JPH112888A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method in which gradation fluctuation caused by temporal change from exposure till amplification development and the stability of gradation balance are improved. SOLUTION: In this image forming method in which silver halide photographic sensitive material image-exposed is amplified and developed under the existence of at least a color developing principal chemical, an oxidant for amplification development and an amplification development activity imparting agent; the oxidant for amplification development is supplied to the silver halide photographic sensitive material after supplying the color developing principal chemical and the amplification development activity imparting agent to the silver halide photographic sensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an image forming method in which gradation fluctuation due to a change in time from exposure to amplification and development and stability of gradation balance are improved.

[0002]

2. Description of the Related Art Silver halide photographic materials (hereinafter, also simply referred to as "photosensitive materials") have extremely excellent characteristics, such as high sensitivity and excellent gradation, as compared with other printing materials. It has been widely used today. The silver halide photographic light-sensitive material has the characteristics described above. Further, the amount of photosensitive silver halide in the light-sensitive material can be reduced, the time required for desilvering processing can be shortened or omitted, and halogen is a preferable means in terms of effective use of resources. A method of forming an image by subjecting a silver halide photographic light-sensitive material to amplification and development processing 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. . Among them, a method using hydrogen peroxide as an oxidizing agent for amplification and development is preferable because it has high amplification efficiency and can greatly reduce the burden on the environment. In an amplification development method using hydrogen peroxide as an oxidizing agent, iodide ions or bromide ions are known to significantly reduce the amplification effect and become a so-called catalyst poison. A light-sensitive material using silver halide grains having a high silver content or an image forming method using the same is disclosed in, for example, JP-A-58-154.
Nos. 840 and 64-44938, and JP-A-5-3466.
Nos. 47 and 6-301128.

[0003] However, silver halide grains having a high silver chloride content tend to have large gradation variations due to changes in the time from exposure to amplification and development. In addition, in amplification development, processing is performed in the co-presence of a developing agent as a reducing agent and an oxidizing agent for amplification development. The magnitude of the effect is likely to fluctuate. Therefore, in the amplification and development processing of a photosensitive material using silver halide grains having a high silver chloride content, when the time from exposure to amplification development changes and the state of the latent image changes, particularly, gradation fluctuation tends to appear. There was a tendency. Further, when the time from exposure to amplification and development is short, there is a problem that the gradation in the low exposure amount region tends to be softened and the minimum density tends to increase, and improvement thereof has been desired. .

[0004] When a photosensitive silver halide having a high silver chloride content is used, the phenomenon that a latent image becomes particularly unstable for several minutes after exposure is widely known in ordinary color development processing. Even in the aspect of the present invention, normal color development occurs in the initial stage, so that the latent image fluctuates, and this is amplified after the supply of the oxidizing agent for amplification and development. On the contrary, the significant improvements were quite unexpected and surprising.

As a method of separating a color developing agent and an oxidizing agent for amplification development and supplying them to a photosensitive material, for example, Japanese Patent Application Laid-Open No.
Nos. 80149, 61-80150 and the like disclose a color developing agent and an oxidizing agent for amplification development and supply them to a photosensitive material, thereby reducing the amount of processing solution required for amplification development processing and improving development unevenness. There is disclosed a technique for preventing such a situation.
Further, WO 9207299 discloses a technique for improving the temporal stability of a processing solution for amplification development by separating a color developing agent and an oxidizing agent for amplification development.

However, in the above-described amplification and development processing of a photographic material using silver halide particles having a high silver chloride content, as described above, gradation fluctuation occurs when the time from exposure to amplification development changes. No mention is made of the problem of easy appearance, and the present invention is not easily presumed from these.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method in which gradation fluctuation and stability of gradation balance due to a change in time from exposure to amplification and development are improved.

[0008]

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

(1) An image forming method for subjecting a silver halide photographic light-sensitive material imagewise exposed to amplification and development in the presence of at least a color developing agent, an oxidizing agent for amplification and an activating agent for amplification and development. After supplying the color developing agent and the amplification developing activity imparting agent to the silver halide photographic material,
An image forming method comprising supplying an oxidizing agent for amplification development to a silver halide photographic light-sensitive material.

(2) The oxidizing agent for amplification and development is adjusted to pH 10.0.
2. The image forming method according to the above item 1, wherein the image forming method is supplied as a photographic processing liquid of less than

(3) The concentration of the oxidizing agent for amplification in the photographic processing solution containing the oxidizing agent for amplification developing is 0.3 mol / L or more and 1.5 mol / L or less. 3. The image forming method according to 1 or 2.

