JPH10246941A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To decrease the changes in the gradation balance with respect to change in the concn. of an oxidant in an amplifying developer, and to decrease the change in the color of an obtd. image, by amplify developing a silver halide photographic sensitive material after exposure, and then immediately treating the material with a photographic treating compsn. in a specified pH range. SOLUTION: After amplify-developing an exposed silver halide photographic sensitive material, the material is immediately treated with a photographic treating agent compsn. in the pH range of 6.5 to 11.0. Namely, no treatment is performed between the amplification developing treatment and the treatment with the photographic treating agent compsn. in the 6.5 to 11.0pH range. If the pH of the photographic treating compsn. used for the treatment immediately after the amplification development is <6.5, improvement in the stability to reproduce gradation or the effect to suppress changes in colors can not be obtd. If the pH is higher than 11.0, changes in colors can be decreased but the effect to improve the stability to reproduce gradation can not be obtd., because, it is supposed, unnecessary amplifying and developing reaction is accelerated by the color developing agent and the oxidant for amplifying development.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for amplifying and developing an imagewise exposed silver halide photographic material. The present invention relates to an image forming method for amplifying and developing a silver halide photographic light-sensitive material in which discoloration of the silver halide is reduced.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials) have very excellent characteristics, such as high sensitivity and excellent gradation, as compared with other printing materials. Are widely used today.
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, 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. . However, in the amplification development processing, the gradation reproducibility tends to be unstable when the processing conditions fluctuate, as compared with the normal processing without amplification development. Further, it has been found that there is a problem that the obtained image is liable to be discolored due to the concentration fluctuation of the oxidizing agent. This discoloration
In particular, the phenomenon is noticeable in a cyan image, and a phenomenon in which the cyan image tends to be greenish is likely to occur, and improvement has been desired.

Regarding the reproducibility of gradation, in a normal color developing process, for a while after a certain development time has passed and a sufficient maximum density has been obtained, the characteristic curve slightly changes in parallel movement. There are areas where the behavior changes, and the rise in minimum density is very small.There is a slight change in density even with a slight change in processing time, but the minimum density is important for printing materials. It was possible to stably obtain a characteristic in which there is almost no increase and no change in gradation and gradation balance.

On the other hand, in the amplification and development processing, the change in gradation is large, and even after reaching a sufficient maximum density, a change in gradation particularly in a high-density portion continues to occur, and the rise in minimum density eventually becomes conspicuous. . Such a phenomenon is that, in the ordinary color development, even if the development time is extended, the amount of the oxidized form of the color developing agent is almost saturated by being restricted by the amount of the exposed silver halide, It has been considered that in the amplification development, when the amplification development time is prolonged, an oxidized form of the color developing agent is generated in a stoichiometric ratio with respect to the exposed silver halide or more.

[0005]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a method for amplifying and developing a silver halide photographic light-sensitive material which has been imagewise exposed to a gradation balance with respect to a change in an oxidizing agent concentration in an amplified developing solution. An object of the present invention is to provide an image forming method for amplifying and developing a silver halide photographic light-sensitive material in which the change is small and the discoloration of the obtained image is reduced.

[0006]

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

(1) Immediately after amplification and development of an imagewise exposed silver halide photographic light-sensitive material, the silver halide photographic material has a pH of 6.5 or more.
0 or less An image forming method of processing with a photographic processing composition.

(2) pH of the photographic processing composition
Is not more than (pH of the amplification developer-1.0) or less.

(3) The photographic processing composition is a processing composition comprising a bleaching composition, a fixing composition, or a combination thereof, which does not substantially contain thiosulfate. The image forming method according to (1) or (2).

(4) The image forming method according to (3), wherein the bleaching composition is a peracid bleaching composition.

(5) The image forming method according to (3), wherein the fixing agent composition is a fixing agent composition containing a sulfite as a fixing agent.

(6) The pH of the amplification developer is 10.0
(1) to (12.5) or less.
The image forming method according to any one of (5).

That is, conventionally, it has been considered that the deterioration of the stability of gradation reproduction and the occurrence of discoloration in the amplification development processing mainly depend on the amplification development processing conditions. However, as the inventors of the present invention proceed with the research on the amplification development processing, the deterioration of the stability of gradation reproduction and the occurrence of discoloration are used not only in the amplification development conditions but also in the processing performed immediately after the amplification development processing. The present invention has been found to be affected by the conditions of the photographic processing composition, and has led to the present invention.

Hereinafter, the present invention will be described in detail.

