JP2000019692A - Production of silver halide emulsion, silver halide photographic sensitive material and color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce silver halide emulsion having high sensitivity, excellent in character quality in high-illuminance exposure and having good latent image stability by multiply exposing silver halide color photosensitive material and specifying maximum point gamma. SOLUTION: The maximum point gamma is set to 60 to 95% from the low illuminance side of an effective exposure area in forming an image by multiply exposing the silver halide color photosensitive material having a blue sensitive emulsion layer, a green sensitive emulsion layer and a red sensitive emulsion layer at least one by one on a supporting body for an exposure time shorter than 10 μsec. In such a case, it is more desirable to set the maximum point gamma to 70 to 90% from the low illuminance side of the effective exposure area, and it is desirable that the difference of the positions from the low illuminance side of the maximum point gamma of the blue sensitive emulsion layer, the green sensitive emulsion layer and the red sensitive emulsion layer is within 10%, more desirably, 5%. The point gamma is dD/ dlogE(D means density and E means exposure), and expresses a differential value at an optional point on a characteristic curve(D-logE curve).

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 a color image forming method, and more particularly, to a method having high sensitivity, excellent character quality under high illuminance exposure, and The present invention relates to a method for producing a silver halide emulsion, a silver halide photographic light-sensitive material, and a color image forming method having good latent image 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 recent years, with the development of computer technology, a method of synthesizing images and characters on a computer and recording the images on a silver halide photosensitive material with a laser beam or the like has been studied. For this reason, sharpness of fine lines, that is, further improvement of character quality is desired.

Various proposals have been made so far to solve these drawbacks, but they are not satisfactory due to problems such as compatibility with the initial latent image regression.

For example, Japanese Patent Application Laid-Open No. 3-132647 discloses 9
A silver halide grain containing 0 mol% or more of silver chloride contains iron ions in an amount of 10 ^-7 to 10 ^-3 mol per mol of silver halide, and further contains iron ions in a surface layer of 50% or less. A silver halide grain localized at a concentration 10 times or more higher than that described is described. Also, US Pat.
No. 20 describes that after a high silver chloride cubic emulsion is subjected to chemical sensitization, iridium-containing silver bromide grains are added.

However, even with these methods, the character quality was not sufficient and the latent image stability was inferior in high illuminance exposure.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a silver halide emulsion having high sensitivity, excellent character quality under high illuminance exposure and good latent image stability, and a method for producing the silver halide emulsion. An object of the present invention is to provide a silver halide photographic light-sensitive material using an emulsion and a color image forming method.

[0007]

The above objects of the present invention are as follows. In an image forming method, a silver halide color light-sensitive material having at least one blue-sensitive emulsion layer, one green-sensitive emulsion layer and one red-sensitive emulsion layer on a support is exposed multiple times with an exposure time shorter than 10 μsec. Is within 60 to 95% from the low illuminance side of the effective exposure area,

[0008] 2. 2. The color image forming method according to the above 1, wherein the difference between the maximum point gamma of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer from the low illuminance side is within 10%.

3. After silver halide grains containing 90 mol% or more of silver chloride are formed and desalted, silver chloride fine grains of 50 mol% or more of silver chloride are added, and then silver bromide fine grains of 50 mol% or more of silver bromide are added. A method for producing a silver halide emulsion, characterized in that:

[0010] 4. 4. The method for producing a silver halide emulsion according to the above 3, wherein both the silver chloride fine particles and the silver bromide fine particles have a particle size of 1/3 or less of the host particles.

5. Silver chloride fine particles and silver bromide fine particles
5. The method for producing a silver halide emulsion according to the above 3 or 4, wherein the method contains a metal ion different from each of the metal ions belonging to Group II.

