JPH11160848A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve color developing property while decreasing fog in amplification development and to maintain the gradation balance even in a short-time process. SOLUTION: This material has at least one silver halide emulsion layer and at least one kind of nonphotosensitive hydrophilic colloid layer on a supporting body. The nonphotosensitive hydrophilic colloid layer contains at least one kind of reaction catalyst for the amplification development. Or, at least one nonphotosensitive hydrophilic colloid layer is formed on the outer surface of the silver halide emulsion layer as the outermost emulsion layer of the supporting body, and at least one layer of nonphotosensitive hydrophilic colloid layers contains at least one kind of oil-soluble org. compd. Moreover, in the nonphotosensitive hydrophilic colloid layer formed on the outer surface of the outermost silver halide emulsion layer on the supporting body, the ratio (A/B) of the whole weight (A) of the oil-soluble org. compd. to the whole weight (B) of gelatin ranges 0.45 to 2.00.

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 material and an image forming method capable of improving color development while reducing fog in an amplification and developing process and maintaining a gradation balance even in a short time process. is there.

[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 content in the light-sensitive material can be reduced. An image forming method has been known for a long time. As an example of the amplification development processing, hydrogen peroxide / cobalt (II
I) A color developing agent (hereinafter referred to as "color developing agent")
A method is known in which an oxidized product (which is referred to as a color developing agent) is formed, and then an image dye is formed by reaction with a coupler.

There are many differences between such an amplification development process and a conventional and widely used conventional development process, and one of them is a difference in a coloring mechanism. In the conventional treatment, an oxidized color developing agent is generated by a redox reaction between the color developing agent and silver halide, and the oxidized color developing agent causes a coupling reaction with a dye-forming compound called a coupler. Produces a coloring dye. Therefore, the generation of the oxidized form of the color developing agent is limited to the vicinity where the reduction reaction of the silver halide to the developed silver occurs, and if the reduced silver halide disappears from the system due to consumption due to the progress of the development reaction. Also, the generation of the oxidized form of the color developing agent stops, and the generation of the coloring dye also stops. Thereafter, no matter how much color development is continued, the color density hardly increases. On the contrary,
In the case of the amplification development processing, as described above, it is considered that an oxidized color developing agent is generated using the developed silver as a catalyst.
Therefore, as long as the developed silver is present in the system, the oxidized form of the color developing agent continues to be generated, and the longer the amplification processing time, the more the color dye is generated. Due to this difference in mechanism, amplification development processing can be said to have the advantage that a higher color density can be obtained with a smaller amount of silver halide, but on the other hand, for example, a conventional conventional photosensitive material is developed and amplified development processing is performed. When the processing is performed in a single-bath amplification development process in which the supply amount of the oxidizing agent such as hydrogen peroxide contained in the amplification developer and the color developing agent to the photosensitive material is larger, the color formation speed is higher and the supply is delayed. The lower the layer, the slower the color developing speed, and the gradation balance of each layer may be greatly disrupted. Further, when the processing is performed in a two-bath amplification development processing in which the development processing and the amplification development processing are performed, the highest color density may not be obtained in some cases.

[0004] Further, another disadvantage is that the sample subjected to the amplification and development treatment has a higher fog as compared with ordinary conventional color paper. As a result of the study by the present inventors, the increase in fog is more remarkable as the activity (processing temperature, developing agent concentration, oxidizing agent concentration, etc.) of the amplification development processing is higher, and the amplification development time is longer.

[0005] In this sense, a silver halide photographic light-sensitive material capable of obtaining color development density and gradation balance equivalent to that of conventional color paper by amplification development processing as short as possible with high color-forming properties and low fog, and its image formation The development of a method was strongly desired.

[0006] The amount of gelatin in the emulsion layer or its adjacent layers of the photographic material of the silver amount 0.3 g / m ² which contains a compound which scavenge oxidized developer to the intermediate layer in the No. WO9,303,418 800mg / m ^Although a technique for increasing the number to ^two or more is disclosed, the objective effect is to improve the color tone of the yellow color-forming layer, and there is no problem point in the amplification and development processing according to the present invention. JP-A-9-80688 discloses a technique in which at least one hydrophilic colloid layer containing a white pigment is provided between a support and a silver halide emulsion layer in a conventional conventional color paper. The effect is an improvement in sharpness and gloss, and there is no description of the constituent elements related to the present invention in the amplification development processing.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material capable of improving color development while reducing fog in an amplification and developing process and maintaining gradation balance even in a short-time process. It is to provide a method.

[0008]

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

(1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one layer is provided between the support and the silver halide emulsion layer closest to the support. A silver halide photographic material comprising a non-photosensitive hydrophilic colloid layer as described above.

(2) A silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, wherein the non-photosensitive hydrophilic colloid layer A silver halide photographic light-sensitive material comprising at least one reaction catalyst for amplification and development.

(3) In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one silver halide emulsion layer is further provided outside the outermost silver halide emulsion layer as viewed from the support. A non-photosensitive hydrophilic colloid layer, wherein at least one of the non-photosensitive hydrophilic colloid layers contains at least one oil-soluble organic compound, and an outermost halogen as viewed from the support. The ratio (A / B) of the total weight (A) of the oil-soluble organic compound to the total weight (B) of the gelatin in the non-photosensitive hydrophilic colloid layer further outside the silver halide emulsion layer is 0.45 to 0.45. 2.00, a silver halide photographic material.