In the image forming method of the present invention, the pH of the imagewise exposed silver halide photographic material is increased immediately after amplification and development.
It is characterized by processing with a photographic processing agent composition of 6.5 or more and 11.0 or less. That is, amplification development processing and pH 6.5
No other processing is performed between the processing with the photographic processing composition of 11.0 or less. When the pH of the photographic processing agent composition used in the processing immediately after the amplification development processing is less than 6.5, it is possible to obtain the effect of improving the stability of gradation reproduction and the effect of suppressing discoloration, which are the effects of the present invention. No, and p
If H is higher than 11.0, although the occurrence of discoloration can be reduced, unnecessary amplification development reaction by the color developing agent and the oxidizing agent for amplification introduced from the amplification processing solution is accelerated. The effect of improving the stability of gradation reproduction cannot be obtained.

The term "photographic processing composition" as used herein refers to a processing composition used for obtaining an image from a silver halide photographic light-sensitive material which has been imagewise exposed, for example, a color developing solution, a B / W developing method. Solution, bleaching solution, bleach accelerating solution, fixing solution, fixing accelerating solution, bleach-fixing solution, bleach-fixing accelerating solution, stabilizing solution, etc., and in a broad sense also includes washing water for removing water-soluble unnecessary substances. . It is preferable to reduce the type of photographic processing agent composition and the number of processing baths as much as possible from the viewpoint of speeding up processing and downsizing of the apparatus, and unnecessary for color images from the viewpoint of image stability and color reproduction. It is preferable to remove the developed silver and silver halide. Therefore, the photographic processing composition used in the processing performed immediately after the amplification development processing is particularly preferably a bleaching composition, a fixing composition, or a combination thereof.

The bleaching composition preferably used in the present invention will be described.

As a bleaching agent as a main composition of the bleaching agent composition preferably used in the present invention, a bleaching agent using a complex of an Fe (III) ion and an aminopolycarboxylic acid, a bleaching agent using a red blood salt, Although bleaching agents using peroxides are well known, there is no possibility that Fe salts causing stains remain in the light-sensitive material, and furthermore, biodegradability and biochemical oxygen demand (BOD) A peracid bleach having a small load on the chemical oxygen demand (COD) and a small load on the environment is preferred. Examples of the peracid bleach include persulfuric acid or a salt thereof, hydrogen peroxide or a salt thereof, perboric acid or a salt thereof, perphosphoric acid or a salt thereof, percarbonate or a salt thereof, perhalic acid or a salt thereof, and hypochlorous acid. Examples thereof include halogen acids or salts thereof, halogen acids or salts thereof, and organic peroxides or salts thereof. Salts of these compounds include lithium salt, sodium salt, potassium salt, ammonium salt and the like. Among these peracid bleaching agents, persulfuric acid or a salt thereof, and hydrogen peroxide or a salt thereof are preferable from the viewpoint of stability of the bleaching composition and shortening of the bleaching time, and hydrogen peroxide or a salt thereof is particularly preferable. The amount of the peracid bleach in the peracid bleach composition is not particularly limited, but is preferably from 0.2 to 5.0 mol / L, particularly preferably from the viewpoint of the stability of the bleach composition and the shortening of the bleaching time. Is 0.5 to 3.0 mol / L.

The peracid bleach composition may contain a halogen ion such as a chloride ion or a bromide ion if necessary. However, from the viewpoint of shortening the bleaching time, the bromide ion concentration is 0.05 mol / mol. L or less, more preferably 0.01 mol / L or less. The most preferred embodiment is a peracid bleach composition that is substantially free of bromide ions. There is no particular limitation on the chloride ion concentration, but when hydrogen peroxide or a salt thereof is used as the peracid bleaching agent, 0.2% is used from the viewpoint of suppressing the occurrence of film failure (blister failure) due to the generation of bubbles. The range of -0.6 mol / L is preferable.

In the peracid bleach composition, in addition to the above-mentioned peracid bleach and halogen ions, a pH buffer, a development inhibitor, a stabilizer, a bleaching accelerator and the like may be used as long as the effects of the present invention are not impaired. Can be added.

Examples of the pH buffer include potassium or sodium carbonate, potassium or sodium borate,
Potassium or sodium phosphate, calcium hydroxide,
Sodium silicate, β-alanine diacetate, arginine,
Use a known buffer such as asparagine, ethylenediamine, ethylenediaminetetraacetic acid, ethylenediaminedisuccinic acid, glycine, histidine, imidazole, isoleucine, leucine, methyliminodiacetic acid, nicotinic acid, nitrilotriacetic acid, piperidine, proline, purine, and pyrrolidine. Among them, a buffer comprising a combination of potassium carbonate (or sodium) / potassium hydrogen carbonate (or sodium) is particularly preferable because it can reduce the cost and has high environmental suitability.

Examples of the development inhibitor include nitrogen-containing heterocyclic compounds such as benzimidazoles, benztriazoles, benzthiazolium salts, and tetrazaindenes.