6. The silver halide according to any one of the above items 3 to 5, wherein the fine particles of silver chloride contain a compound represented by the following general formula (1), and the fine particles of silver bromide contain an iridium compound. Emulsion manufacturing method, General 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. ]

7. 7. A silver halide photographic material comprising a support and a layer containing the silver halide emulsion obtained by the production method according to any one of the above 3 to 6,

8. In an image forming method, a silver halide color light-sensitive material having at least one blue-sensitive emulsion layer, at least one green-sensitive emulsion layer, and at least one red-sensitive emulsion layer on a support is subjected to multiple exposure with an exposure time shorter than 10 μsec. A silver halide emulsion layer containing the silver halide emulsion according to any one of the above 3 to 6, wherein the maximum point gamma is 60 to 95% from the low illuminance side of the effective exposure area;
Each of the color image forming methods is characterized in that the difference in the position of the maximum point gamma of each layer from the low illuminance side is within 10%.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In a method of recording an image and a character on a silver halide light-sensitive material by a laser beam or the like, even if the performance is such that the blur in the image is permissible, the character cannot be recognized and cannot be perceived by the blur of the character. As a method for improving sharpness, an increase in the amount of the anti-irradiation dye can be considered, but there are problems such as a decrease in sensitivity and a residual color after processing such as development.
According to our research, the improvement of character quality is achieved by increasing the maximum point gamma to 60 to 95%, more preferably 70 to 90%, from the low illuminance side of the effective exposure area, and increasing the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion. It has been found that the problem can be solved by setting the difference in the position of each maximum point gamma of the emulsion layer from the low illuminance side within 10%, more preferably within 5%. The “point gamma” of the present invention refers to T.G. H. James ed, "The Theory of the Photog
point, gamma = dD / dlogE (D is the density, E is the exposure) and the derivative of any point on the characteristic curve (D-logE curve) Represents a value. The “effective exposure area” is an area where the density changes with respect to the change in the exposure amount.

The maximum point gamma of the present invention is set at 60 to 95% from the low illuminance side of the effective exposure area, and the positions of the maximum point gammas of the blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer from the low illuminance side. Means to make the difference of 10% or less,
Various methods for adjusting the conditions of the silver halide emulsion are conceivable. A preferable method is to form and desalinate silver halide host grains containing 90 mol% or more of silver chloride, and then to form 50 mol% or more of silver chloride. Of silver chloride fine grains, and then silver bromide fine grains of 50 mol% or more of silver bromide are used. The particle size of both silver chloride fine particles and silver bromide fine particles is preferably 1/3 or less of that of the host particles, and more preferably both fine particles are 0.1 μm or less and subjected to ultrafiltration and desalting. The addition amount of both fine grains is preferably 0.1 to 3.0 mol, more preferably 0.3 to 1.5 mol, per 1 mol of silver halide. The temperature at the time of addition is preferably 55 ° C. or higher.

The silver chloride fine particles of the present invention have the following general formula (1):
It is preferable to contain the compound represented by The content of the general formula (1) is 10 mol per mol of the total silver halide.
^-8 to 10 ^-2 mol is preferred, and more preferably 5 x 1
Is 0 ^-6 ~5 × ^{10 -4} mol.

In the formula (1) (ML ⁶ ) n, M represents a charged frontier orbital polyvalent metal ion, preferably Fe ²⁺ , Ru ²⁺ , Os ²⁺ ,
Co ³⁺ , Rh ³⁺ , Ir ³⁺ , Pd ⁴⁺ , 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 represents -1, -2, -3 or -4.

The silver bromide fine particles of the present invention preferably contain an iridium compound. The content of the iridium compound is 10 ⁻⁹ to 10 based on 1 mol of the total silver halide.
^-5 mol is preferred, more preferably 10 ^-8 to 10
^-6 mol.

The composition of the silver halide emulsion according to the present invention is as follows:
Silver halide, silver chlorobromide, silver chloroiodobromide, silver chloroiodide, etc. may have any halogen composition.
Silver chlorobromide containing substantially 0 mol% or more and substantially not containing silver iodide is preferred. From the viewpoint of rapid processing and processing stability, a silver halide emulsion containing preferably 97 mol%, more preferably 98 to 99.9 mol% of silver chloride is preferred.

The silver halide grains may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, and The Journal Photographic Science (J. Photogr. Sci.) 21), 39 pages (1
973) to produce particles having shapes such as octahedron, tetradecahedron, and dodecahedron,
This can also be used. Further, particles having a twin plane may be used.