(4) The non-photosensitive hydrophilic colloid layer according to (1) contains at least one oil-soluble organic compound,
And a ratio (A / A) of the total weight (A) of the oil-soluble organic compound and the total weight (B) of the gelatin in the non-photosensitive hydrophilic colloid layer.
2. The silver halide photographic material as described in 1 above, wherein the value of B) is from 0.05 to 2.00.

(5) The non-photosensitive hydrophilic colloid layer containing the reaction catalyst according to the above (2), which is present between the support and the silver halide emulsion layer closest to the support. The silver halide photographic light-sensitive material as described above.

(6) The silver halide photographic light-sensitive material contains at least one yellow image coloring layer, at least one magenta image coloring layer, and at least one cyan image coloring layer. Said 1 to
6. The silver halide photographic light-sensitive material according to any one of the above items 5.

(7) An image forming method for obtaining a color image by subjecting the photosensitive material according to any one of the above items 1 to 6 to amplification and development processing using an oxidizing agent.

(8) The image forming method according to the item (7), wherein the amplification and development processing is performed after the development processing.

Hereinafter, the present invention will be described in detail.

According to the present invention, there is provided a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer closest to the support and the silver halide emulsion layer closest to the support are used. It is characterized by having at least one non-photosensitive hydrophilic colloid layer between them. Although any hydrophilic colloid known in the art can be used for the non-photosensitive hydrophilic colloid layer, it is advantageous to use gelatin. If necessary, a hydrophilic colloid such as a gelatin derivative, a graft polymer of gelatin and another polymer compound, a protein other than gelatin, a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer may be used. Can be used.

According to the present invention, there is provided a non-photosensitive hydrophilic colloid layer containing at least one oil-soluble organic compound further outside the outermost silver halide emulsion layer as viewed from the support. Wherein the non-photosensitive hydrophilic colloid layer according to claim 1 contains at least one oil-soluble compound. The oil-soluble organic compound according to the present invention is an organic compound capable of dissolving 1 g or more in 1 liter of ethyl acetate at 20 ° C., and may be a compound having a relatively low molecular weight such as a high-boiling organic solvent, or polystyrene or polyacrylamide. And high molecular weight polymers such as Further, it may be an ultraviolet absorber such as a benzotriazole type or a stain inhibitor such as a dialkylhydroquinone.

Preferred among the oil-soluble organic compounds are high-boiling organic solvents having a boiling point of 150 ° C. or higher. Boiling point 3
More preferably, it is a high-boiling organic solvent having a temperature of 00 ° C. or higher. It is also preferable that the solvent is a high-boiling organic solvent having a vapor pressure at 100 ° C. of 0.5 mmHg or less.

The high boiling organic compound usable in the present invention is preferably an organic compound having 20 or more carbon atoms (which may be branched or substituted by a substituent), and more preferably an organic compound having 24 or more carbon atoms. (Which may be branched or substituted by a substituent).

Preferred high-boiling organic solvents include, for example, phthalic esters, ester phosphates, fatty acid esters, organic acid amides, ketones, hydrocarbon compounds, and the like, as disclosed in JP-A-1-156748. Organic compounds such as H-1 to H-20 described are exemplified.

Also, a compound represented by formula III-3 described in JP-A-1-250944,
No. 646, compounds represented by the general formula III, and JP-A-63-187240 discloses UV-1L to UV-L.
UV absorbers such as 27L, 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 are also preferably used. Can be.

The high boiling organic compounds used in the present invention may be used alone or in combination of two or more.

The high-boiling organic compound of the present invention is prepared by using a low-boiling organic solvent and / or a water-soluble organic solvent in combination with a surfactant in a hydrophilic binder such as an aqueous gelatin solution, using a stirrer, a homogenizer, a colloid. After emulsifying and dispersing using a dispersing means such as a mill, a flow jet mixer, or an ultrasonic device, it is added to the target hydrophilic colloid layer.

When a hydrophilic colloid layer is provided between the support and the silver halide emulsion layer, the preferred amount of gelatin is 0.1.
1 to 3.0 g / m ² , and more preferably 0.5 to 3.0 g / m ^2.
１．５1.5 g / m ² .

When a hydrophilic colloid layer containing an oil-soluble organic compound is provided between the support and the silver halide emulsion layer, the total weight of (A) the oil-soluble organic compound satisfying the characteristics of the present invention and (B) ) Ratio to total weight of gelatin (A / B)
Ranges from 0.05 to 2.00, preferably 0.1.
It is in the range of 1 to 1.25.

When a hydrophilic colloid layer is provided between the support and the silver halide emulsion layer, for example, rutile titanium dioxide, anatase titanium oxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin And the like may be contained in the hydrophilic colloid layer.

In the case where a hydrophilic colloid layer containing an oil-soluble organic compound is provided further outside the silver halide emulsion layer which is the outermost as viewed from the support, (A) the oil-soluble organic compound satisfying the characteristics of the present invention. The range of the ratio (A / B) of the total weight to the total weight of (B) gelatin is from 0.45 to 2.00, and more preferably from 0.50 to 1.50.