(4) The image forming method as described in any one of (1) to (3) above, wherein the photographic processing solution containing the oxidizing agent for amplification development contains at least one kind of sequestering agent.

(5) A photographic processing solution containing an oxidizing agent for amplification and development is directly supplied to the silver halide photographic material, or the thickness of the inside of the tank is 100 times or less the thickness of the photographic material. The image forming method according to any one of the above items 1 to 4, wherein the image forming apparatus is supplied in a state of being held or circulated in a thin tank.

(6) The photosensitive silver halide contained in the silver halide photographic material has an average silver chloride content of 80.
The image forming method according to any one of the above items 1 to 5, wherein the amount is at least mol%.

(7) The image forming method as described in any one of (1) to (6) above, wherein the oxidizing agent for amplification and development is hydrogen peroxide or a compound that gives hydrogen peroxide.

(8) The image forming method as described in any one of (1) to (7) above, wherein the amplification and development processing is performed in the presence of a black-and-white developing agent.

(9) The amount of the photosensitive silver halide contained in the silver halide photographic light-sensitive material is 0.001 g in terms of silver.
/ M ² or more and 0.3 g / m ² or less, the image forming method according to any one of the above items 1 to 8, wherein

Hereinafter, the present invention will be described in detail. The present invention is characterized in that an oxidizing agent for amplification development is supplied to a photosensitive material after supplying a color developing agent and an agent for imparting amplification development activity to the photosensitive material.

After supplying the color developing agent and the amplification developing activator to the silver halide photographic light-sensitive material, the oxidizing agent for amplification development is supplied to the light-sensitive material. The mechanism by which the fluctuation is improved is not clear, but in the case of an amplified developer in which a color developing agent, which is a reducing agent, and an oxidizing agent for amplification are coexistent, the oxidation-reduction level tends to fluctuate, and in addition, a low exposure range In the case where a very weak and unstable part of the latent image generated by the color developing agent and the oxidizing agent for amplification development are strongly affected by the reduction effect of the color developing agent under the coexistence of the color developing agent and the developing agent, the developed silver is formed as it is,
Although it can be a catalyst nucleus for amplification development, it is presumed that, when strongly affected by an oxidizing agent for amplification development, the latent image exists in a delicate balance in which the latent image is bleached by oxidation. In the present invention, it is presumed that the effect of the present invention can be obtained by starting a silver development reaction first, and developing a weak and unstable latent image as developed silver before supplying the oxidizing agent for amplification development. Is done.

In the present invention, the amplification developing activator is a component other than the color developing agent and the oxidizing agent for amplification developing in the components of the amplification developing solution, and the amplification developing activator is present in an appropriate amount. Amplifying developer component capable of improving the image formation speed by amplification development by 3 times or more by performing, preferably, amplification developing solution component capable of improving the image forming speed by 10 times or more. .

Specific examples of the amplification developing activity-imparting agent include alkali agents such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; potassium or sodium carbonate; potassium or sodium borate; and potassium phosphate. Or sodium, calcium hydroxide, sodium silicate, β-alanine diacetate, arginine, asparagine, ethylenediamine, ethylenediaminetetraacetic acid, ethylenediaminedisuccinic acid, glycine,
Histidine, imidazole, isoleucine, leucine,
Known pH buffers such as methyliminodiacetic acid, nicotinic acid, nitrilotriacetic acid, piperidine, proline, purine, and pyrrolidine can be mentioned.

In the present invention, the term "amplification development processing" 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 an image dye by forming an image dye by, for example, a coupling reaction of a coupler with an oxidized color developing agent generated by a redox reaction of a color developing agent and an oxidizing agent using a developed silver as a catalyst and a coupler. Method and the like.

In the amplification development process according to the present invention, a combination of an aromatic primary amine color developing agent and hydrogen peroxide is preferably used, and N, N-diethyl-p-phenylene is used as the aromatic primary amine color developing agent. Diamine,
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 color developing agents, for example, EP-A-565165, EP-A-572054
And 593110, JP-A-8-202002, JP-A-8-227131, JP-A-8-234390 and the like can also preferably use the sulfonylhydrazide and carbonylhydrazide type color developing agents.

As the image forming method of the present invention, for example, a photographic processing solution containing a color developing agent and an amplification developing activator is supplied to a photographic material, and then an oxidizing agent for amplification development is supplied to the photographic material ( P-1) Alternatively, a processing solution containing a color developing agent is supplied to the photosensitive material, and after swelling the photosensitive material, an amplification developing activator is supplied, and an oxidizing agent for amplification development is further added to the photosensitive material. Supply method (P-
2) and the like can be used. In addition, a method in which a color developing agent is incorporated in the photosensitive material in advance, a processing solution containing an activator is supplied to the photosensitive material after imagewise exposure, and an oxidizing agent for amplification development is supplied to the photosensitive material (see P. -4)
Is also one of the aspects of the present invention. Preferred embodiments of the image forming method of the present invention include: P-1) a color developing agent / activator → oxidant P-2) a color developing agent → activator → oxidant P-3) an activator → color development Principal agent → Oxidizing agent P-4) Color developing agent (incorporated in photosensitive material) → Activating agent → Oxidizing agent.