Examples of the stabilizer include compounds known as hydrogen peroxide stabilizers such as phosphoric acid, pyrophosphoric acid, stannic acid, uric acid, hippuric acid, barbital, acetanilide, aminopolycarboxylic acids, pyridinecarboxylic acids, and the like.
Chelating agents such as organic phosphonic acids can be preferably used.

Examples of the bleaching accelerator include, for example, those described in
No. 58532, No. 53-32736, No. 53-374
No. 18, No. 53-72623, No. 53-104232
No. 53-124424 and No. 53-65732.
Bleaching accelerators described in JP-A-54-52534 and the like can be used.

The peracid bleach composition can be used at any temperature, but is preferably at least 20 ° C. and no more than 60 ° C.
The higher the temperature, the shorter the processing time is possible and preferable.
From the viewpoint of the stability of the processing solution, it is preferable not to be very high.
It is particularly preferable to perform the treatment at a temperature of 5 ° C. or more and 55 ° C. or less.

The processing time with the peracid bleach composition varies depending on the type of the light-sensitive material, the processing temperature, the activity of the processing solution and the like, but is preferably within 90 seconds, and more preferably within 60 seconds. preferable.

The fixing agent composition preferably used in the present invention will be described.

The fixing agent as the main composition of the fixing agent composition preferably used in the present invention includes sodium thiosulfate, ammonium thiosulfate, potassium cyanide, sodium cyanide, sodium thiocyanate, ammonium thiocyanate, sodium sulfite, and ammonium sulfite. , Potassium sulfite, a water-soluble thioether compound, a water-soluble mercapto compound, thiourea and its derivatives, thiouracil and its derivatives, and the like. From the viewpoint of suppressing the occurrence of precipitation due to the reaction between the oxidizing agent brought in from the amplification developer and the fixing agent composition, a fixing agent composition containing substantially no thiosulfate is preferred. Further, sodium sulfite and potassium sulfite can be used as particularly preferable fixing agents from the viewpoint of reducing the load on the environment. The preferable concentration of the fixing agent varies depending on the type of the fixing agent.
1.6 mol, preferably 0.0 mol / l
8 mol to 1.2 mol.

In the fixing agent composition, in addition to the above fixing agent, a pH buffer, a development inhibitor, a stabilizer, a fixing accelerator and the like can be added as long as the effects of the present invention are not impaired.

As the pH buffering agent and the development inhibitor, for example, the same compounds as in the case of the above-mentioned bleaching composition can be used.

Examples of the fixing accelerator include a nitrogen-containing heterocyclic compound having a water-soluble group, and among them, a compound having a mercapto group can be preferably used.

The fixing agent composition can be used at any temperature, but is preferably from 20 ° C. to 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, the lower the temperature, the better.
It is particularly preferable to carry out the treatment at a temperature of at least 55 ° C.

The processing time with the fixing agent composition varies depending on the type of the photosensitive material, the processing temperature, the activity of the processing solution, and the like.
It is preferably within 90 seconds, and more preferably within 60 seconds.

It is also possible to apply a composition obtained by combining a preferred compound from the above-mentioned bleaching composition and fixing agent composition as a processing composition (bleach-fixing composition) to the present invention.

In the image forming method of the present invention, the pH of the photographic processing composition applied immediately after the amplification and development processing is 6.5.
There is no particular limitation as long as it is at least 11.0, but there is a case where the difference between the pH of the amplification developer and the pH of the photographic processing agent composition used in the processing performed immediately after the amplification development processing is at least 1.0. Particularly preferred. Increasing the pH of the photographic processing composition used in the processing performed immediately after the amplification processing can reduce the occurrence of discoloration, but the color developing agent and the oxidizing agent introduced from the amplification processing solution. Because the unnecessary amplification development reaction is accelerated due to the above, the stability of gradation reproduction is likely to be impaired, and the preferable pH of the photographic processing composition immediately after the amplification development processing is (the amplification developer pH
−1.0), and more preferably (pH-1.6 of the amplification developer). From amplification processing
The time required for processing with a photographic processing composition having a H of 6.5 or more and 11.0 or less can be appropriately selected within a range that does not affect photographic performance.
Seconds or less are more preferred.

Next, the amplification development processing will be described.

In the present invention, the amplification and development process means that 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 addition compound of hydrogen peroxide, peroxo compounds such as peroxoborate and peroxocarbonate, and cobalt (III) compounds 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 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,
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.

In addition to 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 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-described color developing agent and an oxidizing agent for amplification development to a photographic 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 Japanese Patent Application Laid-Open No. 7-077788, a method of forming a developed silver by processing in a developing bath containing a developing agent, followed by amplifying and developing in a processing bath containing a developing agent and an oxidizing agent is exemplified. 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 developer is 0.2 to 10 g / l, particularly preferably 1 to 5 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 comprising a developing bath and an 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 ml
/ L, more preferably 1 to 5 ml / l.