The present invention according to claim 2 provides at least one
It is characterized in that at least one non-photosensitive hydrophilic colloid layer contains a reaction catalyst in the kind of amplification and development processing. The amplification development according to the present invention is a history development.
of Color Photography by J
oesph S.P. Friedmann, Focal
Press Ltd. , London (1968),
DE 1,813,920, 1,950,102,
No. 1,961,029, No. 2,044,833, No. 2,044,993, No. 2,056,359, and No. 2,056,360. It is about force method. Among the methods described above, from the viewpoints of photographic performance such as amplification factor and fog, and environmental adequacy, the developing agent is oxidized by a redox reaction between the developing agent and an oxidizing agent using developed silver as a catalyst after imagewise exposure. It is presently believed that a method of forming an image dye by a coupling reaction between a body and a coupler is advantageous. Examples of the oxidizing agent include compounds that give hydrogen peroxide such as hydrogen peroxide and an addition compound of hydrogen peroxide, peroxy compounds such as peroxoborate and peroxocarbonate, cobalt (III) complexes such as cobalt hexaammine complex, Halogenous acids such as chlorous acid and periodic acid can be used. Among them, hydrogen peroxide is preferably used as the oxidizing agent because the effect of the present invention is large.

Amplification development includes a one-bath method and a two-bath method. The one-bath method is a method in which a hydrogen peroxide or a hydrogen peroxide releasing compound and a color developing agent such as paraphenylenediamine are contained in an amplification developer. And, if necessary, a method of performing amplification development with a processing solution simultaneously containing a black-and-white developing agent such as hydroquinones and ascorbic acids, and the two-bath method includes a color developing agent or a black-and-white developing agent in advance. This is a method in which after a development process is performed with a processing solution, an amplification development process is performed with a processing solution containing at least hydrogen peroxide or a hydrogen peroxide releasing compound. The processing solution for performing the two-bath amplification processing may contain a color developing agent or a black-and-white developing agent.

The reaction catalyst in the amplification development according to the present invention is a general term for a substance having a catalytic action to catalytically increase the reaction activity of the oxidizing agent in the amplification development. To determine whether a substance is a reaction catalyst in the amplification and development process according to the present invention, when the oxidizing agent is, for example, hydrogen peroxide or a hydrogen peroxide releasing compound, the decomposition rate of hydrogen peroxide in an aqueous alkaline solution ( (For example, residual amount of hydrogen peroxide)
Can be easily evaluated by performing measurement in the presence of a reaction catalyst and performing comparison. In the present invention, a substance having a decomposition rate of 1.2 times or more the decomposition rate of hydrogen peroxide without a reaction catalyst used as a comparison is defined as a reaction catalyst. As the reaction catalyst according to the present invention, specifically, Mg, Ca, Cr, M
n, Fe, Co, Ni, Cu, Zn, As, Se, T
i, Nb, No, Ph, Pd, Ag, Cd, Re, O
s, Ir, Pt, Au, Hg, Pb, Bi, Po, W,
A zero-valent metal selected from metals such as U, or a metal oxide, or a metal halide, or a metal hydroxide, or a metal sulfide, or a metal supported on a mordanto, or
Examples include, but are not limited to, metals held by chelates. Particularly effective metals include those using platinum, palladium, copper, silver, gold and mercury.

As a method of incorporating the reaction catalyst according to the present invention into a hydrophilic colloid, for example, a dispersion may be applied as it is in a water-soluble binder in an aqueous solution of a hydrophilic colloid such as gelatin. A preferable addition amount of the reaction catalyst is 0.01 to 50% by weight, more preferably 0.1 to 10% by weight, based on the hydrophilic colloid, as a metal amount.

When a hydrophilic colloid layer having a reaction catalyst according to the present invention is provided between a support and a silver halide emulsion layer, it is preferable to use a compound which is both a reaction catalyst and a white pigment.

Next, the silver halide photosensitive material according to the present invention will be described in detail. The composition of the silver halide emulsion used in the light-sensitive material according to the present invention is not limited, and may be any of silver chloride, silver bromide, silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver chloroiodide and the like. Although a silver halide emulsion having a halogen composition may be used, when a silver halide emulsion having a silver chloride content of 80 mol% or more is used, the effect as a so-called catalyst poison that suppresses the amplification and development reaction is small, so that a high amplification is used. Advantageously, a development rate can be achieved.

As the silver halide emulsion used in the light-sensitive material of the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration can be 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 used in the light-sensitive material of the present invention may contain heavy metal ions for the purpose of improving photographic characteristics. Examples of such heavy metal ions include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and lead. , Rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These heavy 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, nitrosyl, and ammonia.
Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to incorporate heavy metal ions into the silver halide emulsion used in the light-sensitive material according to the present invention, the heavy metal ions are added before forming silver halide grains, during formation of silver halide grains, and during the formation of silver halide grains. May be added at any place in each step during physical ripening after the formation of. In order to obtain a silver halide emulsion satisfying the above conditions, heavy metal ions can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

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

The shape of the silver halide grains used in the light-sensitive material according to the present invention is arbitrary. One preferred example is
It is a cube having a {100} plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-B-55-42
No. 737 and The Journal of Photographic Science (J. Photogr. Sci.) 2
1, 39 (1973), etc., particles having an octahedral, tetradecahedral, dodecahedral or the like shape 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 also preferable to add two or more monodispersed silver halide emulsions to the same layer.

