JPH1069041A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material which improves rough feeling of a printed picture in amplified development and shows little changes in the gradation balance against changes in the amplified developing time. SOLUTION: In the image forming process by amplified development of a silver halide photographic sensitive material having at least each one yellow image forming silver halide emulsion layer, a magenta image forming silver halide emulsion layer and a cyan image forming silver halide emulsion layer on a support, the number of silver halide particles per unit area in each silver halide emulsion layer is the largest in the magenta image forming silver halide emulsion layer. Moreover, the number of silver halide particles per unit area in the magenta image forming silver halide emulsion layer ranges between >=1.5 times and <=2.1 times as the number of silver halide particles per unit area in the cyane image forming silver halide emulsion layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material which has improved graininess at the time of appreciating a printed image in amplification development processing and has less variation in gradation balance with variation in amplification development processing time. Things.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials are very popular today because they have very high characteristics, such as high sensitivity and excellent gradation, as compared with other light-sensitive materials. It is used for The silver halide photographic light-sensitive material has the features described above, and the silver halide amount in the light-sensitive material can be reduced. As a preferable means in terms of effective use of resources, the silver halide photographic light-sensitive material is amplified and developed. An image forming method has been known for a long time. As an example of the amplification development processing, there is a method in which an oxidized color developing agent is generated with an oxidizing agent such as hydrogen peroxide / cobalt (III) complex using developed silver as a catalyst, and then an image dye is formed by reaction with a coupler. .

In general, it is known that when printing image information recorded on a film onto paper by enlargement projection, the graininess of the film greatly affects the graininess of a printed image. However, in the amplification and development processing of a light-sensitive material having a small amount of silver halide applied,
As the amount of silver halide applied decreases, the effect of the graininess of the film on the graininess at the time of viewing the print image decreases, and the effect of the graininess of the paper on the graininess at the time of directly viewing the print image increases. Come.
Therefore, in the image forming method by the amplification development processing, the graininess is likely to be deteriorated, and the mechanism of occurrence is different from that of the conventional photographic system. Easily occur, and its improvement has been desired.

In a normal color developing process, for a while after a certain development time has elapsed and a sufficient maximum density has been obtained, the characteristic curve shows a behavior of slightly changing in a parallel movement, There is an area where the rise can be suppressed very slightly, and even if there is a slight change in the processing time, a very slight change in density occurs. It was possible to obtain characteristics with almost no problem such as fluctuations in the characteristics.

On the other hand, in the amplification and development processing, the change in gradation is large, and even after reaching a sufficient maximum density, the change in gradation particularly in a high-density portion continuously occurs, and the rise in the minimum density eventually becomes conspicuous. . For this reason, the gradation balance greatly fluctuates with respect to the fluctuation of the amplification processing time, and development of an improved technique for this phenomenon has been desired.

[0006] In order to reduce the amount of silver halide and reduce the graininess at the time of appreciating a printed image, it is preferable to make the grain size of the silver halide grains as small as possible. Since the sensitivity decreases as the diameter decreases, there is a limit in reducing the size of silver halide grains.

Japanese Patent Application Laid-Open No. 6-301128 suggests that the use of tabular silver halide grains can reduce the deterioration in graininess when the amount of silver halide is reduced. Examples in which tabular silver halide grains are applied to a silver emulsion layer are described in Examples.
However, although the graininess of the yellow image is improved by using the tabular silver halide grains in the silver halide emulsion layer for forming the yellow image, the improvement in roughness of the printed image reproducing the gray image is not satisfactory. In addition, there is no description about the problem that the fluctuation of the gradation balance is large with respect to the fluctuation of the amplification development processing time.

The inventors of the present invention have studied and found that, when the number of silver halide grains in each color image forming layer satisfies a certain condition, the feeling of roughness at the time of appreciating a printed image is reduced, and amplification processing is performed. The present inventors have found that the variation of the gradation balance becomes smaller with respect to the variation of time, and have accomplished the present invention.

[0009]

SUMMARY OF THE INVENTION According to the present invention, there is provided a silver halide silver halide emulsion having improved graininess at the time of appreciating a printed image and having a small variation in gradation balance with a variation in the amplification development time. A photographic light-sensitive material is provided.

[0010]

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

(1) A silver halide photographic material having at least one yellow image forming silver halide emulsion layer, a magenta image forming silver halide emulsion layer and a cyan image forming silver halide emulsion layer on a support. In the image forming method of performing the amplification development processing, the number of silver halide grains per unit area of the silver halide emulsion layer is the largest in the magenta image forming silver halide emulsion layer, and
The number of silver halide grains per unit area of the magenta image forming silver halide emulsion layer is from 1.5 times to 2.1 times the number of silver halide grains per unit area of the cyan image forming silver halide emulsion layer. An image forming method comprising:

(2) The amount of silver halide in the magenta image forming silver halide emulsion layer of the silver halide photographic light-sensitive material is 0.9 to 4 times the amount of silver halide in the cyan image forming silver halide emulsion layer. 2. The image forming method according to the item 1, wherein the method is as follows.