In the image forming method of the present invention, a method of transporting a photographic material into a processing bath filled with each of the photographic processing solutions as described above, or forming the processing bath in a slit shape, A method of supplying a processing solution and transporting the photosensitive material, a spray method of spraying the processing solution directly to the photosensitive material, a web method of contacting the carrier impregnated with the processing solution with the photosensitive material, a viscous processing solution. And a method such as a treatment liquid coating method.

In the image forming method of the present invention, when the oxidizing agent for amplification and development is supplied to the photosensitive material, amplification by diffusion of the components of the amplification developing solution which has been supplied to the photosensitive material before the photosensitive material is carried out. In order to suppress the decrease in development efficiency,
A photographic processing solution containing an oxidizing agent for amplification and development is supplied directly to the silver halide photographic material by a spraying method or a coating method without using a processing bath, or the thickness of the inside of the tank is the thickness of the photographic material. It is preferable that the ink is supplied in a state of being held or circulated in a thin tank having a thickness of 100 times or less. Particularly preferred is a mode in which a photographic processing solution containing an amplification developing activity-imparting agent is supplied by spraying directly onto a photosensitive material without using a processing bath.

In the present invention, the photographic processing solution containing the oxidizing agent for amplification and development supplied to the photographic material after the color developing agent and the amplification activator are supplied to the photographic material is contained in the photographic processing solution of the present invention. Known compounds may be added to a photographic processing solution such as a color developing agent, an amplification developing activity-imparting agent, an inhibitor, and a preservative as long as the effect is not impaired. When a color developing agent and an amplification developing activity imparting agent are added to a photographic processing solution containing an oxidizing agent for amplification development, they are preferably used supplementarily. The amount of the color developing agent and the amplification developing activator supplied to the photosensitive material from the photographic processing solution containing the oxidizing agent for amplification is determined by the amount of the sensitizing agent before the oxidizing agent is supplied to the photosensitive material. The amount is preferably １ ／ or less, more preferably １ ／ or less of the amounts of the color developing agent and the amplification developing activity imparting agent supplied.

In the present invention, after supplying a photographic processing solution containing an oxidizing agent for amplification development to a photographic material, an image without supplying a photographic processing solution containing an amplification developing activator or a color developing agent to the photographic material is supplied. The forming method is a particularly preferred embodiment of the present invention since the occurrence of image unevenness can be reduced.

In the present invention, the amount of the oxidizing agent in the photographic processing solution containing the oxidizing agent for amplification and development is preferably from 0.05 to 3.0 mol / l, more preferably from 0.3 to 1. The case is 5 mol / liter. Compounds that give hydrogen peroxide such as hydrogen peroxide, salts of hydrogen peroxide, and adducts of hydrogen peroxide (for example, adducts of hydrogen peroxide with amides, hydrazides, polyhydric allyls, etc.) as oxidizing agents , Peroxo compounds such as peroxoborate and peroxocarbonate, cobalt (III) complexes such as cobalt hexaammine complex, halogenous acids such as chlorous acid, and periodic acid. Among them, a method using a compound that gives hydrogen peroxide such as hydrogen peroxide, a salt of hydrogen peroxide, and an addition compound of hydrogen peroxide as an oxidizing agent is advantageous because the amplification effect is high and the load on the environment is reduced. It is.

In the present invention, the pH of the photographic processing solution containing the oxidizing agent for amplification development is not particularly limited, but from the viewpoint of the storage stability of the photographic processing solution containing the oxidizing agent for amplification development, the pH is adjusted to 10.0. Is preferably less than
It is particularly preferred that H is less than 7.0.

In the present invention, when the photographic material is supplied as a single photographic processing solution containing both a color developing agent and an amplification developing activator, the amount of the color developing agent is 2.5 to 25.0 mmol. Per liter is preferable because the decrease in the maximum density is small even when the amplification development time is shortened, and the deterioration of the processing solution for the desilvering process due to the carry-out of the color developing agent is preferable.