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

The silver halide emulsion used for the light-sensitive material 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 one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

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

Further, JP-A-57-92523, JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in German Offenlegungsschrift 2,921,164, etc. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of a reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant. If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

As the silver halide grains used in the light-sensitive material of the present invention, so-called tabular silver halides are preferably used in order to control gradation balance. As tabular grains containing silver chloride at a high concentration, grains having a {111} major plane and grains having a {100} major plane are known. Particles having a flat surface are particularly preferably used.

The use of tabular silver halide grains in the light-sensitive material of the present invention is particularly preferred because it has the advantage that the bleaching time of the peracid bleaching composition can be shortened.

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

As the chalcogen sensitizer applied to the silver halide emulsion used in the light-sensitive material according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used. Sensitizers are preferred.

In the silver halide emulsion used in the light-sensitive material according to the present invention, fog generated during the preparation process of the light-sensitive material, performance fluctuation during storage is reduced, and fog generated during development is prevented. Known antifoggants and stabilizers can be used for the purpose. Examples of preferred compounds that can be used for such a purpose are described in
The compound represented by the general formula (II) described in the lower column of page 1 of JP-A-146036 can be exemplified. These compounds are added according to the purpose in a step of preparing a silver halide emulsion, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution and the like.

In the light-sensitive material according to the present invention, the total amount of the light-sensitive silver halide contained in the light-sensitive material is 0.3 g / g.
m ² or less, and the amount of silver halide contained in each photosensitive layer is preferably 0.1 g / m ² or less. When the amount of silver halide is in the above range, the load on the desilvering process is small, and the development reaction in the own layer is affected by the development reaction in the other layer, so-called interimage effect is small, and the stability of gradation reproduction is low. Improved and preferred. Preferred silver halide amount the photosensitive layer per are each 0.001 to 0.1 g / m ^2, more preferably in the range of 0.01~0.08g / m ^2.

The coupler used in the light-sensitive material according to the present invention may be 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. Although it is also possible to use, particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical example is a cyan dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

Cyan couplers which can be preferably used in the light-sensitive material of the present invention are described in JP-A-4-11415.
The general formula (C-I) described in the lower left column of page 4, No. 5, page 5,
A coupler represented by formula (C-II):
The general formulas (Ia), (Ia) and
b) and cyan couplers represented by (Ic);
General formulas (IIα) to (VIIIα) described in the lower right column of page 6 to the upper left column of page 7 and the lower right column of page 7
The cyan couplers represented by the general formulas (IIβ) to (VIIIβ) described in the upper left column of page 8 can be mentioned. Especially,
General formulas (IIα) to (VIIIα) and (IIβ) to (VIIIβ)
Cyan couplers represented by are preferred because they have sharp image dye absorption and are excellent in color reproducibility.

The magenta coupler which can be preferably used in the light-sensitive material of the present invention is described in JP-A-4-1141.
General formula (MI) described in the upper right column on page 4 of JP-A No. 54,
The coupler represented by (M-II) can be mentioned.
More preferred among the above magenta couplers are the couplers represented by the general formula (MI) described in the upper right column on page 4 of the publication, and among them, the RM of the above general formula (MI)
Is a tertiary alkyl group, which is excellent in light resistance and particularly preferred.

The yellow couplers which can be preferably used in the light-sensitive material according to the present invention include those described in JP-A-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.

When an oil-in-water emulsion dispersion method is used to add the couplers and other organic compounds used in the light-sensitive material according to the present invention, it is usually added to a high-boiling organic solvent and, if necessary, to a low-boiling organic solvent. And / or dissolved together with a water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. The high-boiling organic solvent that can be used for dissolving and dispersing the coupler 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.

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.

The coupler includes light of the formed dye image,
In order to prevent discoloration due to heat, humidity and the like, it is preferable to use a discoloration inhibitor in combination. Particularly preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541,
No. 174150, a phenolic compound represented by the general formula IIIB, JP-A-64-90445, an amine compound represented by the general formula A, and JP-A-62-18.
Metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP-A-2741 are particularly preferable 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, the fluorescent dye releasing compounds 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 an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity or added to a silver halide emulsion layer. 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.

In the photosensitive material according to the present invention, the above-mentioned ultraviolet absorber can be used as a preferable compound. It is preferable to add the compound to prevent static fog or improve the light fastness of the dye image. Preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are those represented by general formula II described in JP-A-1-250944.
A compound represented by I-3, a compound represented by the general formula III described in JP-A-64-66646, and a compound represented by JP-A-63-1
UV-1L to UV-27L described in JP 87240, compounds represented by general formula I described in JP-A-4-1633, and compounds represented by general formulas (I) and (II) described in JP-A-5-165144. Compounds.

