JP2000010225A - Production of silver halide emulsion, silver halide photographic sensitive material, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide emulsion having high sensitivity, high contrast, excellent gradation in the shoulder part and high stability of a latent image in high illuminance exposure by sensitizing specified silver halide particles with gold and sulfur, adding a substance which is adsorbed to the particle surface, lowering the temp. and then adding a bromide. SOLUTION: Silver halide particles having the following properties are sensitized with gold and sulfur. The particles have >=90 mol.% silver chloride content to the total silver amt., and contains planar particles having (100) planes as the principal planes and >=2 aspect ratio by >=50% of the total projected area. The temp. is lowered, a substance which is adsorbed to the particle surface is added, and further a bromide is added. The planar particles to be used have preferably <=0.3 μm thickness. Preferably, the distribution of the planar particles shows <=30% coefft. of variation to be used. The silver halide particles to be used may be subjected to noodling water washing method after the growth of silver halide particles is completed so as to remove a soluble base and to obtain a PAg ion concn. suitable for the chemical sensitization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silver halide emulsion, a silver halide photographic light-sensitive material and an image forming method. The present invention relates to a method for producing a silver halide emulsion, a silver halide photographic light-sensitive material, and an image forming method which are excellent in tone and have good latent image stability and high production stability.

[0002]

2. Description of the Related Art Hitherto, silver halide grains having a high silver chloride content have been used to improve the rapid processing suitability of silver halide photographic light-sensitive materials. However, the silver halide photographic light-sensitive material containing high silver chloride grains has problems that not only high fog and low sensitivity but also high illuminance exposure characteristics are poor. In order to increase the sensitivity, studies on so-called tabular grains have been actively conducted.

For example, methods for forming tabular grains having a (100) plane as a main plane are described in JP-A-5-204073, US Pat. Nos. 5,264,337 and 5,275,930, and JP-A-6-301131. No., 6-308648, 6
-337489, 6-337490, 6-33
No. 7507 and the like.

[0004] Further, various proposals have been made so far to improve the suitability for high-illumination exposure.
Not enough due to problems such as sensitivity.

[0005] For example, Japanese Patent Application Laid-Open No. 1-105940 discloses 9
20% of silver halide grains containing 0 mol% or more of silver chloride.
% Or more of silver halide grains having a bromine-localized phase in which more than 50% of all iridium is coprecipitated in the bromine-localized phase. Also, JP-A-3-188435 discloses that
It is described that a chemical sensitization is carried out after forming a silver bromide localized phase near the surface, and the temperature at this time is preferably 55 ° C. or lower. JP-A-6-194768 describes a method in which a low chloride concentration epitaxial layer is formed on a (100) silver chloride flat plate, and the epitaxial portion is protected by an adsorbed substance to perform chemical sensitization. JP-A-9-15771 describes that after chemical sensitization, the mixture is cooled to 50 ° C. or lower, and bromide and sensitizing dye are added in this order.

However, even with these methods, softening, latent image stability and production stability were inferior.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a halogen having high sensitivity, high contrast, excellent shoulder gradation, high latent image stability and high production stability in high illuminance exposure. An object of the present invention is to provide a method for producing a silver halide emulsion, and a silver halide photographic material and an image forming method using the silver halide emulsion.

[0008]

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

(1) Tabular grains having a silver chloride content of 90 mol% or more of the total silver, a (100) plane on the main plane and an aspect ratio of 2 or more are 50% or more of the total projected area. A method for producing a silver halide emulsion, comprising sensitizing silver halide grains as described in (1) above with gold / sulfur sensitizer, adding a substance adsorbed on the surface of the grains, lowering the temperature, and then adding bromide.

(2) The coverage of the adsorbed substance on the particle surface is 2 to 2.
2. The method for producing a silver halide emulsion according to the above 1, wherein the content is 80%.

(3) The method for producing a silver halide emulsion as described in (1) or (2) above, wherein an iridium compound is present when bromide is added.

(4) The method for producing a silver halide emulsion as described in any one of (1) to (3) above, wherein the bromide is silver bromide fine particles.

(5) The method for producing a silver halide emulsion as described in any one of (1) to (4) above, wherein the bromide is fine silver bromide particles containing iridium.

(6) The temperature at the time of gold / sulfur sensitization is 55 ° C.
6. The method for producing a silver halide emulsion according to any one of the above items 1 to 5, wherein the temperature at the time of adding the bromide is 50 ° C. or lower.