In the present invention, when the color developing agent and the amplification developing activator are prepared as different photographic processing solutions and supplied to the photosensitive material, the amount of the color developing agent in the photographic processing solution containing the color developing agent Is 5.0 to 50.0 mmol / l, the decrease in the maximum density is small even when the amplification development time is reduced, and the deterioration of the processing solution for the desilvering process due to the removal of the color developing agent is reduced. It is preferable because it can be reduced.

The amplification-developing activity-imparting agent has a pH of 10.
When supplied as a photographic processing solution of 0 or more, the amplification and development processing time can be reduced, and in the present invention, in order to shorten the amplification and development time and stably obtain a high maximum density, The buffer capacity at pH 10.5 of a photographic processing solution containing such an amplification activity-imparting agent is 0.1.
It is preferably at least 05.

In the present invention, when the photographic processing solution containing the oxidizing agent for amplification development contains at least one type of sequestering agent, the concentration fluctuation due to the decomposition of the oxidizing agent for amplification development becomes small, so that the processing temperature This is preferable because the effects of the present invention can be stably reproduced even with respect to fluctuations in the supply timing of the processing solution and the like. Examples of such sequestering agents include, for example, ethylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, iminodiacetic acid, trimethylenetetraaminehexaacetic acid, ethylenediaminetetrapropionic acid, trans-cyclohexane- Aminopolycarboxylic acids such as 1,2-diaminetetraacetic acid, ethylenediamine-N, N'-diacetate-N, N'-dipropionic acid or salts thereof, 1-hydroxy-ethylidene-1,
Examples include 1'-diphosphonic acids or salts thereof, catechol disulfonic acids or salts thereof, and pyridine-2-carboxylic acids or salts thereof. Among them, Fe ²⁺ or A
When a sequestering agent having a stability constant with g ⁺ of 5.0 or more is used, the effect of the present invention can be stably reproduced even with respect to fluctuations in processing temperature, processing solution supply timing, and the like. It is preferable because it is possible. The preferred use amount of the sequestering agent is 1 to 100 mmol / L, more preferably 3 to 60 mmol / L.

In the present invention, the pH at the time of amplification development is preferably from pH 9.0 to 12.5 from the viewpoint of rapid processing, and more preferably from pH 10.5 to 12.0. Here, the pH at the time of amplification development refers to the pH of a photographic processing solution in a state where a color developing agent, an oxidizing agent for amplification development, and an agent for imparting amplification development activity are present.
When the components of the amplification developer are divided into a plurality of photographic processing solutions, each of which is directly supplied to the photosensitive material using a spray method or a coating method, etc., the composition of the amplification developer is determined by the ratio supplied to the photosensitive material. It is preferable to adjust the pH of the solution obtained by mixing the photographic processing solutions containing the components in advance so as to be in the above-mentioned pH range. In addition, when the constituent components of the amplification developer are divided into a plurality of photographic processing solutions, and any of them is in a form using a processing bath, the photosensitive material in a dry state is immersed in the processing bath. 2/3 of the saturated liquid absorption at the time is used as the amount of processing solution supplied to the photosensitive material, and the pH of the solution obtained by premixing each photographic processing solution containing the constituent components of the amplified developer in the ratio supplied to the photosensitive material is used. Is preferably adjusted to be in the pH range.

The processing temperature of the amplification development according to the present invention is 20
The temperature is preferably at least 60 ° C and not more 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 photosensitive material, processing temperature, activity of the processing solution and the like.
It is preferably performed within 0 seconds, more preferably within 90 seconds.

Each photographic processing solution containing a color developing agent, an oxidizing agent for amplification development, or an agent for imparting amplification development activity contains chloride ions, benzotriazoles and the like as long as the effects of the present invention are not impaired. A development inhibitor, a preservative, a chelating agent and the like can be used together.

In the present invention, when the above-described color developing agent and black-and-white developing agent are used in combination during amplification development, the amplification processing time can be further shortened in addition to the effects of the present invention, and the photosensitive material can be used in a plurality of colors. When an image forming layer is provided, the influence of the development of other layers on the image forming speed of the own layer is reduced, and the stability of gradation reproduction is more remarkable, which is preferable.

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.

Next, the light-sensitive material according to the present invention will be described. The composition of the silver halide emulsion used in the light-sensitive material according to the present invention is not particularly limited. However, when a silver halide emulsion having a silver chloride content of 80 mol% or more is used, the time from exposure to amplification and development is increased. This is a mode in which the effect of the present invention is particularly useful because the gradation variation due to the change of the image is easily remarkable.

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 also 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 according to the present invention may contain a heavy metal ion 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, the 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 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 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 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 a time, or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form 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 according to the present invention, so-called tabular silver halide is 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 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.