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 whiteness can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

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

As the spectral sensitizing dye, any known compounds can be used. As the blue-sensitive sensitizing dye, BS-1 to 8 described in JP-A-3-251840, page 28, alone can be used. Or in combination. As the green photosensitive sensitizing dye, the same publication 2
GS-1 to GS-5 described on page 8 are preferably used.
As the red-sensitive sensitizing dye, R 29 described in
S-1 to S-8 are preferably used. 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 light-sensitive sensitizing dyes include supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-6.
Compound S-1 described in No. 6515, pages 15 to 17
It is preferable to use a combination of -S-17.

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, or dimethylformamide or water, or adding it as a solid dispersion. It may be added.

It is advantageous to use gelatin as a binder in the light-sensitive material according to the present invention. If necessary, the above-mentioned hydrophilic colloids can be preferably used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination.
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.

Further, it is more preferable that the value of the center surface average roughness (SRa) of the support is 0.15 μm or less, more preferably 0.12 μm or less, because the effect of good gloss is obtained. 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 of the present invention 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 on 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.

Next, an image forming method according to the present invention will be described. In the image forming method of the present invention, a silver halide photographic material (hereinafter, referred to as a photographic material) is first developed after imagewise exposure. This development is for forming developed silver which is a catalyst nucleus in the subsequent amplification development, and is a black-and-white development for forming only a silver image or a color development for forming a dye image simultaneously with a silver image. There may be. Examples of black-and-white developing agents include hydroquinone and its derivatives, 1-phenyl-3-pyrazolidone and its derivatives,
Known compounds, such as monomethyl-p-aminophenol sulfate and its derivatives, can be mentioned. Examples of color developing agents include N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5- (N-ethyl-N-laurylamino) toluene, and 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-
Known compounds such as ethyl-N- (β-ethoxyethyl) aniline and 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline can be mentioned. These black-and-white developing agents and color developing agents can be used alone or in combination of two or more, or a black-and-white developing agent and a color developing agent may be used in combination.

These developing agents may be used in a state in which they are dissolved in a developer in advance, or a part or all of the necessary developing agents may be incorporated in the photosensitive material in advance to start development of alkali or the like. It may be made to act by immersing in a so-called activator liquid containing a necessary substance. When the term developer is used in the present specification, it may be considered that the activator solution is included in a broad sense.

When the developing agent is incorporated in the light-sensitive material, it is possible to incorporate the developing agent in the form of a precursor in consideration of storability.

In the image forming method of the present invention, the developer can be used in an arbitrary pH range.
It is preferably from 8.5 to 12.0, more preferably from pH 9.0 to 11.5.

The developing temperature is preferably from 20 ° C. to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing liquid and the reduction of fog, it is preferable that the temperature is not too high, and the processing is preferably performed at 35 ° C. or more and 60 ° C. or less. Although the development time varies depending on the development processing temperature, it can be arbitrarily set within a range in which developed silver required for subsequent amplification development is formed and fogging does not occur. In addition to the developing agent, an alkali agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazole, a preservative, a chelating agent, and the like can be used in the developer.

In the image forming method of the present invention, the photosensitive material is developed, before or after the step of processing with an amplification developer.
Processing can be performed in a fixing process using a solution containing a fixing agent other than thiosulfate. As fixing agents other than thiosulfate, for example, potassium cyanide, sodium cyanide,
Sodium thiocyanate, ammonium thiocyanate,
Sodium sulfite, ammonium sulfite, potassium sulfite, water-soluble thioether compound, water-soluble mercapto compound, thiourea and its derivatives, and the like. preferable. The preferred concentration of the fixing agent varies depending on the type of the fixing agent, but in the case of sulfite, it is 5 to 200 g per liter of the fixing solution,
Preferably it is 10 to 150 g per liter. The preferable pH of the fixing solution also varies depending on the type of the fixing agent, but in the case of sulfite, it is preferable to use the pH in the range of 6.0 to 9.0. The fixing processing temperature is optional, but a higher temperature enables fixing in a shorter time. However, if the temperature is too high, the fixing solution becomes unstable. The fixing time varies depending on the amount of silver halide in the light-sensitive material and the temperature of the fixing solution, and is set between approximately 10 seconds and 180 seconds.

In the image forming method of the present invention, a washing process can be provided between the fixing process and the amplification and developing process. However, it is preferable that no washing process is provided from the viewpoint of downsizing of the processing apparatus and rapid processing.

The image forming method of the present invention is characterized by having an amplification and development processing step. Amplification development is a process in which an image dye is formed or released by a chemical reaction using a developed silver as a catalyst.For example, an oxidized developing agent formed by a redox reaction between a developing agent and an oxidizing agent using a developed silver as a catalyst and a coupler. A method of forming an image dye by a coupling reaction of

Examples of the oxidizing agent include compounds that give hydrogen peroxide such as hydrogen peroxide and hydrogen peroxide addition compounds, peroxy 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, hydrogen peroxide is advantageously used as an oxidizing agent because the effect of the present invention is large, the amplification effect is high, and the load on the environment is reduced.

In the amplification development processing according to the present invention, a combination of an aromatic primary amine developing agent and hydrogen peroxide is preferably used, and as the aromatic primary amine developing agent,
Known compounds as described above can be used.