(7) A compound represented by the following general formula (1) is added after forming silver halide tabular grains containing 90 mol% or more of silver chloride and before performing chemical sensitization. 7. The method for producing a silver halide emulsion according to any one of the above items 1 to 6.

Formula (1) (ML ₆ ) ^{n wherein} M represents a filled frontier orbital polyvalent metal ion, and L represents a coordination complex ligand which can be independently selected. However, at least one of the ligands is more electronegative than any halide ligand, and n
Represents -1, -2, -3 or -4. (8) In at least one of the silver halide photographic light-sensitive layers,
8. A silver halide photographic material comprising a silver halide emulsion produced by the method for producing a silver halide emulsion as described in any one of 1 to 7 above.

(9) An image forming method for a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to the item (8) is exposed for an exposure time shorter than 10 μsec.

The present invention will be described in more detail. The silver halide grains used in the present invention have a silver chloride content of 50 mol% or more of the total silver content in at least 50% of the total projected area (1).
The silver halide grains are tabular grains having a (00) plane on the main plane and an aspect ratio of 2 or more.

The aspect ratio as used herein refers to the ratio of the diameter of a circle having the same area as the projected area of tabular grains to 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,
It is particularly preferred that the number be 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, the parallel principal plane is preferably 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). There shall be 1000 or more discriminations.) 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
Cl, AgClBr, AgClI, AgClBrI, etc. can be used arbitrarily, but it is preferable that AgCl is a high silver chloride grain having 90 mol% or more. More preferably, Ag of 95 mol% or more and AgI of 1 mol% or less is used.
Cl, 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 halide having a different composition can be epitaxially grown or shelled on a specific surface portion. In order to control the photosensitive nucleus, dislocation lines may be provided on the surface or inside of the tabular grains.

It is preferable that the nuclei of the particles 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 not less than 70% of the total number of core particles.
It is preferably 2 μm or less, and more preferably 70% or more of the total number of nuclear particles is in the range of 0.1 μm or less and 0.005 μm or more. The coefficient of variation of the core particle size is 30
% Or less, and most preferably 15% or less.

In order to control the growth of grains 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 obtained by removing soluble salts after the completion of the growth of the silver halide grains and removing 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.

In the silver halide photographic material of the present invention, at least one photosensitive silver halide emulsion layer 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. In particular, the ratio of tabular grains is 70%,
More favorable results are obtained with an increase to 80%.

The silver halide grains of the present invention are all tabular grains having a silver chloride content of at least 90 mol% of the total silver, a (100) plane on the main plane and an aspect ratio of at least 2. The silver halide grains that are 50% or more of the projected area
After the sulfur sensitization, the temperature is lowered, and then the surface-adsorbed substance is added, followed by the addition of bromide.

The substance adsorbed on the grain surface of the present invention may be any substance adsorbed on the surface of the silver halide emulsion, but as the substance which does not impair the photographic performance and the suitability for rapid processing, spectral sensitizing dyes and antifoggants are preferred. As the spectral sensitizing dyes, simple cyanine dyes, carbocyanine dyes and dicarbocyanine dyes are preferred, and in particular, JP-A-3-25184.
No. 0, pages 28 to 29, BS-1 to BS-8, GS-1
GS-5, RS-1 to RS-8, JP-A-4-2859
IRS-1 to IRS-11 described in No. 50, pages 6 to 8 are preferably used. Further, as a supersensitizer, Japanese Patent Application Laid-Open No.
SS-1 to SS-9 described on pages 8 to 9 of 285950 are also preferably used.

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.

Further, as an antifoggant, JP-A-2-1
No. 46036, page 7, lower column, compounds represented by the general formula [II] can be mentioned. More preferred specific compounds are IIa-1 to IIa, described on page 8 of the same publication.
-8, compounds of IIb-1 to IIb-7, 1- (3-methoxyphenyl) -5-mercaptotetrazole,
Compounds such as (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned.

The method of adding these compounds is methanol,
It may be added by dissolving in a water-miscible organic solvent such as ethanol, fluorinated alcohol, acetone or dimethylformamide or an aqueous alkaline solution.