In the present invention, the above-mentioned developer, amplifying solution,
The developing / amplifying solution can be used in an arbitrary pH range, but is preferably pH 9.0 to 12.5, more preferably pH 10.0 to 11.5 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 type of the photosensitive material, the processing temperature, the activity of the processing solution, and the like.
It is preferably performed within 0 seconds, more preferably within 90 seconds.

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, a development inhibitor such as a pH buffer, a chloride ion, and benzotriazole, a preservative, and a chelating agent are used.

As the pH buffer, a known buffer can be used. Among them, a buffer composed of a combination of carbonate and / or phosphate is preferable because the cost can be reduced.

In the present invention, it is preferable to use the above-mentioned aromatic primary amine developing agent and black-and-white developing agent in combination in the amplification developer from the viewpoint of improving the stability of gradation reproduction. Although the mechanism of this effect is not clear, the black-and-white developing agent brought out of the amplification developer reacts with the oxidizing agent in the photosensitive material before the color developing agent, and during that time, the color developing agent diffuses out of the system from the photosensitive material. It is presumed to continue.

In the present invention, black-and-white developing agents that can be used include dihydroxybenzenes, 3-pyrazolidones, pyrogallols, glycines, hydroxylamines, hydrazines, aminophenols, reductones, and 3-aminopyranes. Zolins and transition metal complex salts (complex salts of transition metals such as Ti, Cr, Mn, Fe, Co, Ni, Cu, etc.) These may be in any form having a reducing power to be used as a developing solution. ³⁺ , V ²⁺ ,
It takes the form of complex salts such as Cr ²⁺ and Fe ²⁺ , and the ligands are aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and salts thereof, hexametapolyphosphoric acid, and tetrapolyphosphoric acid. And phosphoric acids such as acids and salts thereof). Among them, preferred are dihydroxybenzenes, 3-pyrazolidones, hydroxylamines, and reductones. The amount of the black-and-white developing agent to be used is preferably in the range of 0.1 to 3.0, more preferably 0.25 to 2.0, as a molar ratio to the color developing agent.

As the processing apparatus used in the image forming method of the present invention, even if it is a roller transport type in which the photosensitive material is transported between rollers disposed in a processing bath, the photosensitive material is fixed to a belt and transported. An endless belt method may be used, but a processing bath is formed in a slit shape, and a processing method for supplying a processing liquid to the processing bath and transporting the photosensitive material, and a spray method for spraying the processing liquid,
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid can also be used.

Next, the photosensitive material according to the present invention will be described.

The composition of the silver halide photographic emulsion used in the light-sensitive material according to the present invention includes silver chloride, silver bromide, silver chlorobromide,
It may have any halogen composition such as silver iodobromide, silver chloroiodobromide, silver chloroiodide and the like. In particular, when a high silver chloride emulsion containing 80 mol% or more of silver chloride is present in a light-sensitive material, the stability of gradation reproduction with respect to a change in the concentration of an oxidizing agent in an amplification processing solution is likely to be reduced. The effect is particularly useful. In the present invention, when a silver halide emulsion having a high silver chloride content is used, it is preferable from the viewpoint that the color development time and the bleaching and fixing processing time can be shortened.

As the silver halide emulsion used in the light-sensitive material according to 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.

In order to obtain a silver halide emulsion used in the light-sensitive material according to the present invention, a heavy metal ion may be contained for the purpose of improving photographic characteristics. Such heavy metal ions include iron, iridium, platinum, palladium,
Group 8 to 10 metals such as nickel, rhodium, osmium, ruthenium, and cobalt; and cadmium, zinc, and group 12 transition metals such as mercury; lead, rhenium, molybdenum;
Examples include 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, the ligand may be a 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 contain heavy metal ions in the silver halide emulsion used in the light-sensitive material according to the present invention, the heavy metal compound is added to the silver halide emulsion before the silver halide grains are formed, during the formation of the silver halide grains, and during the formation of the 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, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 ^-9 per mole 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 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.

The particle size of the silver halide grains used in the light-sensitive material of the present invention is not particularly limited, but is preferably 0.1 to 1 in consideration of other photographic properties such as rapid processing and sensitivity. 0.2 μm, more preferably 0.2 to
The range is 1.0 μm.

The size of silver halide grains can be measured by various methods generally used in the art. A typical method is described in Loveland's “Particle Size Analysis Method” (ASTM Symposium on Right Microscopy, pp. 94-122, 195).
5) Or "Theory of Photographic Process Third Edition" (Mies and James, Chapter 2, published by Macmillan, 196)
The method described in 6) can be mentioned.

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 in 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 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 and JP-A-57-92523 describe the same.
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 DE-A-2,921,164. 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 according to 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 has the advantage that the bleaching time of the peracid bleaching composition can be shortened, and is particularly preferred.