The amplification and development method according to the present invention is described in, for example, JP-A Nos. 52-13335 and 55-127555.
JP-A-5-21619, a method in which a developing agent and an oxidizing agent are present in the same processing bath (development / amplification liquid) to carry out amplification development as described in JP-A-5-21619.
As described in JP-A Nos. 2 and 5-346647, a method of separating a bath containing a color developing agent and a bath containing an oxidizing agent, bringing the developing agent into an amplification bath, and carrying out amplification development. In addition to the method of immersing a photosensitive material in a processing bath, a method of spraying a developer or an amplifying solution onto the photosensitive material in a mist state as described in JP-A-61-80150 can be used.

When a bath containing a color developing agent and an amplification bath containing an oxidizing agent are separated, the developing agent concentration is preferably 0.2%.
-20 g / l, particularly preferably 1-10 g / l,
The amount of hydrogen peroxide (30% solution) in the amplification solution is 0.1 to 1
00 ml / l is preferred. When the color developing agent and the oxidizing agent are present in the same processing bath, the preferred amount of the developing agent is 0.5 to 20 g / l, more preferably 1 to 10 g / l.
The preferred amount of hydrogen peroxide (30% solution) is 0.1.
It is 1 to 30 ml / l, more preferably 1 to 20 ml / l.

Next, the configuration of a typical processing step of the image forming method of the present invention will be exemplified, but the present invention is not limited thereto.

1. Color development (and / or black and white development)
1. Amplification development → bleaching / fixing → stabilization 2. Color development (and / or black and white development) / amplification development → bleaching → fixing → stabilization 3. Color development (and / or black and white development) / amplification development → fixing → bleaching → stabilization 4. Color development (and / or black and white development) → amplification development → bleaching / fixing → stabilization 5. Color development (and / or black and white development) → amplification development → bleaching → fixing → stabilization Color development (and / or black-and-white development) → amplification development → fixing → bleaching → stabilization To form a photographic image using the silver halide photographic light-sensitive material of the present invention, an image recorded on a negative is The image may be optically formed on a silver halide photographic material to be printed and printed. Alternatively, the image may be converted into digital information and then formed on a CRT (cathode ray tube). May be formed on a silver halide photographic material to be printed and printed, or may be printed by scanning while changing the intensity of laser light based on digital information.

The image forming method of the present invention is preferably applied to a photosensitive material for forming an image for direct viewing. For example, color paper, color reversal paper, a photosensitive material for directly 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 silver halide photographic light-sensitive material according to the present invention is subjected to bleaching and fixing as required after amplification and development. 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.

The processing apparatus used in the image forming method of the present invention may be a roller transport type in which the photosensitive material is transported between rollers disposed in a processing bath, or may be transported with the photosensitive material fixed to a belt. An endless belt method may be used, but a processing tank is formed in a slit shape, a processing liquid is supplied to the processing tank and a photosensitive material is conveyed and a processing liquid is sprayed.
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid can also be used.

[0095]

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

(Solution A1) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with water (Solution B1) 10 g of silver nitrate 200 ml with addition of water (Solution C1) 102.7 g of sodium chloride 102.7 g of potassium hexachloroiridium (IV) 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g Add water 600 ml (Solution D1) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas Demol After desalting 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 obtain an average particle size of 0.57 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. The above-mentioned EMP-1A was optimally subjected to chemical sensitization at 60 ° C. using the following compounds to give a blue-sensitive silver halide emulsion (Em-B).
1) was obtained.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0099]

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(Preparation of photosensitive material (101)) Basis weight 180
High-density polyethylene was laminated on both sides of g / m ² paper pulp to produce a paper support. However, on the side on which the emulsion layer was applied, a molten polyethylene containing anatase-type titanium oxide having a surface treatment dispersed therein at a content of 15% by weight was laminated. After the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon to prepare a silver halide photographic material (101). In the preparation of the photosensitive material, each coating solution was prepared so as to have the following coating amount, and (H-
1) and (H-2) were added. Surfactants (SU-1), (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² .

The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) Second layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 First layer (blue-sensitive layer) Gelatin 1. 30 Blue-sensitive emulsion (Em-B1) 0.025 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 Support polyethylene-laminated paper The amount of silver halide was shown in terms of silver.

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium DBP: dibutyl phthalate DIDP: diisodecyl phthalate

[0104]

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A non-emulsion layer 1 is newly provided between the support and the first layer of the light-sensitive material (101), and a reaction catalyst and / or an oil-soluble organic compound is provided on the non-emulsion layer 1 and / or the second layer. Light-sensitive materials (102) to (111) having the same constitution as the light-sensitive material (101) were prepared except that was added. Table 1 shows the amounts of gelatin, reaction catalyst, and oil-soluble organic solvent in each layer of each sample.

The photosensitive material (10
1) to (111) are subjected to light wedge exposure in 0.5 seconds with white light, and are subjected to an amplification development process 1 which is a single bath amplification development process.
, Followed by desilvering in a desilvering step. During processing with each photographic processing solution, excess photographic processing solution existing on the surface of the photosensitive material was removed with a blade made of silicon rubber.