The amount of the substance adsorbed on the particle surface is such that the coverage (θ) on the particle surface is 2 to 80%, and more preferably 8 to 50%. The coverage was determined by adding an adsorbed substance to silver halide and centrifuging the supernatant. The supernatant was measured by high performance liquid chromatography to determine the amount of adsorption. The amount at which the amount of adsorption does not change even when the amount of addition of the adsorbing substance is changed is defined as the saturated amount of adsorption, and the coverage θ at this time is 100%. (See "Adsorption" by Tominaga Keii, Kyoritsu Shuppan) The amount of bromide to be added is 0.1 to 1 mol per mol of silver halide.
3.0 mol is preferable, and 0.4 to 2.0 is more preferable.
Is a mole. Preferably, an iridium compound is present when adding the bromide. The addition amount of the iridium compound is preferably from 10 ^-9 to 10 ^-5 mol, more preferably from 10 ^-8 to 10 ^-6 mol, per mol of silver halide.
The bromide is preferably silver bromide fine particles, more preferably silver bromide fine particles having a particle size of 0.1 μm or less, and silver bromide fine particles containing iridium bromide are also preferably used.

In the present invention, it is also preferable to add the compound represented by the above formula (1) after forming silver halide tabular grains containing 90 mol% or more of silver chloride and before performing chemical sensitization. .

In the general formula (1), M represents a charged frontier orbital polyvalent metal ion.
e ²⁺ , Ru ²⁺ , Os ²⁺ , Co ³⁺ , Rh ³⁺ , Ir ³⁺ , Pd
⁴⁺ and Pt ⁴⁺ . L represents a coordination complex ligand that can be independently selected. However, at least one of the ligands is more electronegative than any halide ligand, preferably at least three, and optimally at least four. n is -1, -2, -3 or -4
Represents

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. U.S. Pat.
Nos. 756 and 4,225,666, and JP-A-55-26.
No. 589, Japanese Patent Publication No. 55-42737, and The Journal of Photographic Science (J. Ph.
otogr. Sci. ) Particles having shapes such as octahedron, tetrahedron, and dodecahedron can be prepared and used by methods described in documents such as 21, 39 (1973). 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 a device 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 in which the soluble silver salt and the soluble halide salt are reacted 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.

Also, 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 silver described in German Offenlegungsschrift 2,921,164, etc. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of a 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.

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

The silver halide emulsion is 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, and inorganic sulfur.

The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, 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 the 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 used, ripening conditions, etc., but is usually from 1 × 10 ^-5 to 1 × 10 ^-8 mol per mol of silver halide. Is preferably
More preferably, it is 1 × 10 ^-4 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 fog generated during the preparation of the light-sensitive material, reducing performance fluctuation during storage, and preventing fog generated during development. Agents can be used. When chemical sensitization is performed in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, 1 × 10 ⁻⁶ to 1 × per mol of silver halide is used.
An amount of about 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. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ^-9 to 1 × 10 ^-3 mol per 1 m ² .

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].

Silver halide grains other than the silver halide grains of the present invention are preferably spectrally sensitized. Any known compound can be used as the spectral sensitizing dye at that time.
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.

As a method for adding the sensitizing dye, the sensitizing dye may be dissolved in water or a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, or dimethylformamide, or may be added as a solution, or may be added as a solid dispersion. It may be added.

When the light-sensitive material of the present invention is used as a color light-sensitive material, the light-sensitive material is combined with a yellow coupler, a magenta coupler, and a cyan coupler in a range 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 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 which 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 RM 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 a yellow coupler which can be preferably used, a coupler represented by the general formula [YI] described in the upper right column of 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] wherein RY1 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, particularly preferred examples of the compounds are YC-8 and YC-9 described in JP-A-4-114154, page 4, upper left column, and Nos. (1) to (47) described in JP-A-6-67388, pages 13 to 14. )). 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 higher, if necessary. To dissolve in combination with a low boiling point and / or water-soluble organic solvent, and emulsify and disperse in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill,
A flow jet mixer, an ultrasonic disperser or the like can be used. After or simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be 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 a 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 on page 9 of JP-A-4-114154 and compound A'-1 described in the upper left column on 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 the 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, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, and white pigment. For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. may be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable.

As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is 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 surface 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 support surface, 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).

At the time of coating a 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 is preferably applied to a photosensitive material for forming an image for direct 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.

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-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 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 for color development in the present invention is 3
5-70 ° C is preferred. 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.

Conventionally, the color development time is generally 3 minutes 30 minutes.
Although it is performed in about seconds, in the present invention, it can be performed in a range of 45 seconds or less, and further in 25 seconds or less.