(3) The amount of silver halide in the yellow image forming silver halide emulsion layer of the silver halide photographic light-sensitive material is 1.8 times or more and 5 times or more the amount of silver halide in the magenta image forming silver halide emulsion layer. 3. The image forming method as described in 1 or 2 above, wherein

(4) The total amount of silver halide coated on the support of the silver halide light-sensitive material is 0.01 to 0.15 g / m ² or less in terms of silver. The image forming method according to any one of claims 1 to 3.

Hereinafter, the present invention will be described in detail. Silver halide photographic light-sensitive material according to the present invention (hereinafter referred to as light-sensitive material)
Has at least a yellow image forming silver halide emulsion layer, a magenta image forming silver halide emulsion layer and a cyan image forming silver halide emulsion layer on a support, and the number of silver halide grains per unit area is magenta. It is characterized by being the largest in an image forming silver halide emulsion layer.

The number of silver halide grains per unit area of each layer can be measured by various methods generally used in the art. For example, after a photosensitive material having a fixed area is subjected to a peeling treatment for each layer, an electron micrograph is taken, and the number of silver halide grains contained in each image forming silver halide emulsion layer can be directly counted. However, it can be easily performed by image processing using a computer. When the silver halide emulsion is a so-called monodispersed emulsion, the number of grains per unit area can be calculated from the amount of silver halide applied and the average grain size of the silver halide grains.

In the light-sensitive material according to the present invention, when a certain color image forming silver halide emulsion layer comprises a plurality of layers such as a high-speed layer and a low-speed layer, the color image-forming silver halide emulsion The total number of silver halide grains contained per unit area of a plurality of layers constituting the layer is defined as the number of silver halide grains per unit area of the color image forming silver halide emulsion layer.

In the light-sensitive material according to the present invention, the number of silver halide grains per unit area of the magenta image-forming silver halide emulsion layer is one of the number of silver halide grains per unit area of the cyan image-forming silver halide emulsion layer. 0.5 to 2.1 times.
When the ratio is 1.5 times or more, the effect of the present invention for improving the feeling of roughness at the time of appreciating the printed image is particularly remarkable. The effect of improving the gradation balance is particularly remarkable with respect to the fluctuation.

The composition of the silver halide photographic emulsion according to the present invention has an arbitrary halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chloroiodobromide and silver chloroiodide. However, from the viewpoint of rapid processability, processing stability, and maintenance of amplification development activity, silver chloride is preferably contained in an amount of 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. Silver halide emulsions containing 〜99.9 mol% of silver chloride are preferred.

In order to obtain the silver halide emulsion according to the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is also preferably used. In this case, the portion containing a high concentration of silver bromide may be a so-called core / shell emulsion in which a complete layer is formed, or a region in which the complete layer is not formed and the composition is merely partially present. In this case, what is called an epitaxy junction may be used. Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide is present at a high concentration is present at the top of silver halide grains.

The silver halide emulsion according to the present invention preferably contains a heavy metal ion for improving photographic performance. Heavy metal ions include iron, iridium, platinum,
Group 8-10 metals such as palladium, nickel, rhodium, osmium, ruthenium, cobalt and cadmium,
Group 12 transition metals such as zinc and mercury, lead, rhenium,
Examples include molybdenum, tungsten, gallium, and chromium ions. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

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

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

In order for the silver halide emulsion according to the present invention to contain heavy metal ions, the heavy metal compound is physically added before, during, and after the formation of silver halide grains. What is necessary is just to add in arbitrary places of each process during ripening. The heavy metal compound can be dissolved together with the halide salt and added continuously over the whole or a part of the grain formation process.

When the heavy metal ion is added to the silver halide emulsion, the amount is 1 × 10 ^-9 per mol of silver halide.
Mol or more and 1 × 10 ^-2 mol or less, particularly preferably 1 × 10 ⁻² mol or less.
It is preferably at least 10 ^-8 mol and not more than 5 10 ^-5 mol.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a {100} plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,666;
JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) 21, 39.
(1973), etc., particles having an octahedral, tetradecahedral, dodecahedral shape or the like can be prepared and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape are preferably used, but it is particularly preferable to add two or more monodispersed silver halide emulsions to the same layer. The monodispersed silver halide emulsion referred to here has a coefficient of variation of 0.2 which represents the width of the particle size distribution of silver halide grains.
It is a silver halide emulsion having a coefficient of variation of 0.15 or less, preferably a silver halide emulsion having a coefficient of variation of 0.15 or less. The coefficient of variation is defined by the following equation.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution and R is the average grain size) The grain size of the silver halide grains according to the present invention is not particularly limited, but rapid processing is possible. Considering other photographic performances such as properties and sensitivity, it is preferably in the range of 0.1 to 1.2 μm, more preferably 0.2 to 1.0 μm.

In the present invention, the diameter of the photosensitive silver halide grains is defined as the diameter of a circle having an area equal to the projected area of the silver halide grains, and the unit is expressed in μm. The particle size of the silver halide grains can be measured by various methods generally used in the art. A typical method is Loveland's “particle size analysis method”.
(A.S.T.M. Symposium on Right Microscopy, pp. 94-122, 1955) or
The method described in "Theory of Photographic Process, Third Edition" (co-authored by Mies and James, Chapter 2, published by Macmillan, 1966) can be mentioned.

