Glacial acetic acid 61 ml Add water to make 1 liter, and use ammonia water or glacial acetic acid. The pH is adjusted to 3.5, and the pH of the bleaching tank solution is adjusted appropriately so as to maintain the pH.

The compositions of the fixing solution and fixing replenisher used are as follows.

Ammonium thiosulfate 100 g Ammonium thiocyanate 150 g Anhydrous sodium bisulfite 20 g Sodium metabisulfite 4.0 g Disodium ethylenediaminetetraacetate 1.0 g Water was added to 700 ml, and the pH was adjusted to 6.5 using glacial acetic acid and aqueous ammonia. I do.

The composition of the used stabilizing solution and stabilizing replenisher is as follows.

1,2-benzisothiazolin-3-one 0.1 g pn-octyl-decaethyleneoxy-phenol 50% aqueous solution 2.0 ml hexamethylenetetramine 0.2 g hexahydro-1,3,5-tris (2- Hydroxyethyl) -5-triazine 0.3 g Water was added to make up to 1 liter, potassium hydroxide and 50%
The pH was adjusted to 7.0 using sulfuric acid.

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[Table 4]

As shown in Table 4, even when rapid processing was performed in the color negative processing, the present invention exhibited lower fog and higher sensitivity as compared with the comparative emulsion.

According to the present invention, silver halide grains having high sensitivity, low fog and excellent in rapid processing, a method for producing the same, and a silver halide photographic material are obtained.

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According to the present invention, a silver halide emulsion having high sensitivity and excellent in rapid processing, a method for producing the silver halide emulsion, a silver halide photographic material containing the silver halide emulsion, and a photothermographic material. Materials, photosensitive materials for activator development,
And an image forming method using such a photosensitive material.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/407 G03C 7/407 (54) [Title of the Invention] Silver halide emulsion, Manufacturing method, silver halide photo-sensitive material containing the silver halide emulsion, photo-sensitive material for heat development, photo-sensitive material for activator development, and image forming method using these photo-sensitive materials

Claims (9)

[Claims] 1. A silver halide emulsion containing a dispersion medium and silver halide grains, wherein the silver halide grains have a silver chloride content of 50 mol% or more of the total silver, and (100)
Tabular grains having a major plane and an aspect ratio of 2 or more account for at least 50% of the total projected area, and the silver halide emulsion has at least a) a process of forming nucleus grains; A) a step of forming an anisotropic growth defect by adding a different halogen; c) a step of growing a tabular grain, wherein the methionine content in the dispersion medium in the step c) is at least selected from the steps a) and b). A method for producing a silver halide emulsion, characterized in that it is not more than 70% of one. 2. The method according to claim 1, wherein the concentration of the dispersing medium is at least 1 w% in at least one selected from a) a step of forming a core particle and b) a step of forming an anisotropic growth defect by adding a halogen having a different composition from the core particle. The method for producing a silver halide emulsion according to claim 1, wherein 3. A silver halide emulsion produced by the method for producing a silver halide emulsion according to claim 1. Description: 4. A silver halide photographic material comprising at least one layer containing the silver halide emulsion according to claim 3. 5. An image forming method, comprising developing the silver halide photographic material according to claim 4 after imagewise exposure. 6. A photothermographic material comprising at least one layer containing the silver halide emulsion according to claim 3. 7. An image forming method, comprising subjecting the photosensitive material for heat development according to claim 6 to imagewise exposure and then subjecting the material to heat development. 8. A photosensitive material for activator development, wherein at least one layer contains the silver halide emulsion according to claim 3. 9. An image forming method, comprising subjecting the activator developing photosensitive material according to claim 8 to imagewise exposure and then subjecting it to heat development.