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

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

The particle size distribution of the silver halide grains is preferably a monodispersed silver halide grain having a coefficient of variation of preferably 0.05 to 0.22, more preferably 0.05 to 0.15.
Particularly preferably, a monodispersed emulsion layer of 0.05 to 0.15
More than one kind is added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

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

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

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

The form of reacting the soluble silver salt with the soluble halide may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but the method obtained by the simultaneous mixing method is preferable. . Further, as one 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, JP-A-57-92523.
No.-92524, etc., a device for supplying a water-soluble silver salt and a water-soluble halide aqueous solution from an addition device disposed in a reaction mother liquor, and a water-soluble silver described, for example, in DE-A-2,921,164. Apparatus for continuously adding a salt and an aqueous solution of a water-soluble halide while changing the concentration, JP-A-56-501
No. 776, etc., a reaction mother liquor may be taken out of the reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. After the completion of silver halide grain formation, the silver halide emulsion is washed with water by a known method such as a precipitation method or an ultrafiltration method, but the water washing method of the precipitation method using a mixed solution of a surfactant and magnesium sulfate is used. Is preferred.

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

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

The amount of the sulfur sensitizer to be added is preferably changed depending on the kind of silver halide emulsion to be applied, the expected effect, and the like.
10 ^{−10 to} 5 × 10 ⁻⁵ mol, preferably 5 × 10
The range of ^{-8 to} 3 × 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 the silver halide emulsion, the type of the compound to be used, the ripening conditions, etc., but is usually from 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ mol per mol of silver halide. And more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

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

The silver halide emulsion may contain a known antifoggant for the purpose of preventing 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. Preferred examples of the compound used for such purpose include a compound represented by the general formula [II] described in the lower section of page 7 of JP-A-2-14636. II described on page 8 of the gazette
Compounds such as a-1 to IIa-8 and IIb-1 to IIb-7, and compounds such as 1- (3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole Can be mentioned.

These compounds are added according to the purpose in the steps of preparing silver halide emulsion grains, chemical sensitizing step, completion of the chemical sensitizing step, coating liquid preparing step and the like. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ^{−5 to} 5 × 10 5 per mole 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 × per mole of silver halide
The amount is preferably about 10 ⁻⁶ to 1 × 10 ⁻² mol, and 1 ×
^{10-5 to} 5 x ^10-3 mol is more preferred. When it is added to the silver halide emulsion layer in the coating solution preparation step, it is 1 × 10 ⁻⁶ to 1 × 10 ⁶ per mol of silver halide.
An amount of about ^-1 mol is preferred, and 1 × 10 ⁻⁵ to 1 × 10
^-2 mol is 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 .

As 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 the known compounds can be used. Particularly, as dyes having absorption in the visible region, dyes of AI-1 to 11 described in JP-A-3-251840, p. -3770
The compounds described in JP-A-1-280750, page 2, lower left column, represented by general formulas (I), (II), and (III) are preferable as the infrared absorbing dye. It has no effect on the photographic characteristics of the photographic emulsion and does not cause contamination 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. In order to improve sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is preferably 0.7 to 3.0, more preferably 0.8 to 3.0.

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

When the light-sensitive material of the present invention is used as a color light-sensitive material, the light-sensitive material is used in combination with a yellow coupler, a magenta coupler, and a cyan coupler 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 spectral sensitizing dye used in the present invention, any of the known compounds can be used. Examples of the blue sensitizing dye include BS-1 to BS-1 described in JP-A-3-251840, page 28. BS-8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferable, and as the red photosensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferred. Is preferably used. In the case of performing image exposure with infrared light using a semiconductor laser or the like, an infrared-sensitive sensitizing dye must be used.
No. 50, pages 6 to 8, IRS-1 to IRS-11 dyes are preferably used. In addition, these infrared, red,
Green and blue photosensitive sensitizing dyes are disclosed in JP-A-4-285950,
Supersensitizers SS-1 to SS-9 described on pages 9 to 19 and compound S-1 described on JP-A-5-66515, pages 15-17.
It is preferable to use a combination of -S-17.

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

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

Examples of cyan couplers that can be preferably used include couplers represented by general formulas [CI] and [C-II] described in the lower left column of page 5 of JP-A-4-114154. Specific compounds include those described as CC-1 to CC-9 in page 5, lower right column to page 6, lower left column in the same publication.