The silver halide emulsion according to the present invention 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 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.

Further, JP-A-57-92523, 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 arranged in a reaction mother liquor, and a water-soluble silver salt and a water-soluble solution described in German Patent Publication No. 292,164. Apparatus for continuously changing the concentration of an aqueous halide salt solution, JP-B-56-50
The reaction mother liquor was taken out of the reactor described in No. 1776, etc.
An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by ultrafiltration may be used.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide grains according to the present invention include:
It is preferable to use a so-called tabular silver halide. # 1 as tabular grains containing silver chloride in high concentration
Grains having a {11} major plane and grains having a {100} major plane are known, but grains having a {100} major plane are preferred from the viewpoint of the stability of silver halide grains.

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

As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, etc. can be used, but a sulfur sensitizer is preferable.

The silver halide emulsion according to the present invention is intended to prevent fogging that occurs during the process of preparing a silver halide photographic material, reduce performance fluctuation during storage, and prevent fogging that occurs during development. And known antifoggants and stabilizers can be used. Examples of preferred compounds that can be used for such purposes include JP-A-2-146.
Compounds represented by the general formula (II) described in the lower column on page 7 of JP-A No. 036 can be mentioned. These compounds are added in a step of preparing silver halide emulsion grains, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution or the like according to the purpose.

In the present invention, the photosensitive halogenated
The amount of silver refers to the amount of photosensitive halide applied per unit area.
Is the amount of silver halide converted to silver, and the unit is g
/ M ^TwoNotation. The amount of photosensitive silver halide is conventionally known.
Method, for example, if necessary, photosensitive material
After the photographic layer was peeled off, the atomic absorption analysis and fluorescence X
It can be determined by performing a line analysis.

In the light-sensitive material according to the present invention, the silver halide grains only need to be present in an amount necessary to produce developed silver which serves as a catalyst during amplification development described later. The amount of silver halide can be greatly reduced as compared with a general color developing method in which a necessary oxidized color developing agent is produced by a redox reaction between silver halide and the developing agent. There is no lower limit to the amount of silver halide as long as an image having a sufficient density is formed, but the total amount is preferably 0.01 g / m ² or more in terms of silver. Further, the total amount of silver halide coated on the support is 0.15 g / m ² or less in terms of silver amount, and particularly preferably 0.1 g / m ² or less.
It is preferably 1 g / m ² or less because the effect of improving gradation balance fluctuation is large. In this case, the amount of silver halide per each color image forming layer is preferably from 0.05 g / m ² or less of silver amount conversion, and further preferably not 0.03 g / m ² or less.

In order to reduce the roughness at the time of appreciating the printed image and to stably reproduce the gradation balance with respect to the fluctuation of the amplification processing time, the amount of silver halide in the silver halide emulsion layer for forming a yellow image is particularly important. The amount of silver halide in the silver halide emulsion layer for forming a magenta image is preferably 1.8 times or more and 5 times or less, since the effect of improving gradation balance fluctuation with respect to fluctuation in amplification development processing time is preferred. Further, the amount of silver halide in the magenta image forming silver halide emulsion layer was 0.1% of the amount of silver halide in the cyan image forming silver halide emulsion layer.
It is preferable that the ratio be 9 times or more and 4 times or less, because the effect of improving the gradation balance fluctuation with respect to the fluctuation of the amplification development processing time is large.

In the light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, dyes having absorption in the visible region include those described in JP-A-3-2518.
The dyes of AI-1 to 11 described on page 308 of JP-A-40 and the dyes described in JP-A-6-3770 are preferably used.
General formula (I) described in the lower left column of page 2 of JP-A-750-750,
The compounds represented by (II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and do not cause contamination due to residual color.

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

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

The light-sensitive material according to the present invention comprises a layer containing a silver halide emulsion spectrally sensitized to a specific region in the wavelength region of 400 to 900 nm in combination with a yellow dye-providing substance, a magenta dye-providing substance, and a cyan dye-providing substance. Having. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye for use in the silver halide emulsion according to the present invention, any known compounds can be used.
BS-1 to 8 described on page 28 of JP-A-251840 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 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. Nos. S-1 to S-17 described on pages 15 to 17
Are preferably used in combination.

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

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

When a coupler is used as a dye-donating substance in the light-sensitive material according to the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent. Any compounds capable of forming a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 5
A magenta dye-forming coupler having a spectral absorption maximum wavelength in the range of 00 to 600 nm and a cyan dye-forming coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm are known.

Cyan couplers which can be preferably used in the light-sensitive material according to the present invention include those described in JP-A-4-114.
No. 154, page 5, lower left column, formula (C-
Couplers represented by I) and (C-II);
The general formula (I) described in the lower left column on page 4 of JP-A-5056
a) a cyan coupler represented by (Ib) or (Ic),
JP-A 1-222461, page 6, lower right to page 7, upper left column, general formulas (IIα) to (VIIIα) and page 7, lower right, page 8, upper left column, general formulas (IIβ) to
And a cyan coupler represented by (VIIIβ). In particular, the general formulas (IIα) to (VIIIα) and (IIβ)
Cyan couplers represented by the formulas (VIII) to (VIIIβ) are preferable because they have a sharp absorption of image dyes and have excellent color reproducibility.