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 a 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, etc. 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 step 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 amount of silver halide contained in each light-sensitive layer is preferably 0.1 g / m ² or less for the following reasons. That is, the load on the desilvering process is reduced, and the development reaction in the own layer is affected by the development reaction in the other layer, so that the occurrence of the so-called inter-image effect is small. As a result, the oxidizing agent in the amplification developer is reduced. The effect of the present invention of improving the stability of gradation reproduction with respect to density fluctuation is more remarkably exhibited. 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.

As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by coupling reaction with an oxidized form of a color developing agent is used. Although it is also possible to use, particularly typical 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 thus are preferable. Further, the most preferred compound is disclosed in
No. 81847, page 1 and pages 11 to 17
It is a compound represented by the general formula [Y-1] described on the page.

When the oil-in-water emulsion dispersion method is used to add the coupler or other organic compound 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 a water-soluble organic solvent, and then 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.

Preferred examples of the compound used as a surfactant for dispersing a photographic additive or adjusting the surface tension during coating include a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. Containing. 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 after the addition are preferably 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 compounds represented by the general formula I described on page 3 of JP-A-2-66541.
Phenyl ether compounds represented by II, JP-A-3-1
A phenolic compound represented by the general formula IIIB described in JP-A-74150, an amine-based compound represented by the general formula A described in JP-A-64-90445, and JP-A-62-182.
Metal complexes represented by general formulas XII, XIII, XIV and XV described in JP-A-741 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 preferred for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and the compound (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 of 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 to prevent fog. It is preferable to improve the above. 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, 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-3-25184.
The dyes of AI-1 to 11 described in JP-A No. 308, page 308 and the dyes described in JP-A-6-3770 are preferably used. As the infrared absorbing dye, JP-A 1-28075 is used.
No. 0, page 2, lower left column, formulas (I) and (I)
The compounds represented by I) and (III) have preferable spectral characteristics, and do not affect the photographic characteristics of the silver halide photographic emulsion.
It is also preferable because there is no contamination due to residual color.

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

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention because 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. Further, the silver halide emulsion contained in each dye image forming layer contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye for use in the silver halide emulsion according to the present invention, any known compounds can be used.
BS-1 to 8 described in page 28 of JP 51840 can be preferably used alone or in combination. Examples of the green photosensitive sensitizing dye include G
S-1 to S-5 are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. Issue 1
It is preferable to use the compounds S-1 to S-17 described on pages 5 to 17 in combination.

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

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

It is advantageous to use gelatin as a binder in the light-sensitive material according to the present invention. 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.
It is preferable to use the compounds described in JP-A Nos. 054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability. Further, in order to improve the physical properties of the surface of the light-sensitive material or the processed sample, a protective layer is disclosed in
It is preferable to add a slip agent or a matting agent described in JP-A-118543 and JP-A-2-73250.

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

The light-sensitive material according to 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 properties of the support surface, It may be applied via one or more undercoat layers for improving dimensional stability, friction resistance, hardness, antihalation property, frictional 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. After the image is once converted to digital information, 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. Printing may be performed by scanning while changing the intensity or irradiation time of the laser light.

The image forming method of 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 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.

[0101]

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

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

(Solution A1) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B1) 10 g of silver nitrate 200 ml with addition of water (Solution C1) 102.7 g of sodium chloride 102.7 g of potassium hexachloroiridium (IV) 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 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 0.55 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, (A1
Solution) and (B1 solution) and (C1 solution) and (D1 solution)
Liquid monodisperse cubic emulsion EMP-1B having an average particle size of 0.50 μm, a variation coefficient of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained in the same manner except that the addition time of the liquid was changed. .

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

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

[0107]

Embedded image

(Preparation of silver halide photographic light-sensitive material (101)) A high-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side 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 light-sensitive material. 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 as hardening agents. Surfactants (SU-1), (SU-2), (SU-
3) was added to adjust the surface tension. In addition, (F-
1) was added so that the total amount was 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) 0.026 Cyan coupler (C-1) 0.28 Dye image stabilizer (ST-1) 0.10 Stain inhibitor (HQ-1) 0.004 DBP 10 DOP 0.20 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 DOP : Dioctyl phthalate HQ-1: 2,5-di-t-octyl hydroquinone

[0112]

Embedded image

The photosensitive material (10
In contrast to 1), light wedge exposure was performed for 0.5 seconds with white light, and after the following processing steps, the densitometer PDA-65 was used.
The reflection density was measured using (manufactured by Konica Corporation) to determine the gradation (γS). The gradation was defined as the average gradient of the characteristic curve with respect to the exposure amount between the reflection density of 0.75 and the reflection density of 1.75.