As magenta couplers which can be preferably used, there can be mentioned those represented by the 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 [M-
A coupler represented by the general formula [M]
-I], in which the RM is a tertiary alkyl group, is particularly preferred because of its excellent light resistance. MC-8 to MC-11 described in the upper column of page 5 of the same publication are excellent in reproducing colors ranging from red to purple and red, and are also excellent in detail description power, and are therefore preferable.

As a yellow coupler which can be preferably used, a coupler represented by the general formula [Y-I] described in the upper right column on page 3 of JP-A-4-114154 can be mentioned. YC on the lower left column of page 3
-1 to YC-9. Among them, a coupler of the formula [Y-I] 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 type emulsion dispersion method is used to add a coupler or other organic compound used in a light-sensitive material, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or more, if necessary. To dissolve it 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 organic solvent which can be used for dissolving and dispersing the coupler include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate, 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. And emulsifying and dispersing in a hydrophilic binder such as an aqueous gelatin solution by using various kinds of dispersing means using a surfactant. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

Preferred compounds as surfactants used for dispersing photographic additives and adjusting the surface tension at the time of 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 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, and within 10 hours each. It is 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, and phenolic compounds represented by general formula [IIIB] described in JP-A-3-174150. Compounds, amine compounds represented by the general formula [A] described in JP-A-64-90445,
General formulas [XII] and [XII] described in US Pat.
The metal complexes represented by I], [XIV] and [XV] are particularly preferred for magenta dyes. Also, Japanese Unexamined Patent Publication No.
Compounds represented by the general formula [I] described in JP-A No. 049 and compounds represented by the general formula [II] described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.

Compounds such as compound d-11 described in the lower left column of page 9 of JP-A-4-114154 and compound A'-1 described in the upper left column of page 10 are used for the purpose of shifting the absorption wavelength of the coloring dye. be able to. In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material, a compound which reacts with an oxidized developing agent is added between the light-sensitive layers to prevent color turbidity, and is added to a silver halide emulsion layer to improve fog and the like. Is preferred. As the compound for this, a hydroquinone derivative is preferred, and more preferably 2,5-
Dialkyl hydroquinones such as di-t-octyl hydroquinone. Particularly preferred compounds are disclosed in
A compound represented by the general formula [II] described in JP-A-1333056, and a compound II-1 described in page 13 to 14 of the same.
II-14 and Compound-1 described on page 17.

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. Preferred examples of the ultraviolet absorber include bent triazoles. Particularly preferred 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,
UV-1L to UV-27L described in JP-A-187240, compounds represented by the general formula [I] described in JP-A-4-1633, compounds represented by the general formula (I) described in JP-A-5-165144,
The compound shown by (II) is mentioned.

It is advantageous to use gelatin as a binder in the light-sensitive material of the present invention. If necessary, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative, 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 or 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 a fungicide 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 photosensitive material, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, and white pigment. For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. may be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable.

As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is 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 can be 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 undercoating (adhesion, antistatic property, dimensional stability on the support surface). , One or more undercoat layers for improving friction resistance, hardness, antihalation property, frictional properties and / or other properties).

In 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 simultaneously applied, are particularly useful as an application method.

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, a preferable exposure time is 10 ⁻⁴ seconds or less, and more preferably 10 ⁻⁶ seconds or less. Specific examples of the method include a method using a light emitting diode as a light source described in JP-B-62-1305 and JP-A-63-18-18.
No. 346, there is a method using a second harmonic obtained by using a semiconductor laser and an 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) aminoaniline 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-Exethyl) 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, known developing component compounds can be added in addition to the above color developing agents. 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 photosensitive material is subjected to bleaching and fixing. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed.
Further, as an alternative to the washing process, a stabilizing process may be performed.

The developing apparatus used in the processing of the photosensitive material of the present invention is a roller transport type in which the photosensitive material is conveyed between rollers arranged 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 run using an automatic developing machine. At this time, the smaller the replenishment amount of the replenisher, the more preferable the replenishment amount is. 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, 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, JP-A-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] to [0] in the upper right column of the page, No. 4-289856,
[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, page 4, upper left to page 7, lower left column, etc., using a compound that generates a base by thermal decomposition, JP-A-8-87097, European Patent Publication 210,6
No. 60, 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 may 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, 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, 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.

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 usual components of the color developing solution, 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.

[0087]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto. Example 1 A high-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon to prepare a silver halide photographic light-sensitive material. The coating solution was prepared as follows.