The magenta coupler which can be preferably used for the light-sensitive material according to the present invention is described in JP-A-4-11.
The general formula (M-
Couplers represented by I) and (M-II) can be mentioned. More preferred of the magenta coupler,
It is a coupler represented by the general formula (MI) described in the upper right column of page 4 of the publication, among which the above-mentioned general formula (MI)
Are particularly preferred because of their high light resistance.

The yellow coupler preferably usable in the light-sensitive material according to the present invention is described in JP-A No. 4-11.
The general formula (Y-
The couplers represented by I) can be mentioned. Of these, couplers in which RY1 in the general formula [Y-1] is an alkoxy group or couplers represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone and are preferable. The most preferred compounds are those represented by the general formula [Y-1] described in JP-A-4-81847, page 1 and pages 11 to 17 of the same.

The following are specific examples of couplers that can be preferably used in the light-sensitive material according to the present invention.

[0053]

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[0054]

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When an oil-in-water emulsion dispersion method is used to add a dye-providing substance or other organic compound used in the light-sensitive material according to the present invention, a water-insoluble high-boiling organic compound having a boiling point of 150 ° C. or higher is usually used. If necessary, a low boiling point and / or water-soluble organic solvent is used in combination in the solvent, and the mixture is dissolved and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. The high-boiling point organic solvent that can be used for dissolving and dispersing the dye-providing substance has a dielectric constant of 3.
It is preferably from 5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means.

As a compound preferable as a surfactant used for dispersing a photographic additive or adjusting the surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution to the coating are preferably as short as 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

It is preferable to use an anti-fading agent in combination with the dye-providing substance 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, phenolic compounds represented by general formula IIIB described in JP-A-3-174150, and Amine compounds represented by the general formula A described in JP-A-64-90445;
General formulas XII, XIII, XIV, XV described in -182741
Are particularly preferred for magenta dyes. Further, compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and the compound (A'-1) described in the lower left column of page 10 of the same publication are disclosed. And the like. In addition, a fluorescent dye-releasing compound described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material according to the present invention, 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. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone.

It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog or to improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by the formula III-3 described in JP-A-1-250944, and JP-A-64-6664.
6, a compound represented by the general formula III,
UV-1L to UV-27 described in 3-187240
L, compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

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

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-24
It is preferable to use the compounds described in JP-A Nos. 9054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the photosensitive material or the processed sample.

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

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used.

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

The light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or undercoating (adhesion, antistatic properties of the support surface, It may be applied via one or more undercoat layers for improving dimensional stability, friction resistance, hardness, antihalation properties, friction properties and / or other properties.

At the time of coating the light-sensitive material according to the present invention, 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.

To form a photographic image using the photosensitive material according to the present invention, the image recorded on the negative may be optically focused on the photosensitive material to be printed and printed. Also, the image may be once converted into digital information, then the image may be formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed. The printing may be performed by scanning while changing the light intensity or the irradiation time.

The present invention is particularly preferably applied to a photosensitive material for forming an image for direct viewing. For example, 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 can be used. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

The light-sensitive material according to the present invention exhibits the effects of the present invention when subjected to amplification and development processing. Hereinafter, the amplification development processing will be described.

In the present invention, the term “amplification development” refers to a process in which a latent image generated by exposure of a photosensitive material is developed with a color or black-and-white developer to form developed silver, and a chemical reaction using the developed silver as a catalyst is utilized. Is defined as a method of forming or releasing image dyes by, for example, a method of forming image dyes by a coupling reaction of a coupler with an oxidized developing agent formed by a redox reaction of a developing agent and an oxidizing agent using a developed silver catalyst as a catalyst, and the like. Is raised.

Examples of the oxidizing agent include compounds that give hydrogen peroxide such as hydrogen peroxide and an adduct of hydrogen peroxide, peroxo compounds such as peroxoborate and peroxocarbonate, and cobalt (III) such as cobalt hexaammine complex.
Complexes, halogenous acids such as chlorous acid, periodic acid and the like can be used. Above all, a method using hydrogen peroxide as an oxidizing agent is advantageous because the effect of amplification is high and the load on the environment is reduced.

In the amplification and development process according to the present invention, a combination of an aromatic primary amine developing agent and hydrogen peroxide is preferably used.
N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5
(N-ethyl-N-laurylamino) toluene, 4-
(N-ethyl-N- (β-hydroxyethyl) amino)
Aniline, 2-methyl-4- (N-ethyl-N- (β-
Hydroxyethyl) amino) aniline, 4-amino-3
-Methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline, N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide,
N, N-dimethyl-p-phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (β
-Ethoxyethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline and the like.