Next, the same processing was performed except that the amount of hydrogen peroxide in the amplification developer (CDA-1) was changed to 50 ml.
The minimum density (DminO) and gradation (γO) were determined.
Using γS as a reference gradation, a ratio between γO and γS (γO / γ) is used as a value representing a change in gradation when the amount of hydrogen peroxide changes.
The value of S) was obtained, and the stability of gradation reproduction was evaluated using this value. The closer the value of γO / γS is to 1, the more stable the layer can reproduce the gradation with respect to the concentration fluctuation of the oxidizing agent in the amplification developer.

Further, the reflection density (DG) in green light at the point where the reflection density in red light was 1.0 was measured.
The smaller the value is, the smaller the discoloration that the cyan image becomes greenish is, which is preferable.

<< Processing Step >> Processing Processing Temperature Time Developer (CDA-1) 35.0 ± 0.5 ° C. Table 1 Bleach (BL-1) or (BL-2) 35.0 ± 0 0.5 ° C. 45 seconds Fixing solution (F-2) 30.0 ± 0.5 ° C. 45 seconds 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 Disodium hydrogen phosphate 10 g Potassium carbonate 20 g Hydrogen peroxide (5.99%) 25 ml Adjust the pH with potassium hydroxide or sulfuric acid, and add water to make the total volume 1 liter.

(PH is described in Table 1) Bleach (BL-1) 800 ml of pure water 1-hydroxyethylidene-1,1'-diphosphonic acid 0.35 g sodium picolinate 4.3 g sodium chloride 11.7 g sodium carbonate 20 0.0 g Potassium dihydrogen phosphate 20.0 g Hydrogen peroxide solution (30%) 100 ml Adjust the pH with potassium hydroxide or sulfuric acid, and add water to make the total volume 1 liter.

(PH is described in Table 1) Bleach (BL-2) Pure water 800 ml Ethylenediaminetetraacetic acid Na · Fe salt 100 g Sodium chloride 11.7 g Ammonia water (20%) 6 ml Ammonia water or nitric acid to pH = 6. Adjust to 0 and add water to bring the total volume to 1 liter.

Fixer (F-2) Pure water 800 ml Sodium sulfite 100 g Sodium bicarbonate 25 g Water was added to make up to 1 liter, and the pH was adjusted to 8.2 with sulfuric acid or potassium hydroxide.

Stabilizing liquid 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) 1.0 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. .

Table 1 shows the results.

[0123]

[Table 1]

From the results shown in Table 1, it can be seen that the pH of the treating composition immediately after the amplification and development treatment is 102 or more, and that the pH of the treating composition is 6.5 or more.
It can be seen that all of the samples treated with 06, 107, 110, and 111 have improved stability of gradation reproduction with respect to fluctuations in the concentration of hydrogen peroxide in the amplification developer, and further reduce the occurrence of discoloration. Among them, 102, 103, 106, and 110 in which the pH of the processing agent composition immediately after the amplification development processing is 1.0 or more lower than the pH of the amplification development processing solution are particularly preferred embodiments of the present invention, and the value of γO / γS is 1 It can be seen that the gradation variation width is small and particularly high.

Example 2 Using the photosensitive material (101) prepared in Example 1, processing and evaluation were performed in the same manner as in Example 1 except that the processing steps were changed as described below. However, the pH of the fixing solution (F-2) was adjusted as shown in Table 2 using sulfuric acid or potassium hydroxide. The results are shown in Table 2.

Processing Step Processing Processing Temperature Time Developing Solution (CDA-1) 35.0 ± 0.5 ° C. Table 2 Fixing Solution (F-1) or (F-2) 30.0 ± 0.5 45 ° C. Stabilizing solution 30-34 ° C. 60 seconds Drying 60-80 ° C. 30 seconds Fixing solution (F-1) Pure water 800 ml 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 Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

[0127]

[Table 2]

From the results in Table 2, it can be seen that the pH of the processing composition immediately after the amplification development processing is 202 or higher, and that the pH of the processing composition is 6.5 or higher.
The samples processed at 06, 207, 210 and 211 are:
In each case, the stability of gradation reproduction with respect to the change in the concentration of hydrogen peroxide in the amplified developer was improved, and the occurrence of discoloration was further reduced. Among them, 202, 203, 206, 207 and 210 in which the pH of the processing agent composition immediately after the amplification development processing is 1.0 or more lower than the pH of the amplification development processing liquid are particularly preferred embodiments of the present invention, and the gradation reproduction stability is high. It can be seen that the effect of improving is particularly high and preferable.

Example 3 Using the photosensitive material (101) prepared in Example 1, processing and evaluation were performed in the same manner as in Example 1 except that the processing steps were changed as described below. However, bleaching solution (BL-1)
Was adjusted with potassium hydroxide or sulfuric acid as shown in Table 3. The results are shown in Table 3.