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

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

Further, (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 .

[0091]

[Table 1]

[0092]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: bis (2-ethylhexyl) sulfosuccinate
Sodium salt SU-3: bis sulfosuccinate (2, 2, 3, 3, 4,
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-o Butylphenol

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image

[0097]

Embedded image

(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 simultaneously added over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437.
The pH was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) 102.7 g of sodium chloride 102.7 g of K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol _{AgX K 4 Fe (CN) 6} 2 × 10 -5 mol / mol AgX potassium bromide was added to 1.0g water 600ml (D solution) was added silver nitrate 300g water 600ml

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
And a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm, a variation coefficient of particle size distribution of 0.07, and a silver chloride content of 99. A 5 mol% monodispersed cubic emulsion EMP-1A was obtained.

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

The above-mentioned EMP-1A was optimally chemically sensitized at 60 ° C. using the following compounds. Also, 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

(Preparation of Green-Sensitive Silver Halide Emulsion) (A
Liquid) and (solution B) and the addition time of (liquid C) and (liquid D) in the same manner as EMP-1, except that the addition time was changed, the average particle diameter was 0.40 μm, the coefficient of variation was 0.08, and the silver chloride was changed. Content 9
A 9.5 mol% monodispersed cubic emulsion EMP-2A was obtained.

Next, a monodispersed 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 mol% was obtained.

The above EMP-2A was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also, EMP-2
Similarly, after optimally chemical sensitizing B, the sensitized EMP-2A and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G1). I got

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX

(Preparation of Red-Sensitive Silver Halide Emulsion)
Liquid) and (solution B) and the addition time of (liquid C) and (liquid D) in the same manner as EMP-1, except that the addition time was changed, the average particle diameter was 0.40 μm, the coefficient of variation was 0.08, and the silver chloride was changed. Content 9
A 9.5 mol% monodispersed cubic emulsion EMP-3A was obtained.

Next, a monodisperse cubic emulsion EMP-3B having an average particle size of 0.45 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol% was obtained.

After maintaining the above EMP-3A at 60 ° C. and adding a stabilizer (STAB-1), sodium thiosulfate and chloroauric acid in this order and optimally chemical sensitizing, the sensitizing dyes RS-1 and R
Color sensitization was performed by adding S-2 and SS-1, and finally stabilizers (STAB-2, STAB-3) were added. Also, EM
Similarly to P-3B, after optimally chemical sensitization and color sensitization, the sensitized EMP-3A and EMP-3B are mixed at a silver ratio of 1: 1 to obtain a red-sensitive silver halide. Emulsion (Em
-R1) was obtained. 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 In the red-sensitive emulsion, SS-1 was used per mole of silver halide. 2.0 × 10 ^{−3 was} added.

[0112]

Embedded image

[0113]

Embedded image

Emulsion EMP-1A refers to K ₂ I in (solution C)
EMP-1C was an emulsion which differed only in that rCl ₆ was changed to 5.0 × 10 ⁻⁷ mol / mol AgX.

Emulsion EMP-1A refers to K ₂ I in (solution C)
rCl ₆ at 1.0 × 10 ⁻⁶ mol / mol AgX, K ₄ F
EMP-1D was a different emulsion except that e (CN) ₆ was changed to 5.5 × 10 ⁻⁶ mol / mol AgX.

Emulsions EMP-2A and EMP-3A were similarly prepared for K ₂ IrCl ₆ and K ₄ Fe (CN) ₆ in (C solution).
EMP-2C, EMP-2D,
EMP-3C and EMP-3D were used.

EMP-1C and EMP-1D were replaced with EMP-1
As in A, chemical sensitization was performed optimally.

EMP-2C and EMP-2D were converted to EMP-2
As in A, chemical sensitization was performed optimally.

EMP-3C and EMP-3D were converted to EMP-3
As in A, chemical sensitization was performed optimally.

The blue-sensitive emulsions include EMP-1A to EMP
Sample 1 was prepared by selecting an arbitrary emulsion of -1D and changing the position of the maximum point gamma variously by changing the mixing ratio.
01 was replaced with the first layer. Green sensitive emulsion is EMP-2A
~ EMP-2D, red-sensitive emulsion is EMP-3A ~ EMP-
Similarly, the position of the maximum point gamma was variously changed by changing the mixing ratio of 3D, and samples 102 to 108 were produced by replacing the third layer and the fifth layer of sample 101, respectively.