Further, besides the aromatic primary amine developing agents, for example, European Patents 565,165 and 572,05
Nos. 4, 593, 110, and JP-A-8-202002.
And the sulfonyl hydrazide and carbonyl hydrazide developing agents described in JP-A Nos. 8-227131 and 8-234390 can also be preferably used.

In the present invention, it is possible to supply a processing solution containing the above color developing agent and an oxidizing agent for amplification development to a photosensitive material as a co-existing solution. A liquid containing the agent is divided into a plurality and prepared,
It is also possible to supply to a photosensitive material.

The amplification and development method according to the present invention is described in, for example, JP-A Nos. 52-13335 and 55-127555.
As described in JP-A-61-77851 and the like, a developing agent and an oxidizing agent are present in the same processing bath (developing / amplifying solution) to produce developed silver as a catalyst and the subsequent amplification development processing. A method performed in the same bath, JP-A-5-216192,
As described in JP-A-5-346647 and the like, a method in which a developing bath containing a developing agent and an amplification bath containing an oxidizing agent are separated, silver is formed in the developing bath, and the developing agent is brought into the amplification bath and amplified and developed. Or JP-A-61-88259.
As described in JP-A No. 7-077788, etc., after processing in a developing bath containing a developing agent to form developed silver, and then performing amplification development in a processing bath containing a developing agent and an oxidizing agent. Can be Further, as a processing method without using a processing bath, for example, a method of spraying a developing solution or an amplifying solution onto a silver halide photosensitive material in a mist as described in JP-A-61-80150 can be used.

When the developing bath and the amplification bath are separated, the preferred amount of the developing agent in the developing solution is 0.2 to 50 g / l, particularly preferably 1 to 25 g / l. The amount of hydrogen peroxide (30% solution) in the amplification solution is 0.1 to 100 ml / l.

When the processing is carried out in a single bath of the developing bath and the amplification bath, the preferred amount of the developing agent in the developing / amplifying solution is 0.5 to
15 g / l, more preferably 1 to 7 g / l, and the preferred amount of hydrogen peroxide (30% solution) is 0.1 to 30 m
1 / l, more preferably 1 to 5 ml / l.

In the present invention, the above-mentioned developer, amplifying solution,
Although the developing / amplifying solution can be used in an arbitrary pH range, the pH is preferably from 9.5 to 13.0, and more preferably from 9.8 to 12.0, from the viewpoint of rapid processing.

The processing temperature of the amplification development according to the present invention is 20
The temperature is preferably not less than 60 ° C and not less than 60 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, it is preferable that the temperature is not too high.

The amplification development time varies depending on the processing temperature, the activity of the processing solution, etc., but is preferably within 180 seconds, more preferably within 90 seconds in the present invention.

To the developing solution, the amplifying solution, and the developing / amplifying solution, a known developer component compound can be added in addition to the color developing agent and the oxidizing agent. Usually, an alkali agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazoles, a preservative, a chelating agent and the like are used.

After the color development, the light-sensitive material of the present invention may be subjected to a bleaching process and a fixing process, if necessary. 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 water washing treatment, a stabilization treatment may be performed. As a processing apparatus used for processing the silver halide photographic light-sensitive material of the present invention, even if it is a roller transport type in which the light-sensitive material is conveyed between rollers arranged in a processing bath, the light-sensitive material is fixed to a belt. Endless belt type may be used for transporting the processing bath, but the processing bath is formed in a slit shape,
A method in which the processing solution is supplied to this processing bath and the photosensitive material is conveyed, a method in which the processing solution is sprayed, a method in which the processing solution is impregnated with a carrier impregnated with the processing solution, and a method in which a viscous processing solution is used. Can be.

[0085]

Next, the present invention will be described based on examples, but embodiments of the present invention are not limited to these examples.

Example 1 (Preparation of Blue-Sensitive Silver Halide Emulsion Em-B1) The following (A1) was placed in 1 liter of a 2% aqueous gelatin solution kept at 40 ° C.
Solution B) and (B1 Solution) were added simultaneously while controlling pAg = 7.3 and pH = 3.0, and the following (C1 Solution) and (D1 Solution) were further added.
Solution) was added simultaneously while controlling pAg = 8.0 and pH = 5.5. At this time, the control of pAg is described in JP-A-59-454.
The pH was controlled using a sulfuric acid or sodium hydroxide aqueous solution.

(A1 solution) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B1) Silver nitrate 10 g Water was added to 200 ml (Solution C1) Sodium chloride 102.7 g Potassium hexachloroiridium (IV) ate 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g Add water 600 ml (Solution D1) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas Demol After desalting was performed using a 5% aqueous solution of N and a 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1A was obtained. Next, in the preparation of EMP-1A, the average particle size was 0.64 μm and the particle size was the same except that the addition time of (A1 solution) and (B1 solution) and the addition time of (C1 solution) and (D1 solution) were changed. A monodisperse cubic emulsion EMP-1B having a distribution variation coefficient of 0.07 and a silver chloride content of 99.5 mol% was obtained.