The silver halide emulsion used in the light-sensitive material according to the present invention prevents fog generated during the preparation of the light-sensitive material, reduces performance fluctuations during storage, and prevents fog generated during development. 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.
In the present invention, the amount of photosensitive silver halide contained in the photosensitive material is represented by a value converted to silver.

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 that can be preferably used in the light-sensitive material of the present invention include those 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
General formulas (IIβ) to (VIII) described in the upper left column of page 8
and a cyan coupler represented by β).
In particular, the general formulas (IIα) to (VIIIα) and (IIβ)
The cyan coupler represented by (VIIIβ) is preferable because it has sharp absorption of image dyes and is excellent in color reproducibility.

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

When the 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 a surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. 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, compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and compound (A'-1) described in the lower left column of page 10 of JP-A-4-114154 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.

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-3-2518.
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 of the known compounds can be used. As the blue-sensitive sensitizing dye, BS-1 to 8 described in page 28 of JP-A-3-251840 are used alone. 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, dimethylformamide or the like or water, or adding it as a solid dispersion. It may be added.

In the light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder. If necessary, another gelatin, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein 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. 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.

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

The 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.

In the image forming method of the present invention, after the amplification and development, bleaching and fixing may be performed as necessary. The bleaching process may be performed simultaneously with the fixing process.
After the fixing process, a water washing process is usually performed. Also,
As an alternative to the water washing treatment, a stabilization treatment may be performed.

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 conveyed between rollers arranged in a processing bath, the photosensitive material is fixed on a belt and conveyed. 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.

[0089]

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 added water (Solution B1) 10 g of silver nitrate 200 ml with added 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 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, average silver chloride content 9
A 9.5 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-1A).
-B1) 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

[0093]

Embedded image

(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 photosensitive 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

[0098]

Embedded image

The photosensitive material (10
The thickness of 1) was about 230 μm. This photosensitive material (1
01), light wedge exposure was performed with white light for 0.5 seconds,
After allowing to stand for 5 minutes after the exposure, amplification and development processing was performed in any of the following amplification and development processing steps 1 to 7, followed by desilvering processing in desilvering processing step 1. In each of the amplification and development processing steps, the supply method of each photographic processing solution is as follows: processing bath: immersing and stirring the photographic material in 10 liter of photographic processing solution contained in a 20 cm thick tank Spray: 1 m of the photographic material Either spraying and supplying 80 ml of photographic processing solution per ² was used.

Regarding the processing temperature, the processing bath: the temperature of the photographic processing solution was controlled at 35.0 ± 1.0 ° C. Spray: the temperature of the photographic processing solution and the ambient temperature of the spray section were 35.0 ± 1. It controlled to 0.0 degreeC. 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 gradation (γ) were determined. The gradation was defined as the average gradient of the characteristic curve with respect to the exposure amount between the reflection density of 0.25 and the reflection density of 0.75. Next, the same processing and measurement were performed except that the time from exposure to amplification and development was changed to 1 minute. Gradation (γ5) when the time from exposure to amplification and development is 5 minutes for each sample
(Γ5−γ1) from the gradation (γ1) when the time from exposure to amplification and development was 1 minute. The closer these values are to 0, the smaller the gradation fluctuation, which is preferable, even if the time from exposure to amplification and development varies.

Table 1 shows the results.

Amplification development process 1 Processing time Supply method Amplification developer (CDA-1) 50 seconds Processing bath Amplification development process 2 Processing time Supply method Color developing solution (CD-1) 20 seconds Processing bath activating solution (AA) -1) 20 seconds Spray Oxidizing agent solution (OX-1) 45 seconds Spray Amplification and development process 3 Processing time Supply method Activating solution (AA-1) 20 seconds Processing bath Color developing solution (CD-1) 20 seconds Spray Oxidation Agent solution (OX-1) 45 seconds Spray Amplification and development processing step 4 Processing time Supply method Color developer (CD-1) 20 seconds Processing bath Oxidizing agent solution (OX-1) 20 seconds Spray Activator (AA-1) 45 seconds Spray Amplification development processing step 5 Processing time Supply method Activating solution (AA-1) 20 seconds Processing bath Oxidizing agent solution (OX-1) 20 seconds Spray Color developing solution (CD-1) 45 seconds Sp Lae Amplification development process 6 Processing time Supply method Oxidizer solution (OX-1) 20 seconds Processing bath Color developer (CD-1) 20 seconds Spray Activation solution (AA-1) 45 seconds Spray Amplification development process 7 Process Time Supply method Color developing solution (CD-2) 20 seconds Processing bath activating solution (AA-1) 20 seconds Spray Oxidizing agent solution (OX-1) 45 seconds Spray Desilvering process 1 Processing time Processing temperature Bleaching fixer ( BF-1) 45 seconds 30.0 ± 0.5 ° C. Stabilizing solution 60 seconds 30 to 34 ° C. Drying 30 seconds 60 to 80 ° C. 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 Hydroxylamine sulfate 1.0 g Potassium carbonate 20 g Hydrogen peroxide 0.05 mol Adjust the pH to 10.3 with potassium hydroxide or sulfuric acid, and add water to adjust the total amount. 1 liter.