Processing Step Processing Temperature Temperature Developer (CDA-2) 35.0 ± 0.5 ° C. 60 seconds Bleach (BL-1) 35.0 ± 0.5 ° C. 45 seconds Fixer (F- 2) 30.0 ± 0.5 ° C. 45 seconds Stabilizing solution 30-34 ° C. 60 seconds Drying 60-80 ° C. 30 seconds Amplifying developer (CDA-2) 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 g N, N-diethylhydroxylamine 4.7 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g 1-hydroxyethylidene -1,1'-diphosphonic acid 0.35 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g Disodium hydrogen phosphate 10 g Potassium carbonate 20g black and white developer Table 3 wherein the hydrogen peroxide solution (5.99%) was adjusted to pH = 11.5 with 25ml of potassium hydroxide or sulfuric acid, to make 1 liter by adding water.

[0131]

[Table 3]

BW-1: hydroxylamine sulfate BW-2: 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone BW-3: hydroquinone From the results in Table 3, the composition of the processing agent immediately after the amplification and development processing was obtained. Object p
302, 303, 305 to 30 where H is 6.5 or more
9, 311, 312, 314, and 315, the stability of gradation reproduction with respect to the change in the concentration of hydrogen peroxide in the amplified developer was improved, and the occurrence of discoloration was reduced. . Among them, 305 to 309, 311 and 31 treated with an amplification developing solution containing a black and white developing agent
2, 314 and 315 are particularly preferable embodiments of the present invention, and it can be seen that the effect of improving the tone reproduction stability is particularly high and preferable.

Example 4 In the preparation of the light-sensitive material (101) of Example 1, except that the amount of silver halide in the light-sensitive layer was changed as shown in Table 4, the light-sensitive materials (401) and (402) were prepared in the same manner. )made.

The light-sensitive material (40
1) and (402) were processed and evaluated in the same manner as in Example 1. However, the pH of the amplification developer (CDA-1) was adjusted to 11.5, and the amplification development time was 60 seconds. Table 4 shows the results.

[0135]

[Table 4]

From the results shown in Table 4, it can be seen that the pH of the processing composition immediately after the amplification and development processing was 402 or more, and that the pH of the processing composition was 6.5 or more.
It can be seen that the samples processed in Nos. 06, 407, 410, and 411 all have improved stability of gradation reproduction with respect to fluctuations in the concentration of hydrogen peroxide in the amplified developer, and the occurrence of discoloration has been reduced. Among them, a photosensitive material in which the amount of silver halide contained in each photosensitive layer was 0.1 g / m ² or less was used.
02, 403, 406, and 407 are particularly preferable embodiments of the present invention, and it can be seen that the effect of improving the tone reproduction stability is particularly high and preferable.

Example 5 (Preparation of silver halide emulsions (Em-B2) to (Em-B3)) The silver halide emulsions EMP-1 and EMP of Example 1
(A1 solution) and (C1 solution) used for the preparation of
A liquid monodisperse cubic emulsion having a silver chloride content of 85 mol% was prepared in the same manner as in Example 1 except that the composition was changed to Liquid 2 and Liquid C2. A silver halide emulsion (Em-B2) was prepared. (A1 solution),
A monodisperse cubic emulsion having a silver chloride content of 75 mol% was prepared in the same manner except that (C1 solution) was changed to (A3 solution) and (C3 solution), respectively. To prepare a blue-sensitive silver halide emulsion (Em-B3).

(Solution A2) 2.92 g of sodium chloride 1.05 g of potassium bromide 200 ml with addition of water (Solution C2) 87.7 g of sodium chloride Potassium hexachloroiridate (IV) 4 × 10 ⁻⁸ mol Hexacyanoiron (II) Potassium acid 2 × 10 ⁻⁵ mol Potassium bromide 31.5 g Water 600 ml (solution A3) Sodium chloride 2.58 g Potassium bromide 1.75 g Water added 200 ml (C3 solution) Sodium chloride 77.4 g Hexachloroiridium (IV) Potassium acid 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 52.4 g Add water 600 ml (for silver halide photographic light-sensitive materials (501) and (502) Preparation) In the preparation of the photosensitive material (101) of Example 1,
Light-sensitive materials (501) and (502) were prepared in the same manner except that the photosensitive silver halide was changed as shown in Table 5.

The light-sensitive material (50
For 1) and (502), the same processing as in the first embodiment is performed.
An evaluation was performed. However, the pH of the amplification developer (CDA-1)
Was adjusted to 11.5, and the amplification development time was 60 seconds. Further, after the sample of the present invention subjected to the entire surface exposure with white light was subjected to the treatment of the present invention (the bleaching treatment time was changed between 0 and 60 seconds), the silver remaining in the obtained sample became fluorescent. The bleaching time (TB) at which no bleaching was detected by X-ray analysis was determined, and the desilvering property was evaluated. The results are shown in Table 5.