Maximum Point Gamma The sample prepared as described above was evaluated as follows. As a light source, a YAG solid laser (oscillation wavelength: 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength: 808.5 nm) as an excitation light source is converted into a wavelength by a KNbO3 SHG crystal and extracted at 473 nm; Solid-state laser (oscillation wavelength 1064n)
m) is converted to a wavelength of 532 nm by an SHG crystal of KTP and taken out with AlGaInP (oscillation wavelength of about 670 nm).
m) 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 is 80
A light wedge exposure was performed with a scanning pitch of 400 μm and an exposure amount controlled by an external modulator. At this time, the average exposure time per pixel was 5 × 10 ⁻⁸ seconds. The exposed sample was developed by the following image processing steps to obtain sensitometry. The point gamma of each color was determined from the obtained sensitometry, and the position from the low illuminance side of the effective exposure area was represented by the ratio of the total effective exposure area.

Character Quality The samples 101 to 108 were scanned and exposed to 6 lines / mm of fine lines at an exposure amount giving a density of 2.0, and developed. The obtained material was visually observed, and the color and the bleeding of the character were expressed based on the following criteria. Character bleeding evaluation criteria ◎: Fine lines can be clearly distinguished ○: Fine lines can be clearly distinguished but slightly blurred △: Fine lines have blurred and slightly difficult to distinguish ×: Fine lines are large and hard to distinguish

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleaching and fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 seconds 150 ml Drying 60- 80 ℃ 30 seconds

The composition of the developing solution is shown below. Color developing solution tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl-N- (Β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g sodium diethylenetriaminepentaacetate 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, and the tank solution was pH = 1.
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fixer tank 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 2.0 g ammonia water (25% aqueous ammonium hydroxide solution) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make a total volume of 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water.

[0127]

[Table 3]

The maximum p-γ is the ratio of the total effective exposure area at the position from the low illuminance side of the effective exposure area of the maximum point gamma. Character bleeding evaluation criteria ：: Fine lines can be clearly distinguished. ：: Fine lines can be clearly distinguished, but slightly There is bleeding △: The outline of the thin line is slightly blurred and it is difficult to distinguish ×: The thin line is large and it is difficult to distinguish it

From Table 3, it can be seen that when the maximum point gamma is 60 to 95% from the low illuminance side of the effective exposure area, the bleeding of the character is small, and when the difference between the positions of the maximum point gamma of each color is within 10%, the character It can be seen that the color tone of the color is also improved.

Example 2 Emulsion EMP-3A was similarly chemically sensitized, and pure AgBr fine particles having a particle size of 0.08 μm and previously doped with 1.0 × 10 ⁻⁴ mol / mol AgX of K ₂ IrCl ₆ were added.
Emulsion to which RS-1, RS-2, SS-1, and a stabilizer were added in the same manner as EMP-3A after 20 minutes had elapsed was added to mol / mol AgX to obtain Em-R2.

Emulsion EMP-3A was kept at 60 ° C., and pure AgCl fine particles having a particle size of 0.1 μm were used before chemical sensitization.
After adding 0 mol / mol AgX and further performing chemical sensitization simultaneously with EMP-3A, pure AgBr fine particles having a particle size of 0.08 μm were added thereto at 1.0 mol / mol AgX, and after 20 minutes, EMP-3 was added.
The emulsion to which RS-1, RS-2, SS-1 and a stabilizer were added was designated Em-R3 as in the case of -3A.

From EMP-3A (solution C) to K ₂ IrCl
₆ , the liquid excluding K ₄ Fe (CN) ₆ was divided at 9: 1, and the addition was divided into two times, and the total amount of K ₄ F was added to 10% of the liquid added later.
emulsion containing only e (CN) ₆ was added to EMP-
3E.

Emulsion EMP-3E was kept at 60 ° C., and K ₂ IrCl ₆ was previously added to 1.0 × 10 5 before chemical sensitization.
^-4 mol / mol AgX doped pure AgBr fine particles having a particle size of 0.08 μm were added at 1.0 mol / mol AgX, and then E was added.
An emulsion to which chemical sensitization, a dye and a stabilizer were added in the same manner as MP-3A was designated as Em-R4.