Color developing agent solution (CD-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 10.0 g N, N-diethylhydroxylamine 4.7 g Hydroxylamine sulfate 1.0 g Adjust the pH to 6.5 with potassium hydroxide or sulfuric acid, and add water to make the total amount 1 liter.

Color developing agent solution (CD-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 10.0 g N, N-diethylhydroxylamine 4.7 g Adjust the pH to 6.5 with potassium hydroxide or sulfuric acid, and add water to make the total amount 1 liter.

Oxidizing agent liquid (OX-1) Pure water 800 ml Hydrogen peroxide 0.35 mol Adjust the pH to 6.5 with potassium hydroxide or sulfuric acid, and add water to make the total amount 1 liter.

Activating Solution (AA-1) (Processing Solution for Photography Containing Amplifying Activating Agent) 800 ml of pure water 25 g of potassium carbonate The pH is adjusted to 11.6 with potassium hydroxide or sulfuric acid, and water is added to the whole amount. Is 1 liter.

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

Stabilizing 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) 1.0g 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.

[0111]

[Table 1]

From the results shown in Table 1, it can be seen that in the image forming method of the present invention, when the time from exposure to amplification and development changes, the gradation change is small and preferable. Also, N
o. 102 and no. In 107, the activating solution (AA-
When the supply time of 1) is reduced to 10 seconds, 107
In No. 5, although a decrease in the maximum density was observed, the black and white developing agent was used in combination with the color developing agent. In No. 102, the decrease in the maximum concentration was hardly observed.

Example 2 Using the photosensitive material (101) prepared in Example 1, an oxidizing agent solution (OX) for amplification and development in the amplification and development processing step 2 of Example 1 was used.
No. 1 of Example 1 except that the pH of -1) was adjusted with sodium hydroxide or sulfuric acid as shown in Table 2. The same processing and evaluation as those of Sample No. 102 were performed, and the sample subjected to amplification development processing after being left for 5 minutes after exposure was subjected to the highest density (Dmax).
I asked. Then, in the same manner except that each of the oxidizing agent solutions for amplification and development was left at room temperature for 3 weeks after preparation,
Processing and evaluation were performed. The results are shown in Table 2.

[0114]

[Table 2]

In Example 2, amplification and development processing was performed by changing the pH of a photographic processing solution containing an oxidizing agent for amplification and development. From the results in Table 2, it can be seen that when the pH of the photographic processing solution containing the oxidizing agent for amplification is less than 10.0, the effect of the present invention is maintained even when the oxidizing agent for amplification is stored for 3 weeks after preparation. Is high, and a higher maximum concentration can be maintained, which is a preferable embodiment of the present invention.

Example 3 Using the photosensitive material (101) prepared in Example 1, an oxidizing agent solution (OX) for amplification and development in the amplification and development processing step 2 of Example 1 was used.
No. 1 of Example 1 except that a sequestering agent was added as shown in Table 3 in Table -1). The same processing and evaluation as those of Sample No. 102 were carried out, and further, the sample which was left for 5 minutes after exposure and subjected to amplification and development processing was determined for the maximum density (Dmax). Then, the supply temperature of the oxidizing agent solution for amplification development (OX-1) was increased to 40.0.
Processing and evaluation were carried out in the same manner except that the temperature was set to ± 1.0 ° C. Table 3 also shows the results.

Sequestering agent K-1: pyridine-2-carboxylic acid K-2: diethylenetriaminepentaacetic acid K-3: 1-hydroxyethylidene-1,1'-diphosphonic acid

[0118]

[Table 3]

In Example 3, amplification processing was performed by adding a sequestering agent to a photographic processing solution containing an oxidizing agent for amplification development. From the results in Table 3, when the photographic processing solution containing the oxidizing agent for amplification development contains a sequestering agent, when the supply temperature of the photographic processing solution containing the oxidizing agent for amplification development changes, It can be seen that this is a preferred embodiment of the present invention because the effect of the present invention is large and a higher maximum concentration can be maintained.