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

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (green-sensitive silver halide emulsion Preparation) Silver halide emulsion E
In the preparation of MP-1A, the average particle size was 0.40 μm, and the content of silver chloride was changed in the same manner except that the addition time of (A1 solution) and (B1 solution) and the addition time of (C1 solution) and (D1 solution) were changed. Cubic emulsion EMP-11A having a percentage of 99.5 mol%
Further, a monodispersed cubic emulsion EMP-11B having an average particle size of 0.45 μm and a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-11A was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also EMP-
Similarly, after optimally chemical sensitizing 11B, the sensitized EMP-11A and EMP-11B 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) Silver halide emulsion E
In the preparation of MP-1A, the average particle size was 0.43 μm, and the content of silver chloride was changed in the same manner except that the addition time of (solution A1) and (solution B1) and the addition time of (solution C1) and (solution D1) were changed. Monodisperse cubic emulsion EMP-21A having a percentage of 99.5 mol%
Further, a monodispersed cubic emulsion EMP-21B having an average particle size of 0.40 μm and a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-21A was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also EMP-
Similarly, after optimally sensitizing 21B, the sensitized EMP-21A and EMP-21B were mixed at a silver amount of 1: 1 to prepare a red-sensitive silver halide emulsion (Em-R1). Obtained.

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

[0094]

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(Preparation of silver halide photographic light-sensitive material) 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 on which the emulsion layer was applied, a molten polyethylene containing anatase-type titanium oxide having a surface treatment dispersed therein at a content of 15% by weight was laminated. After subjecting this reflective support to corona discharge treatment, a gelatin undercoat layer was provided, and further, each layer having the following constitution was provided, and the silver halide photographic light-sensitive materials 101 to
114 was created. The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) 7th layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 6th layer (UV absorbing layer) Gelatin 0.40 AI-1 0.01 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Stain inhibitor (HQ-5) 0.04 PVP 0.03 Fifth layer (red-sensitive layer) Gelatin 1.30 Red-sensitive emulsion (Em-R1) Table 1 Cyan coupler (C-1) 0.25 Cyan coupler (C-2) 0.08 Dye image stabilizer (ST-1) 0.10 Stain inhibitor (HQ-1) 0.004 DBP 0.10 DOP 0.20 Fourth layer (ultraviolet absorbing layer) Gelatin 0.94 Ultraviolet absorbing agent (UV- 1) 0.28 UV absorption Absorbent (UV-2) 0.09 Ultraviolet absorber (UV-3) 0.38 AI-1 0.02 Stain inhibitor (HQ-5) 0.10 Third layer (green photosensitive layer) Gelatin 1. 30 AI-2 0.01 Green light-sensitive emulsion (Em-G1) described in Table 1 Magenta coupler (M-1) 0.20 Dye image stabilizer (ST-3) 0.20 Dye image stabilizer (ST) -4) 0.17 DIDP 0.13 DBP 0.13 Second layer (intermediate layer) Gelatin 1.20 AI-3 0.01 Stain inhibitor (HQ-2) 0.03 Stain inhibitor (HQ-3) 0.03 Stain inhibitor (HQ-4) 0.05 Stain inhibitor (HQ-5) 0.23 DIDP 0.04 DBP 0.02 Fluorescent brightener (W-1) 0.10 First layer (blue) Photosensitive layer) Gelatin 1.20 Blue photosensitive emulsion (Em-B1) 1. Yellow coupler (Y-1) 0.70 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer (ST-2) 0.10 Dye image stabilizer (ST-5) 0 .10 Anti-stain agent (HQ-1) 0.01 Image stabilizer A 0.15 DBP 0.10 DNP 0.05 Support Polyethylene laminated paper Also, as a hardening agent (H-1), (H-2) Was added.
Surfactant (SU-1) as a coupler dispersing aid
And as a coating aid, a surfactant (SU-2),
(SU-3) was 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 .

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium DBP: dibutyl phthalate DIDP: diisodecyl phthalate DOP : Dioctyl phthalate DNP: dinonyl phthalate PVP: polyvinylpyrrolidone HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di- sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butylhydroquinone Image stabilizer A : Pt-octylpheno Rule

[0098]

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[0099]

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[0100]

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[0101]

[Table 1]

In Table 1, the amount of silver halide is shown in terms of silver.

QY / QM represents the ratio of the amount of silver halide in the yellow image forming layer to the amount of silver halide in the magenta image forming layer.

QM / QC represents the ratio of the amount of silver halide in the magenta image forming layer to the amount of silver halide in the cyan image forming layer.

NM / NC represents the ratio of the number of silver halide grains in the magenta image forming layer to the number of silver halide grains in the cyan image forming layer.

NM / NY represents the ratio of the number of silver halide grains in the magenta image forming layer to the number of silver halide grains in the yellow image forming layer.