[0140]

[Table 5]

From the results shown in Table 5, it can be seen that the pH of the treating composition immediately after the amplification and development treatment is not less than 6.5, that is, 502, 503 and 5
It can be seen that the samples processed in Nos. 06, 507, 510 and 511 have improved stability of gradation reproduction with respect to fluctuations in the concentration of hydrogen peroxide in the amplification developer, and furthermore have reduced occurrence of discoloration. In the case of the light-sensitive materials (101) and (501) prepared using silver halide having a silver chloride content of 80 mol% or more, the bleaching time is short, and the concentration fluctuation of the oxidizing agent in the amplification developing solution is sufficient. It can be seen that the range of improvement in the gradation fluctuation at the time is a particularly preferable embodiment of the present invention.

Example 6 (Preparation of Green-Sensitive Silver Halide Emulsion (Em-G1)) In the preparation of the silver halide emulsion EMP-1A of Example 1, the addition time of (A1 solution) and (B1 solution) and (C1 liquid)
A monodisperse cubic emulsion EMP-11A having an average particle size of 0.30 μm and a silver chloride content of 99.5 mol%, and the average particle size of 0.25
A monodispersed cubic emulsion EMP-11B having a thickness of 9 μm and a silver chloride content of 99.5 mol% was obtained. The above-mentioned EMP-11A was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Similarly, after optimally chemical sensitizing EMP-11B, the sensitized EMP-11A and EMP-11B are mixed at a silver ratio of 1: 1 to obtain a green photosensitive silver halide emulsion ( Em-G1) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-3 3 × 10 ⁻⁴ mol / mol AgX (Preparation of red-sensitive silver halide emulsion (Em-R1)) 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 monodisperse cubic emulsion EMP-21A having an average particle size of 0.35 μm and a silver chloride content of 99.5 mol%, and the average particle size of 0.30 μm were obtained in the same manner except that the addition time of the solution (D1) was changed.
A monodispersed cubic emulsion EMP-21B having a thickness of 9 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. Similarly, after optimally chemical sensitizing EMP-21B, the sensitized EMP-21A and EMP-21B are mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion ( Em-R1) was obtained.

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

[0145]

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(Preparation of silver halide photographic light-sensitive material (601)) After the reflective support used in Example 1 was subjected to corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further provided. To prepare a silver halide photographic light-sensitive material. In the preparation of the photosensitive material, each coating solution was prepared so as to have the following coating amount, and (H-1), (H-
2) was added. Surfactants (SU
-1), (SU-2) and (SU-3) were added to adjust the surface tension. The total amount of (F-1) is 0.04 in each layer.
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) 0.026 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 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) 0.028 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- 1) 0.70 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer (ST-2) 0.10 Dye image stabilizer (ST-5) 0.10 Stain inhibitor (HQ-) 1) 0.01 Image stabilizer A 0.15 DBP 0.10 DNP 0.05 Support polyethylene laminated paper The amount of silver halide was shown in terms of silver.

DNP: dinonyl phthalate PVP: polyvinylpyrrolidone 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

[0150]

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[0151]

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[0152]

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[0153]

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The light-sensitive material (60
For 1), Konica Color LV that has been photographed and developed
After performing image exposure through a 400 color negative film, processing was performed under the processing conditions described in Example 1, and the resulting printed image was observed. As a result, the print image processed under the processing conditions satisfying the conditions of the present invention has a small change in gradation with respect to a change in the amount of hydrogen peroxide in the amplification developer,
Further, almost no discoloration of the cyan image was observed, and it was confirmed that a stable image was obtained.

[0155]

According to the present invention, during amplification and development of an imagewise exposed silver halide photographic light-sensitive material, a change in gradation balance with respect to a change in an oxidizing agent concentration in an amplification developing solution is small, and discoloration of an obtained image is achieved. Thus, it was possible to provide an image forming method for amplifying and developing a silver halide photographic light-sensitive material, in which the amount of light was reduced.

Claims (6)

[Claims] 1. An image forming method wherein an imagewise exposed silver halide photographic material is immediately processed after amplification and development with a photographic processing composition having a pH of 6.5 to 11.0. 2. The image forming method according to claim 1, wherein the pH of the photographic processing composition is not more than (pH of an amplification developer-1.0). 3. The photographic processing composition according to claim 1, wherein the photographic processing composition is a bleaching composition, a fixing composition or a combination thereof substantially free of thiosulfate. Item 3. The image forming method according to Item 1 or 2. 4. The image forming method according to claim 3, wherein the bleaching composition is a peracid bleaching composition. 5. The image forming method according to claim 3, wherein the fixing agent composition is a fixing agent composition containing a sulfite as a fixing agent. 6. The amplification developer has a pH of 10.0 or more and 1 or more.
The image forming method according to claim 1, wherein the number is 2.5 or less.