Example 4 Using the photosensitive material (101) prepared in Example 1, an oxidizing agent solution (OX) for amplification and development in the amplification and development processing step 2 of Example 1 was used.
No. 1 of Example 1 except that the amount of hydrogen peroxide was changed as shown in Table 4. The same processing and evaluation as those of Sample No. 102 were carried out, and further, the sample which was left for 5 minutes after exposure and subjected to amplification and development processing was determined for the maximum density (Dmax). Table 4 also shows the results.

[0121]

[Table 4]

In Example 4, amplification and development processing was performed by changing the amount of the oxidizing agent in the photographic processing solution containing the oxidizing agent for amplification and development. From the results in Table 4, the concentration of the oxidizing agent for amplification in the photographic processing solution containing the oxidizing agent for amplification was 0.
No. 3 mol / liter or more and 1.5 mol / liter or less. Nos. 102, 403, and 404 have the remarkable effect of the present invention that the gradation fluctuation when the time from exposure to amplification and development changes is small, and can obtain a higher maximum density. It turns out that it is an aspect.

Example 5 The photosensitive material (101) prepared in Example 1 was mixed with an oxidizing agent solution (OX) for amplification and development in the amplification and development step 2 of Example 1.
Processing and evaluation were performed in the same manner except that the supply method of -1) was changed as shown in Table 5, and the maximum density (Dmax) was determined for the sample which was left for 5 minutes after exposure and then subjected to amplification and development processing. . The results are shown in Table 5.

Processing bath: immersing and stirring the photosensitive material in 10 liters of a photographic processing solution contained in a 20 cm thick tank Thin processing bath: immersing the photosensitive material in a 5 mm thick thin tank to obtain a 250 ml photograph Circulation of processing solution for coating Coating: 80 ml of a photographic processing solution is applied and supplied in a kiss coat method per 1 m ^{2 of the} photosensitive material.

[0125]

[Table 5]

In Example 5, processing was performed by changing the method of supplying a photographic processing solution containing an oxidizing agent for amplification development to a photosensitive material. From the results shown in Table 5, among the image forming methods of the present invention, the method of supplying a photographic processing solution containing an oxidizing agent for amplification development in a mode of circulating through a thin tank, and the spray method and the coating method The method of directly supplying the amplification and development activating solution to the light-sensitive material can obtain a high maximum concentration, and it is understood that this is a particularly preferred embodiment of the present invention.

Example 6 (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)
The average particle size was 0.30 μm and the average silver chloride content was 99.5 mol% in the same manner except that the addition time of the solution (D1) was changed.
To obtain a monodispersed cubic emulsion EMP-11A. The above EMP
-11A was optimally subjected to chemical sensitization at 60 ° C. using the following compound to give a green-sensitive silver halide emulsion (Em-G
1) 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)
The average particle size was 0.35 μm, and the average silver chloride content was 99.5 mol%, except that the addition time of (D1 solution) was changed.
To obtain a monodispersed cubic emulsion EMP-21A. The above EMP
-21A was optimally subjected to chemical sensitization at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion (Em-R
1) 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

[0130]

Embedded image

(Preparation of silver halide photographic light-sensitive material (601)) On the support used in Example 1, a gelatin undercoat layer was provided, and each layer having the following constitution was further coated. Materials were made. In the production of 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

[0135]

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[0136]

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[0137]

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The light-sensitive material (60
For 1), processing, measurement and evaluation were performed in the same manner as in Example 1. However, the measurement was performed with blue light, green light, and red light, and the change in gradation was determined for each of them. Table 6 shows the results.

[0139]

[Table 6]

In Example 6, processing was performed on a photosensitive material having a plurality of color image forming layers having different hues on a support. From the results shown in Table 6, when the image forming method of the present invention was used, the gradation fluctuation in each color image forming layer was small, and the difference in the gradation fluctuation width between each color image forming layer was also small. It can be seen that the stability of the gradation and the gradation balance with respect to the change in the time until the amplification development is improved.

Further, after the photosensitive material (601) was subjected to image exposure through a Konica Color LV400 color negative film which had been photographed and developed, the processing was performed by changing the amplification and development processing method as described above. The resulting printed image was observed. As a result, it was confirmed that in the image forming method of the present invention, a beautiful printed image was obtained even when the time from exposure to amplification and development changed.

Example 7 (Preparation of photosensitive material (701)) After a corona discharge treatment was applied to the reflective support prepared in Example 1, a gelatin undercoat layer was provided, and each layer having the following structure was further provided. A silver halide photographic material (701) was prepared. 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) and (S
U-2) and (SU-3) were added to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² .