(Evaluation of photosensitive material) The photosensitive materials (101) to (114) thus produced were exposed to white wedges for 0.5 seconds each with a light wedge, and subjected to the following amplification and development processing steps. After performing the processing, the reflection densities of blue light, green light, and red light were measured using a densitometer PDA-65 (manufactured by Konica Corporation), and the reflection density between the reflection density of 0.75 and the reflection density of 1.75 was measured. The average gradient was defined as a gradation, and a gradation when amplification and development were performed in 60 seconds and a gradation when the amplification development time was set to 70 seconds were obtained for each photosensitive material. Valence obtained by dividing gradation was measured tone measured by blue light green light at 60 seconds and Y / M ^60, its 70 seconds was Y / M ^70. Similarly, the value obtained by dividing the gradation of red light at 60 seconds by the gradation of green light is C / M ^60, and the value at 70 seconds is C / M ^60.
70 . Considered as a reference tone when amplified and developed with 60 seconds, Y / M = | Y / M 70 -Y / M 60 | C / M = | C / M 70 -C / M 60 | , respectively, the processing time Was evaluated as the stability of the reproduction of the gradation balance with respect to the fluctuation of the image. The smaller this value is, the more stable the gradation balance reproduction is.

The exposure condition was adjusted to adjust the reflection density to 0.7.
A gray patch of .about.0.8 was prepared and presented to 20 subjects, and a judgment was made as to whether or not the graininess was conspicuous. Table 2 shows the results.

Processing Step Processing Temperature Amplification Developer (CDA-1) 33.0 ± 0.5 ° C. 60 seconds, 70 seconds Bleaching / Fixing Solution (BF-1) 35.0 ± 0.5 ° C. 20 Second stabilizing solution 30-34 ° C 60 seconds Drying 60-80 ° C 30 seconds The composition of the processing solution is shown below.

Amplification developer (CDA-1) Pure water 800 ml Potassium bromide 0.001 g Potassium chloride 0.35 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4 0.0 g N, N-diethylhydroxylamine 4.7 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g 1-hydroxyethylidene-1,1'-diphosphonic acid 0.35 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative 2.0 g Potassium carbonate 20 g Hydrogen peroxide solution (30%) 5.0 ml Add water to make the total volume 1 liter, and adjust to pH = 10.3.

Bleaching / fixing solution (BF-1) Pure water 700 ml Diethylenetriaminepentaacetate ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4 -Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust the pH to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution Pure water 800 ml 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 0.0 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 (polyvinylpyrrolidone) 1.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water. .

[0113]

[Table 2]

From the results shown in Table 2, the photosensitive material (101),
(102), (107), (111), and (112)
The ratio of the number of silver halide grains in the magenta image forming layer to the number of silver halide grains in the cyan image forming layer was 1.5 or less, indicating that the gray image was less tolerant to roughness. In the light-sensitive materials (106), (108) and (114), the ratio of the number of silver halide particles in the magenta image forming layer to the number of silver halide particles in the cyan image forming layer is 2.1 or more, and the gray image Is highly tolerant to the roughness feeling, but there is a large difference between the gradations of the cyan image and the magenta image, and the effect of the present invention that a stable gradation balance can be reproduced with respect to fluctuations in the amplification development time cannot be obtained.
On the other hand, the photosensitive materials (103) to (105), (1)
09), (110), and (113) show that the gray image has a high tolerance for the roughness, and can reproduce a stable gradation balance with respect to the fluctuation of the amplification development time. In particular, the photosensitive material (1) satisfying the preferred conditions of the present invention.
03), (104), (109) and (110), the effect of the present invention for reproducing a stable gradation balance with respect to fluctuations in the amplification and development time is small, since the difference in gradation between the respective color image forming layers is small. It turns out that it is high.

Example 2 In preparing photosensitive materials (101), (104) and (109), the cyan coupler of the red photosensitive layer was changed from (C-1) to (C-3) and (C-4). In the same manner as above, photosensitive materials (201) to (206) were prepared, and the same evaluations as in Example 1 were performed. Table 3 shows the results.

[0116]

[Table 3]

From the results in Table 3, it is found that the imidazole nucleus having a sharp absorption spectrum of the image dye was formed in the cyan image forming layer.
And the photosensitive materials (203) to (206) satisfying the conditions of the present invention using a coupler of a pyrazoloazole nucleus, the photosensitive material (1) using a coupler of a phenol nucleus is used.
04) and (109), the effect of improving the roughness of the gray image is further enhanced.

Example 3 (Preparation of Blue-Sensitive Silver Halide Emulsion) Silver Halide Emulsion E
In the preparation of MP-11A, (A1 solution) and (B1 solution)
Monodisperse cubic emulsion EMP-31 having an average particle size of 0.50 [mu] m and a silver chloride content of 99.5 mol%, except that the addition time of (C1 solution) and (D1 solution) were changed.
A, average particle size 0.45 μm, silver chloride content 99.5
A mol% monodisperse cubic emulsion EMP-31B was obtained.

The above-mentioned EMP-31A and EMP-31B were optimally chemically sensitized similarly to EMP-1A and EMP-1B, and then sensitized EMP-31A and EMP-31B.
B was mixed at a silver amount of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B2).

(Preparation of Green-Sensitive Silver Halide Emulsion) In the preparation of silver halide emulsion EMP-11A, (A1 solution)
The average particle diameter was 0.34 in the same manner except that the addition time of (B1 solution) and (C1 solution) and (D1 solution) were changed.
μm, monodisperse cubic emulsion EMP-41A having a silver chloride content of 99.5 mol%, and monodisperse cubic emulsion EMP-41B having an average particle size of 0.39 μm and a silver chloride content of 99.5 mol%.
I got

The above-mentioned EMP-41A and EMP-41B were optimally chemically sensitized similarly to EMP-11A and EMP-11B, and then sensitized EMP-41A and EMP-41B.
41B was mixed at a silver ratio of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G2).