The reflection density of the obtained sample was measured using a PDA-65 densitometer (manufactured by Konica Corporation), and the minimum density (Dmin) and the maximum density (Dmax) were determined.
The results are shown in Table 1. It can be seen that the sample satisfying the characteristics of the present invention has low fog and a high maximum density. The bleach-fixing process during the desilvering process is described in
The same results as in Table 1 were obtained by performing the same evaluation in place of the bleaching treatment containing hydrogen peroxide described in JP-A-346647 and then the fixing treatment containing sulfurous acid.

Processing Step 1 Processing Time Temperature Amplified developer (CDA-1) 40 seconds 35.0 ± 1.0 ° C. Bleach-fix solution (BF-1) 45 seconds 30.0 ± 0.5 ° C. Stabilizing solution 60 seconds 30-34 ° C drying 30 seconds 60-80 ° C The composition of the treatment liquid 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 hydroxylamine sulfate 1.0 g diethylenetriaminepentaacetic acid sodium salt 2.0 g 1-hydroxyethylidene-1,1′-diphosphonic acid 0.35 g potassium carbonate 20 g hydrogen peroxide ( (5.99%) 25 ml Adjust the pH to 10.3 with potassium hydroxide or sulfuric acid, and add water to make the total amount 1 liter.

Bleaching / fixing solution (BF-1) Pure water 700 ml Diethylenetriaminepentaacetic acid ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4 -Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml 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 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 (polyvinylpyrrolidone) 1.0g Ammonia water (25% aqueous solution of ammonium hydroxide) 2.5g Nitrilotriacetic acid trisodium salt 1.5g Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or ammonia water. I do.

[0112]

[Table 1]

Table 1 shows that the sample of the present invention has low fog and excellent color development.

Example 2 (Preparation of Green-Sensitive Silver Halide Emulsion (Em-G1)) In the preparation of silver halide emulsion EMP-1A of Example 1, the addition time of (A1 solution) and (B1 solution) and (C1 liquid)
A monodispersed cubic emulsion EMP-11A having an average particle size of 0.30 μm and a silver chloride content of 99.5 mol% was obtained in the same manner as above except that the addition time of the solution (D1) was changed. The above EMP-1
1A was optimally chemically sensitized at 60 ° C. using the following compound to obtain a green light-sensitive silver halide emulsion (Em-G1).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-3 3 × 10 ⁻⁴ mol / mol AgX (Preparation of red-sensitive silver halide emulsion (Em-R1)) Halogenation of Example 1 In the preparation of silver emulsion EMP-1A, the addition time of (A1 solution) and (B1 solution) and (C1 solution)
A monodispersed cubic emulsion EMP-21A having an average particle size of 0.35 μm and a silver chloride content of 99.5 mol% was obtained in the same manner as above except that the addition time of the solution (D1) was changed. EMP-2 above
1A was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion (Em-R1).

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

[0117]

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(Preparation of silver halide photographic light-sensitive material (201)) The support used in Example 1 was provided with a gelatin undercoat layer, and further, each layer having the following constitution was coated thereon. Materials were made. In making photosensitive materials,
Each coating solution was prepared so as to have the following coating amount, and (H-1) and (H-2) were added as hardening agents. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² .

The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) 7th layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 6th layer (UV absorbing layer) Gelatin 0.40 AI-1 0.01 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Stain inhibitor (HQ-5) 0.04 PVP 0.03 Fifth layer (red-sensitive layer) Gelatin 1.30 Red-sensitive emulsion (Em-R1) 0.020 Cyan coupler (C-1) 0.28 Dye image stabilizer (ST-1) 0 .10 Anti-stain agent (HQ-1) 0.004 DBP 0.10 DOP 0.20 Fourth layer (ultraviolet absorbing layer) Gelatin 0.94 Ultraviolet absorbing agent (UV-1) 0.28 Ultraviolet absorbing agent (UV- 2) 0.09 UV absorption Collector (UV-3) 0.38 AI-1 0.02 Stain inhibitor (HQ-5) 0.10 Third layer (green-sensitive layer) Gelatin 1.30 AI-2 0.01 Green-sensitive emulsion (Em-G1) 0.025 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 (middle layer) gelatin 1.20 AI-3 0.01 anti-stain agent (HQ-2) 0.03 anti-stain agent (HQ-3) 0.03 anti-stain agent (HQ-4) 0 0.05 Stain inhibitor (HQ-5) 0.23 DIDP 0.04 DBP 0.02 Fluorescent brightener (W-1) 0.10 First layer (blue-sensitive layer) Gelatin 1.20 Blue-sensitive emulsion (Em-B1) 0.062 Yellow coupler (Y- ) 0.70 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer (ST-2) 0.10 Dye image stabilizer (ST-5) 0.10 Stain inhibitor (HQ-1) ) 0.01 Image stabilizer A 0.15 DBP 0.10 DNP 0.05 Support Polyethylene laminated paper The amount of silver halide applied was shown in terms of silver.