EMP-3A and K ₂ IrCl in (solution C)
The _{6, K} 4 Fe _(CN) only differ emulsion contains no ₆ was EMP-3F.

Emulsion EMP-3F was kept at 60 ° C., and a K ₄ Fe (CN) ₆ solution was added at 2 × 10 ⁻⁵ mol / mol AgX before chemical sensitization, and then chemically sensitized in the same manner as EMP-3A. After that, K ₂ IrCl ₆ was previously added to 1.
0 × 10 ⁻⁴ mol / mol AgX-doped particle size 0.08
1.0 μm / mol AgX of pure AgBr fine particles of μm was added, and then RS-1, RS-2,
The emulsion to which SS-1 and the stabilizer were added was designated as Em-R5.

Emulsion EMP-3F was kept at 60 ° C., and K ₄ Fe (CN) ₆ was added 2.0 × before chemical sensitization.
10 ^-3 mol / mol AgX-doped particle size 0.05 μm
1.0 mol / mol AgX of pure AgCl fine particles of
After that, after chemical sensitization in the same manner as in EMP-3A, K ₂ IrCl ₆ was previously added to 1.0 × 10 ⁻⁴ mol / mol AgX.
1. Doping pure AgBr fine particles having a particle size of 0.08 μm;
An emulsion to which 0 mol / mol AgX was added, and then RS-1, RS-2, SS-1, and a stabilizer were added in the same manner as EMP-3A was designated as Em-R6.

Emulsion EMP-3F was kept at 60 ° C., and K ₄ Fe (CN) ₆ was added 2.0 × before chemical sensitization.
10 ^-3 mol / mol AgX-doped particle size 0.05 μm
1.0 mol / mol AgX of pure AgCl fine particles of
After 10 minutes, further add K ₂ IrCl ₆ to 1.0 ×
10 ⁻⁴ mol / mol AgX doped particle size 0.05 μm
Em-R7 was obtained by adding 1.0 mol / mol AgX of pure AgBr fine particles and then adding chemical sensitization, a dye and a stabilizer similarly to EMP-3A.

The emulsion Em-R8 was different from the emulsion Em-R7 only in that the particle diameter of the AgCl fine particles was 0.2 μm.

EMP-1A and EMP-2A and (Solution C)
EMP-1E and EMP-2E were emulsions which differed only in that they did not contain K ₂ IrCl ₆ and K ₄ Fe (CN) ₆ .

Emulsion EMP-1E was kept at 60 ° C., and K ₄ Fe (CN) ₆ was added 2.0 × before chemical sensitization.
10 ^-3 mol / mol AgX-doped particle size 0.05 μm
1.0 mol / mol AgX of pure AgCl fine particles of
After 10 minutes, further add K ₂ IrCl ₆ to 1.0 ×
10 ⁻⁴ mol / mol AgX doped particle size 0.05 μm
Of pure AgBr fine particles of 1.0 mol / mol AgX, and then chemically sensitized in the same manner as EMP-1A.
And

Emulsion EMP-2E was kept at 55 ° C., and K ₄ Fe (CN) ₆ was added 2.0 × before chemical sensitization.
10 ^-3 mol / mol AgX-doped particle size 0.05 μm
1.0 mol / mol AgX of pure AgCl fine particles of
After 10 minutes, further add K ₂ IrCl ₆ to 1.0 ×
10 ⁻⁴ mol / mol AgX doped particle size 0.05 μm
Of pure AgBr fine particles of 1.0 mol / mol AgX and then chemically sensitized in the same manner as EMP-2A.
And

The red-sensitive emulsion of the fifth layer of Sample 104 was em-
Samples 202 to 208 replaced with R2 to R8 were prepared. Further, the blue-sensitive emulsion of the first layer of Sample 207 was em-B2
Then, Sample 209 was prepared in which the green-sensitive emulsion in the third layer was replaced with Em-G2.

Photographic Performance The sample 104 of Example 1 and the samples 202 to 209 prepared as described above were exposed to light wedge in 0.1 seconds by a conventional method using a sensitometer KS-7 (manufactured by Konica). After that, development processing was performed in the following development processing steps.

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.