In the preparation of the green photosensitive emulsion (Em-G2), EMP-41A and EMP-41B
A green photosensitive emulsion (Em-G3) was prepared in the same manner except that P-31A and EMP-31B were used.

(Preparation of Red-Sensitive Silver Halide Emulsion) In the preparation of a red-sensitive silver halide emulsion (Em-R1),
MP-21A and EMP-21B were replaced with EMP-1A and EMP, respectively.
A red-sensitive silver halide emulsion (Em-R2) was obtained in the same manner except that MP-1B was used. In the preparation of the red-sensitive silver halide emulsion (Em-R1), EMP-
21A and EMP-21B were converted to EMP-41A and EMP, respectively.
A red-sensitive silver halide emulsion (Em-R3) was obtained in the same manner except that -41B was used.

(Preparation of photosensitive material) In the preparation of the photosensitive material (101), the type of silver halide emulsion of each photosensitive layer,
Light-sensitive materials (301) to (313) were prepared in the same manner except that the amounts of silver halide and silver halide were adjusted as shown in Table 4.

[0125]

[Table 4]

With respect to the photosensitive materials (301) to (313), the same evaluation as in Example 1 was performed. Table 5 shows the results.

[0127]

[Table 5]

From Table 5, it can be seen that the photosensitive materials (307) and (31)
In 3), the number of silver halide grains in the magenta image forming layer is not the maximum, and photosensitive materials (301), (302),
In (308), the ratio of the number of silver halide grains in the magenta image forming layer to the number of silver halide grains in the cyan image forming layer was 1.5 or less, indicating that the gray image was less tolerant to roughness.

Further, photosensitive materials (306) and (310)
Indicates that the ratio of the number of silver halide grains in the magenta image forming layer to the number of silver halide grains in the cyan image forming layer is 2.1 or more, and the gray image has high tolerance to roughness, but the cyan image and the magenta image The deviation of the gradation of is large,
The effect of the present invention that a stable gradation balance can be reproduced with respect to the fluctuation of the amplification development time cannot be obtained.

Photosensitive materials (303), (304), (30)
9) and (311) show that the ratio of the amount of silver halide in the magenta image forming layer to the amount of silver halide in the cyan image forming layer is 0.9.
This is a preferable range of the present invention of 4 or less, and the effect of the present invention that a difference between the gradations of the cyan image and the magenta image is small and a stable gradation balance can be reproduced with respect to the fluctuation of the amplification development time is particularly remarkable. Is preferable.

Photosensitive materials (304), (305), (31)
2) is a preferred range of the present invention in which the ratio of the amount of silver halide in the yellow image forming layer to the amount of silver halide in the magenta image forming layer is 1.8 or more and 5 or less, and the gradation of the yellow image and the magenta image is The effect of the present invention, in which the deviation is small and the gradation balance can be reproduced stably with respect to the fluctuation of the amplification development time, is particularly remarkable and preferable. The photosensitive material (304) which satisfies all the preferable conditions of the present invention has a high tolerance to the graininess of a gray image, and has a great effect of the present invention that a stable gradation balance can be reproduced with respect to the fluctuation of the amplification development time. I understand.

[0132]

According to the present invention, in the amplification development processing,
It was possible to provide a silver halide photographic light-sensitive material in which the roughness at the time of appreciating a printed image was improved, and the variation in gradation balance was small with respect to the variation in amplification processing time.

Claims (4)

[Claims] Amplifying a silver halide photographic material having at least one yellow image forming silver halide emulsion layer, a magenta image forming silver halide emulsion layer and a cyan image forming silver halide emulsion layer on a support. In the image forming method for developing, the number of silver halide grains per unit area of the silver halide emulsion layer is the largest in the magenta image-forming silver halide emulsion layer, and the unit of the magenta image-forming silver halide emulsion layer is An image forming method wherein the number of silver halide grains per area is 1.5 times or more and 2.1 times or less the number of silver halide grains per unit area of a cyan image forming silver halide emulsion layer. 2. The silver halide photographic light-sensitive material, wherein the amount of silver halide in the magenta image-forming silver halide emulsion layer is 0.9 to 4 times the amount of silver halide in the cyan image-forming silver halide emulsion layer. 2. The method according to claim 1, wherein
2. The image forming method according to 1., 3. The silver halide content of the silver halide emulsion layer for forming a yellow image of the silver halide photographic light-sensitive material is 1.8 times or more and 5 times or less of the silver halide amount of a silver halide emulsion layer for forming a magenta image. 2. The method according to claim 1, wherein
Alternatively, the image forming method according to claim 2. 4. The total amount of silver halide coated on a support of said silver halide light-sensitive material is 0.00 in terms of silver amount.
The image forming method according to claim 1, wherein the weight is 1 to 0.15 g / m ² or less.