To the color developing solution, a known developer component compound can be added in addition to the above 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 color development, the light-sensitive material is subjected to bleaching and fixing. 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 for processing the photosensitive material of the present invention may be a roller transport type in which the photosensitive material is transported by interposing the photosensitive material between rollers disposed in a processing tank. An endless belt system for conveying may be used, but a processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and a photosensitive material is conveyed and a spray method for spraying the processing liquid,
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid 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 image forming method according to the present invention can be preferably applied to a heat development system. In the present invention,
Thermal development refers to a method of performing development by heating an exposed photosensitive material to 50 ° C to 250 ° C, preferably 60 ° C to 150 ° C. The heat treatment is performed, for example, as described in JP-A-63-7
No. 1850, etc., a method in which a photosensitive material is heated and conveyed while being sandwiched between a heat drum and a drum belt, or a method in which a photosensitive material is set between a heater and a support and heated simultaneously with pressurization. A so-called direct heating method, a method of passing a photosensitive material between far-infrared heaters described in JP-A-4-240642, or a so-called indirect heating method of heating by irradiating a microwave. Further, a system combining a direct heating system and an indirect heating system 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. 2-1
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
[0015]-[0]
[018] 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 thermal 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, and 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, a compound capable of forming or releasing an image dye (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 and the like, or JP-A-59-60434 and JP-A-59-6583.
No. 9, No. 59-71046, No. 59-87450,
Compounds described in JP-A-59-165055 and the like;
No. 55430, No. 59-165054, No. 59-1
No. 54445, No. 59-116655, No. 59-12
No. 4327, No. 59-152440, No. 64-135
No. 46, JP-A-6-51474 and the like can be preferably used compounds capable of forming image dyes in a manner opposite to silver development.

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.

In the light-sensitive material according to the present invention, a mode in which a developing agent or a precursor thereof is incorporated can also be used. 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 a developing agent satisfying such requirements, a paraphenylenediamine-based agent described in JP-A-62-288835 and the like;
5806 and the like, JP-A-5-241282 and JP-A-8-234388.
No. 8-286340, No. 9-152700, No. 9-152701, No. 9-152702, No. 9-1
Hydrazine-based drugs described in JP-A-52703 and JP-A-9-152704, JP-A-7-202002, JP-A-8-234
And hydrazone-based drugs described in JP-A-390 / 390 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. The activator solution in this case is characterized in that it does not contain the color developing agent contained in the ordinary color developing solution components, 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.

[0102]

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 paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side 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 liquid: 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 solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer so that the coating amounts were as shown in Tables 1 and 2.

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

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[Table 1]

[0108]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium 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

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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) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. 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.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) 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 (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the 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-1 was obtained.

Next, EMP was carried out except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed.
As in the case of -1, the average particle diameter is 0.64 μm, and the coefficient of variation is 0.1.
07, a monodispersed cubic emulsion EMP-1B having a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization 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 ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

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) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%.

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-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° 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-G).

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 Stable 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) (solution A) and (solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%.

The above-mentioned EMP-3 was maintained at 60 ° C. and the stabilizer (S
TAB-1), sodium thiosulfate, and chloroauric acid were added in this order, and after optimal chemical sensitization, sensitizing dyes RS-1 and RS-
2 and SS-1 were added to perform color sensitization, and finally a stabilizer (S
TAB-2 and STAB-3) were added to obtain a red-sensitive silver halide emulsion (Em-R1). The amount of each additive is as follows.

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 STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole -1 was added in an amount of 2.0 × 10 ^-3 per mol of silver halide.

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After performing chemical sensitization in the same manner as in Em-R1,
1.0 × 10 ^-4 mol / mol A of K ₂ IrCl ₆ in advance
1.0 mol% / mol AgX doped with gX-doped AgBr fine particles having a particle diameter of 0.05 μm was added, and after 30 minutes, sensitizing dyes RS-1, RS-2, SS-1 and a stabilizer (STAB-
The emulsion to which 2, STAB-3) was added was designated as Em-R2.

<Preparation of tabular grains> The following solutions were prepared.

Solution G1 Ossein gelatin 18.41 g NaCl 1.26 g Make up 1534.5 ml with distilled water Solution Ag1 1.18 N aqueous silver nitrate solution X1 1.21 N aqueous NaCl 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 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 EMP-T was obtained.