High Illumination Exposure Characteristics Similarly, the samples 104 and 202 to 209 were evaluated as follows. Semiconductor laser GaAlAs as light source
(Oscillation wavelength of 808.5 nm) using a YAG solid-state laser (oscillation wavelength of 946 nm) as an excitation light source and SH of KNbO3
473 nm wavelength-converted and extracted by a G crystal, and a semiconductor laser GaAlAs (oscillation wavelength: 808.7 nm)
Solid-state laser (oscillation wavelength 10
532 nm, which is obtained by converting the wavelength of a 64 nm) by using a KTP SHG crystal, and AlGaInP (having an oscillation wavelength of about 6 nm).
70 nm). 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. Light wedge exposure was performed in which 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. At this time, the average exposure time per pixel was 5 × 10 ⁻⁸ seconds. After exposure, the same development processing and density measurement as in "photographic performance" were performed, and the relative sensitivity was expressed. Further, at this time, the density is 1.5 and the density is 2.2.
A gradation * 1 between 5 was obtained and represented as a shoulder gradation.

* 1: A 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 at the time of development at 10 seconds after exposure in the above high illuminance exposure was defined as 100, and the latent image stability was expressed as a relative value to the sensitivity at the time of development after standing for 24 hours after exposure. .

Character quality Evaluation was made in the same manner as in Example 1.

[0149]

[Table 4]

Table 4 shows that the sample using the silver halide emulsion of the present invention has a high sensitivity, has excellent shoulder gradation in high illuminance exposure, and has good latent image stability. Furthermore,
The sample using the silver halide emulsion of the present invention can easily set the maximum point gamma at a position far from the low illuminance side, giving a silver halide photographic light-sensitive material having extremely excellent character quality.

Example 3 In Example 2, an NPS manufactured by Konica Corporation 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 2, and it was confirmed that the effects of the present invention were obtained.

[0152]

According to the present invention, there is provided a method for producing a silver halide emulsion having high sensitivity, excellent character quality under high illuminance exposure, and good latent image stability, and a silver halide photograph using the silver halide emulsion. A photosensitive material and a color image forming method were obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/20 G03C 7/20

Claims (8)

[Claims] (1) a blue-sensitive emulsion layer, a green-sensitive emulsion layer,
In an image forming method in which a silver halide color light-sensitive material having at least one red-sensitive emulsion layer is subjected to multiple exposures with an exposure time shorter than 10 .mu.sec, the maximum point gamma is 60 to 95% from the low illuminance side of the effective exposure area. A color image forming method, comprising: 2. The color according to claim 1, wherein the difference between the maximum point gamma of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer from the low illuminance side is within 10%. Image forming method. 3. Silver halide grains containing 90 mol% or more of silver chloride are formed and desalted, and then silver chloride fine grains of 50 mol% or more of silver chloride are added. A method for producing a silver halide emulsion, characterized by adding silver halide fine particles. 4. The method for producing a silver halide emulsion according to claim 3, wherein both the silver chloride fine particles and the silver bromide fine particles have a particle size of 1/3 or less of the host particles. 5. The method according to claim 1, wherein the fine silver chloride particles and the fine silver bromide particles are of the formula VIII
5. The method for producing a silver halide emulsion according to claim 3, wherein each of said metal ions contains a different one of the metal ions belonging to the group III. 6. The silver chloride fine particles contain a compound represented by the following general formula (1), and the silver bromide fine particles contain an iridium compound. 3. The method for producing a silver halide emulsion as described in 1. above. Formula (1) (ML ⁶ ) n [wherein M represents a charged 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. ] 7. A silver halide photographic light-sensitive material comprising, on a support, a layer containing the silver halide emulsion obtained by the production method according to claim 3. 8. A blue-sensitive emulsion layer, a green-sensitive emulsion layer,
7. An image forming method comprising multiple exposure to a silver halide color light-sensitive material having at least one red-sensitive emulsion layer with an exposure time shorter than 10 .mu.sec, wherein at least one silver halide emulsion layer comprises at least one silver halide emulsion layer. Wherein the maximum point gamma is 60 to 95% from the low illuminance side of the effective exposure area, and the difference in the maximum point gamma of each layer from the low illuminance side is 1%.
A color image forming method characterized by being within 0%.