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-octylphenol

[0122]

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[0123]

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[0124]

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Further, a non-emulsion layer 1 is newly provided between the support and the first layer of the above-mentioned light-sensitive material, and a reaction catalyst and / or a non-emulsion layer are added to one non-emulsion layer and / or the seventh and / or sixth layers. Alternatively, photosensitive materials (202) to (229) having the same constitution as the photosensitive material (201) except that an oil-soluble organic compound was added were prepared. Table 2 shows the amount of gelatin, the amount of the reaction catalyst, and the amount of the oil-soluble organic solvent in each layer of each sample.

The photosensitive material (20
For 1) to (229), light wedge exposure was performed for 0.5 second with white light, and the following two-bath amplification and development processing was performed in a processing bath system, followed by desilvering processing by a desilvering processing step. went.

The reflection density of blue, green and red light was measured using a PDA-65 type densitometer (manufactured by Konica Corporation) on the obtained sample, and the minimum density of yellow, magenta and cyan was measured. (DminSY, DminSM, Dmin
SC) and gradation (γSY, γSM, γSC). Next, the development time of the amplification solution during the two-bath amplification development process was set to 30.
The same processing is performed except that the time is changed from 20 seconds to 20 seconds, and the same minimum density (DminOY, DminOM, Dm
inOC) and gradation (γOY, γOM, γOC). Using γS as a reference gradation in each color image, a ratio of γO and γS (γO / γS) is obtained as a value representing a gradation change when the processing time during amplification and development is reduced, and this value is used for short-time processing. Was evaluated for stability of gradation reproduction.
The closer the value of (γO / γS) is to 1.0, the more stable the tone is reproduced even when the amplification development time is shortened. Table 3 shows the results. The sample satisfying the features of the present invention is:
It can be seen that the minimum density is low and the gradation balance is stable even in short-time processing. The bleach-fixing process in the desilvering process was performed in the same manner as in the bleaching process containing hydrogen peroxide described in JP-A-5-346647, followed by the fixing process containing sulfurous acid. The same results as in Table 3 were obtained.

Processing step 2 Processing time Supply method Color developing solution (CDA-1) 10 seconds Processing bath Amplifying solution (AD-1) 30 seconds Processing bath Color developing solution (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 12.0 g N, N-diethylhydroxylamine 2.0 g Diethylenetriaminepentaacetic acid sodium salt 0.6 g 1-hydroxyethylidene-1,1'-diphosphonic acid 0.5 g Potassium carbonate 20 g Adjust the pH to 9.0 with potassium hydroxide or sulfuric acid, and add water to bring the total amount to 1 liter.

Amplification solution (AD-1) Pure water 800 ml Potassium bromide 0.001 g Potassium chloride 0.35 g N, N-diethylhydroxylamine 2.0 g Diethylenetriaminepentaacetic acid sodium salt 0.6 g 1-hydroxyethylidene-1,1 '-Diphosphonic acid 0.5 g Potassium carbonate 20 g Hydrogen peroxide solution (5.99%) 10 ml Adjust the pH to 10.5 with potassium hydroxide or sulfuric acid, and add water to make 1 liter.

[0130]

[Table 2]

[0131]

[Table 3]

Tables 2 and 3 show that the sample of the present invention has low fog and excellent tone reproduction.

[0133]

According to the present invention, in the amplification development processing,
A silver halide photographic light-sensitive material and an image forming method capable of improving color development while reducing fog and maintaining gradation balance even in short-time processing can be provided.

Claims (8)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic material comprising at least one non-photosensitive hydrophilic colloid layer between the support and a silver halide emulsion layer closest to the support. 2. A silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, wherein the non-photosensitive hydrophilic colloid layer comprises And a silver halide photographic material comprising at least one reaction catalyst in the amplification and development process. 3. A silver halide photographic material having at least one silver halide emulsion layer on a support,
At least one non-photosensitive hydrophilic colloid layer further outside the outermost silver halide emulsion layer as viewed from the support, and at least one non-photosensitive hydrophilic colloid layer in at least one of the non-photosensitive hydrophilic colloid layers; Containing an oil-soluble organic compound,
And the ratio of the total weight of oil-soluble organic compounds (A) to the total weight of gelatin (B) in the non-photosensitive hydrophilic colloid layer further outside the outermost silver halide emulsion layer as viewed from the support. A silver halide photographic material, wherein the value of (A / B) is from 0.45 to 2.00. 4. The non-photosensitive hydrophilic colloid layer according to claim 1, wherein the non-photosensitive hydrophilic colloid layer contains at least one oil-soluble organic compound, and the total weight (A) of the oil-soluble organic compound in the non-photosensitive hydrophilic colloid layer. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the value of the ratio (A / B) of the total weight (B) of gelatin and gelatin is 0.05 to 2.00. 5. A non-photosensitive hydrophilic colloid layer containing the reaction catalyst according to claim 2, which is present between the support and the silver halide emulsion layer closest to the support. 2. The silver halide photographic material as described in 2. above. 6. The silver halide photographic light-sensitive material comprises at least one yellow image coloring layer, at least one magenta image coloring layer, and at least one cyan image coloring layer. 6. The silver halide photographic light-sensitive material according to claim 1. 7. An image forming method for obtaining a color image by subjecting the photosensitive material according to claim 1 to amplification development processing using an oxidizing agent. 8. The image forming method according to claim 7, wherein the amplification and development processing includes an amplification and development processing subsequent to the development processing.