The obtained silver halide grains had a ratio of tabular grains having an aspect ratio of 2 or more to the total projected area of 0.85,
Particle size distribution 17 of tabular silver halide grains having an average thickness of 0.13 μm, an average aspect ratio of 13.1, an aspect ratio of 3 or more and a thickness of 0.3 μm or less It is a numerical value obtained by multiplying the number divided by the diameter by 100), and the tabular grains having (100) on the main plane having the same volume cubic side length of 0.67 μm.

The above-mentioned EMP-T was maintained at 60 ° C., and the stabilizer (S
TAB-1), sodium thiosulfate, and chloroauric acid were added in this order, and after optimal chemical sensitization, sensitizing dyes RS-1 and RS-
2 and SS-1 were added to perform color sensitization, and finally a stabilizer (S
The emulsion to which TAB-2 and STAB-3) had been added was em-R
It was set to 3. The amount of each additive is as follows.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 2 × 10 ⁻³ mol / mol AgX stabilizer STAB-2 2 × 10 ⁻³ mol / mol AgX stable Agent STAB-3 2 × 10 ⁻³ mol / mol AgX sensitizing dye RS-1 7 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 7 × 10 ⁻⁴ mol / mol AgX The above EMP-T was prepared at 60 ° C. And keep KBr at 1.5 mol% /
After the addition of mole AgX, sodium thiosulfate, chloroauric acid, stabilizer (STAB-1), sensitizing dyes RS-1, RS
After the same amount of Em-2 and SS-1 as Em-R3 and optimal chemical sensitization, an emulsion containing stabilizers (STAB-2, STAB-3) was designated Em-R4.

After maintaining EMP-T at 60 ° C. and adding sodium thiosulfate and chloroauric acid for chemical sensitization, the mixture was cooled to 45 ° C., and KBr was added at 1.0 mol% / mol AgX. An emulsion containing the same amount of sensitizing dyes RS-1, RS-2 and SS-1, and stabilizers (STAB-2, STAB-3) as Em-R3 was designated as Em-R5.

An emulsion Em-R6 differed only in that RS-1 and RS-2 were added as particle adsorbing substances immediately before the addition of Em-R5 and KBr. At this time, the coverage is 90
%was.

An emulsion Em-R7 was obtained only by adding STAB-1 as a particle adsorbing substance immediately before adding Em-R5 and KBr. At this time, the coverage was 55%.

Em-R6 and particle adsorbing substances RS-1, RS
Emulsion Em-R8 was different except that the addition amount of -2 was 3.5 × 10 ^-4 mol / mol AgX. At this time, the coverage was 44%.

An emulsion different from Em-R9 only in that K ₂ IrCl ₆ was added at the same time as adding 1.0 × 10 ⁻⁶ mol / mol AgX when Em-R8 and KBr were added.

The particle size of Em-R9 was 0.3 instead of KBr.
An emulsion that was different only in that AgBr fine particles of 05 μm was used was named Em-R10.

With Em-R10, AgBr fine particles and K ₂ Ir
The emulsion Em-R11 was different only in that, instead of adding the Cl ₆ solution, the same amount of K ₂ IrCl ₆ was added in advance but AgBr fine particles having a particle size of 0.05 μm were added.

Em-R11 means K ₄ Fe before chemical sensitization.
An emulsion different only in that 2.0 × 10 ⁻⁵ mol / mol AgX of (CN) ₆ was added was designated as Em-R12.

Samples 101 to 112 differing only in that Em-R1 to Em-R12 were replaced with the red-sensitive silver chlorobromide emulsion of the fifth layer (red-sensitive layer) in Table 1 were prepared.

Photographic Properties The samples prepared as described above were exposed to light wedges in a conventional manner for 0.1 second using a sensitometer KS-7 (manufactured by Konica Corporation), and then developed by the following developing process. Was done.

The density of the obtained sample was measured using a PDA-65 type densitometer (manufactured by Konica Corporation).
Express the sensitivity as the reciprocal of the exposure required to obtain a high density,
The sensitivity of the sample 101 was defined as 100 and expressed as relative sensitivity. Further, the gradation is represented by a value obtained by dividing the density difference 1.5 by the difference between the logarithms of the exposure amounts giving the color density 0.5 and 2.0.