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 photosensitive layer) Gelatin 1. 30 Blue photosensitive emulsion (Em-B1) 0.025 Cyan coupler (C-2) 0.30 Color developing agent (HCD-1) 0.12 Color developing agent (HCD-2) 0.10 Dye image stabilizer (ST-1) 0.10 Stain inhibitor (HQ-1) 0.004 DBP 0.30 DOP 0.60 Support polyethylene laminated paper The amount of silver halide is shown in terms of silver.

[0145]

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The light-sensitive material (70
For 1), light wedge exposure was performed for 0.5 seconds with white light, and after standing for 5 minutes after exposure, the following amplification and development processing steps 71 to 73 were performed.
And the desilvering process in the desilvering process step 2 was performed. In each of the amplification and development processing steps, the supply method of each photographic processing solution is described in Example 1.
The same was done. Next, the same processing and measurement were performed except that the time from exposure to amplification and development was changed to 1 minute, and the same measurement and evaluation as in Example 1 were performed on each of the obtained samples. Table 7 shows the results.

Amplification Development Step 71 Processing Time Supply Method Amplification Developer (CDA-2) 50 seconds Processing Bath Amplification Development Step 72 Processing Time Supply Method Activating Solution (AA-1) 20 seconds Processing Bath Oxidizer Solution (OX) -1) 45 seconds Spray Amplification and development processing step 73 Processing time Supply method Oxidizer liquid (OX-1) 20 seconds Processing bath Activating liquid (AA-1) 45 seconds Spray Desilvering processing step 2 Processing time Processing temperature Bleaching fixer (BF-1) 45 seconds 30.0 ± 0.5 ° C. Stabilizing solution 60 seconds 30-34 ° C. Alkaline solution (AL-1) 30 seconds 30-34 ° C. Drying 30 seconds 60-80 ° C. It is shown below.

Amplification developer (CDA-2) Pure water 800 ml Potassium bromide 0.001 g Potassium chloride 1.0 g N, N-diethylhydroxylamine 4.7 g Hydroxylamine sulfate 1.0 g Diethylenetriaminepentaacetate 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 to 11.6 with potassium hydroxide or sulfuric acid, and add water to make the total amount 1 liter.

Alkaline solution (AL-1) Pure water 800 ml Disodium hydrogen phosphate 10 g Potassium carbonate 20 g Adjust the pH to 10.0 with potassium hydroxide or sulfuric acid, and add water to make the total amount 1 liter.

[0150]

[Table 7]

Example 7 relates to a photosensitive material in which a color developing agent is incorporated in advance. From the results shown in Table 7, even when the image forming method of the present invention is used, the gradation variation when the time from exposure to amplification and development is small is preferable even in the photosensitive material in which the color developing agent is previously incorporated. You can see that.

[0152]

According to the present invention, it is possible to provide an image forming method in which the gradation fluctuation and the stability of gradation balance due to the change in the time from exposure to amplification and development are improved.

Claims (9)

[Claims] Claims: 1. An imagewise exposed silver halide photographic light-sensitive material comprises at least a color developing agent, an oxidizing agent for amplification development,
And in an image forming method of performing amplification development in the presence of an amplification developing activity-imparting agent, after supplying a color developing agent and an amplification developing activity-imparting agent to a silver halide photographic light-sensitive material, An image forming method comprising supplying a photosensitive material. 2. An oxidizing agent for amplification development is supplied as a photographic processing solution having a pH of less than 10.0.
2. The image forming method according to 1., 3. A photographic processing solution containing an oxidizing agent for amplification, wherein the concentration of the oxidizing agent for amplification is not less than 0.3 mol / l and not more than 1.5 mol / l. 3. The image forming method according to 1 or 2. 4. The image forming method according to claim 1, wherein the photographic processing solution containing the oxidizing agent for amplification and development contains at least one sequestering agent. 5. A thin photographic processing solution containing an oxidizing agent for amplification and development is supplied directly to a silver halide photographic material or the thickness of the inside of a tank is 100 times or less the thickness of the photographic material. The image forming method according to claim 1, wherein the image forming apparatus is supplied in a state of being held or circulated in a tank. 6. The photosensitive silver halide contained in the silver halide photographic material has an average silver chloride content of 80 mol%.
The method according to any one of claims 1 to 5, wherein
Item. 7. The image forming method according to claim 1, wherein the oxidizing agent for amplification and development is hydrogen peroxide or a compound that gives hydrogen peroxide. 8. The image forming method according to claim 1, wherein the amplification development processing is performed in the presence of a black-and-white developing agent. 9. An amount of photosensitive silver halide contained in a silver halide photographic light-sensitive material is 0.001 g / m ^{2 in} terms of silver.
Above, the image forming method according to any one of claims 1 to 8, characterized in that 0.3 g / m ² or less.