High Illumination Exposure Characteristics Similarly, the above samples were evaluated as follows. As a light source, a semiconductor laser GaAlAs (oscillation wavelength: 808.5 n)
m) as an excitation light source with a YAG solid-state laser (oscillation wavelength 9
46 nm) was converted into a wavelength by KNbO ₃ SHG crystal, and 473 nm was taken out.
s (oscillation wavelength of 808.7 nm) as excitation light source
Four solid-state lasers (oscillation wavelength 1064 nm)
532 nm extracted by wavelength conversion by an HG crystal,
AlGaInP (oscillation wavelength: about 670 nm) was used.
The 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 the sample. The effective beam diameter of the laser beam was 80 μm, the scanning pitch was 400 dpi, and the exposure amount was controlled by an external modulator to perform light wedge exposure. At this time, the average exposure time per pixel is 5 × 1
^0-8 seconds. After exposure, the same development processing and density measurement as in "photographic performance" were performed, and the relative sensitivity was expressed. Further, a gradation * 1 between the density 1.5 and the density 2.25 at this time was obtained and expressed as a shoulder gradation.

* 1: The value obtained by dividing the density difference 0.75 by the difference in the exposure amount LogE for giving each density. Latent image stability The sensitivity when developed 10 seconds after exposure with the above high illuminance exposure is assumed to be 100. Latent image stability was expressed as a relative value to the sensitivity when developed after standing for 24 hours after exposure.

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 to 80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml 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 acetate sodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make a total volume of 1 liter. At 10.10, the replenisher should have a pH = Adjusted to 0.60.

Bleach-fix solution and replenisher solution 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 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 0.02 g Diethylene glycol 1.0 g Fluorescent whitening agent (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 is added to make up to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

[0150]

[Table 3]

From Table 3, it can be seen that the sample using the silver halide emulsion of the present invention is a silver halide photographic material having high sensitivity, excellent shoulder gradation and high latent image stability in high illuminance exposure. You can see that there is.

Example 2 In Example 1, a Konica NPS was used as an automatic developing machine.
-868J, ECOJET-P was used as a processing chemical, and a running process was performed according to process 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 3 After preparing the emulsion of Example 1 as a coating solution for the fifth layer,
After stagnation at 6 ° C for 2 hours, the applied sample
And 2.

Samples 201 to 212 were evaluated for the same high illuminance exposure characteristics as in Example 1.

[0155]

[Table 4]

Table 4 shows that the sample using the silver halide emulsion of the present invention was a silver halide photographic light-sensitive material which was excellent in production stability without deterioration over time due to stagnation of the coating solution.

[0157]

According to the present invention, high sensitivity and high contrast can be obtained.
In high-illumination exposure, a method for producing a silver halide emulsion which is excellent in shoulder gradation and has good latent image stability and high production stability, and a silver halide photographic material using the silver halide emulsion, An image forming method was obtained.

Claims (9)

[Claims] 1. A tabular grain having a silver chloride content of 90 mol% or more of the total silver, a (100) plane on a main plane and an aspect ratio of 2 or more accounts for 50% or more of the total projected area. A method for producing a silver halide emulsion, which comprises subjecting certain silver halide grains to gold / sulfur sensitization, lowering the temperature, adding a grain surface adsorbent, and then adding bromide. 2. The coating ratio of the substance adsorbed on the particle surface is 2 to 80%.
2. The method for producing a silver halide emulsion according to claim 1, wherein 3. The method for producing a silver halide emulsion according to claim 1, wherein an iridium compound is present when bromide is added. 4. The method for producing a silver halide emulsion according to claim 1, wherein the bromide is silver bromide fine particles. 5. The method according to claim 1, wherein the bromide is fine silver bromide particles containing iridium.
The method for producing a silver halide emulsion according to the above item. 6. The silver halide emulsion according to claim 1, wherein the temperature at the time of gold / sulfur sensitization is 55 ° C. or higher and the temperature at the time of bromide addition is 50 ° C. or lower. Manufacturing method. 7. A compound represented by the following general formula (1) is added after forming silver halide tabular grains containing 90 mol% or more of silver chloride and before performing chemical sensitization. A method for producing a silver halide emulsion according to any one of claims 1 to 6. Formula (1) (ML ₆ ) ⁿ [wherein, M represents a filled frontier orbital polyvalent metal ion, and L represents a coordination complex ligand that can be independently selected. However, at least one of the ligands is more electronegative than any halide ligand, and n
Represents -1, -2, -3 or -4. ] 8. At least one of the silver halide photographic light-sensitive layers
A silver halide photographic material comprising a layer containing a silver halide emulsion produced by the method for producing a silver halide emulsion according to any one of claims 1 to 7. 9. An image forming method for a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to claim 8 is exposed for an exposure time shorter than 10 μsec.