JPH10288832A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the image forming method capable of attaining both of the high maximum density and the low minimum density at the same time in amplification development processing in the case of high illuminance short time exposure by supplying an oxidant for amplification development and an amplification development activator to a silver halide photographic sensitive material and then, a color developing agent to the photosensitive material. SOLUTION: The oxidant for the amplification development and the amplification development activator has been supplied to the image-wise exposed silver halide photographic sensitive material, and then, the color developing agent is added to this material, preferably, in an amount of 12-60 mmol/l of the processing solution, thus permitting drop of the maximum density to be small even in the case of shortening an amplification developing time, and deterioration of a processing solution for a desivering process due to a amount of the developing agent carried out to be relieved by controlling an amount of the color developing agent. The color developing solution containing this developing agent is preferably adjusted in <= pH 10.0 from the view point of its storage stability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method capable of simultaneously achieving a high maximum density and a low minimum density even when exposed to high illuminance for a short time in an amplification development process.

[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 features described above, furthermore, the silver halide content in the light-sensitive material can be reduced, the silver halide processing time can be reduced or omitted, and silver halide is a preferable means in terms of effective use of resources. A method for forming an image by subjecting a photographic light-sensitive material to amplification development processing has been known for a long time. As an example of the amplification development processing, hydrogen peroxide
There is a method in which an oxidized color developing agent is formed with an oxidizing agent such as a cobalt (III) complex and then reacted with a coupler to form an image dye.

In recent years, the number of opportunities for handling image information as digital information has increased. As a light source for exposing a photosensitive material based on the digitized image information, an L light source has been proposed.
EDs, semiconductor lasers, and light sources combining non-linear optical crystals and solid-state lasers have attracted attention from the viewpoint of easy control and high resolution. In the conventional method of exposing a photosensitive material through a negative film on which image information is recorded, the exposure time is about 10 ^-2 to 10 seconds, whereas in the exposure using a laser or the like, the illuminance is reduced. Irradiate high light for a very short time of 10 ^-3 to 10 ^-7 seconds,
This is a so-called high-illuminance short-time exposure.

Normally, when exposing digitized image information to a photosensitive material, a conversion table (LUT) that associates the relationship between the exposure amount and the color density is placed in an exposure system control circuit to digitize the image information. The image information refers to the LUT, and derives an exposure amount that will give an appropriate color density when developed.
Based on this, exposure of the photosensitive material is performed. However, there is generally a limit on the exposure range that can be controlled digitally.
When light-sensitive material exposed to high-intensity light for a short time is subjected to amplification and development processing, gradation from medium density to high density range (shoulder gradation)
And the characteristic curve tends to be sharply bent, and at the same time, the tone (leg gradation) from the middle density to the low density range tends to be softened by amplification and development in the low exposure area. It was difficult to achieve sufficient maximum and minimum concentrations within the control range of the amount. In particular, when the silver chloride content is 8
When a photosensitive silver halide having a high silver chloride content of 0 mol% or more is used, the effect as a so-called catalyst poison that suppresses the amplification development reaction is small, so that a high amplification development rate can be achieved. When the maximum exposure is adjusted so as to obtain a sufficiently low minimum density in the exposure range that can be controlled digitally, it is difficult to obtain a sufficient maximum density, The improvement was desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an image forming method capable of simultaneously achieving a high maximum density and a low minimum density even when exposed to high illuminance for a short time in an amplification development process. .

[0006]

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

(1) In an image forming method, an imagewise exposed silver halide photographic material is subjected to amplification development processing in the presence of at least a color developing agent, an oxidizing agent for amplification development, and an agent for imparting amplification development activity. An image forming method, comprising: supplying an oxidizing agent for amplification development and an amplification development activator to a silver halide photographic material, and then supplying a color developing agent to the photographic material.

(2) The color developing agent is supplied as a photographic processing solution having a pH of 10.0 or less.
2. The image forming method according to 1.,

(3) The image forming method as described in (1) or (2) above, wherein the concentration of the color developing agent in the photographic processing solution containing the color developing agent is 12 mmol / L or more and 60 mmol / L or less. Method.

(4) The image forming method as described in (3) above, wherein the concentration of the color developing agent in the photographic processing solution containing the color developing agent is from 25 mmol / L to 60 mmol / L.

(5) A photographic processing solution containing a color developing agent is supplied directly to a silver halide photographic light-sensitive material or in a thin tank in which the thickness inside the tank is 100 times or less the thickness of the light-sensitive material. The image forming method according to any one of claims 1 to 4, wherein the image forming apparatus is supplied in a state of being held or circulated.

(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 oxidizing agent for amplification and development is a compound that gives hydrogen peroxide, such as hydrogen peroxide or a salt of hydrogen peroxide and an addition compound of hydrogen peroxide. The image forming method according to claim 1.

(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 silver halide photographic material described above, wherein the amount of photosensitive silver halide is 0.001 g / m ² or more and 0.3 g / m ² or less. 9. The image forming method according to any one of 8.

(10) One of silver halide photographic materials
The image forming method according to any one of the above items 1 to 9, wherein the exposure is performed so that the exposure time per pixel is 10 ^-3 seconds or less.

With the above structure, when the photosensitive material exposed to high illuminance for a short time is amplified and developed, the phenomenon that the leg gradation is softened is improved, and a high maximum density and a low minimum density can be simultaneously achieved. Although the mechanism by which the effects of the present invention can be obtained is not clear, it is considered that when short-time exposure with high illuminance is performed, a relatively weak and unstable latent image is likely to be formed in a low exposure amount region. By supplying the oxidizing agent for amplification development and the amplification development activator to the photosensitive material, and then supplying the color developing agent to the photosensitive material, bleaching is performed before the weak and unstable latent image as described above is developed. When the maximum value of the exposure is set so as to obtain a sufficient maximum density in the digitally controlled exposure method, the minimum value due to the softening in the amplification development especially in the low exposure range. It is considered that the minimum density can be kept low by improving the increase in density and further by bleaching the fog nuclei of the silver halide grains in advance.

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

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. This means an amplification developer component capable of increasing the image formation speed by amplification development by a factor of 3 or more.

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

In the present invention, the term "amplification development" 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.

Hydrogen peroxide, oxidizing agent for amplification development
Compounds that give hydrogen peroxide such as salts of hydrogen peroxide and adducts of hydrogen peroxide; peroxo compounds such as peroxoborates and peroxocarbonates; cobalt (III) complexes such as cobalt hexaammine complexes; chlorite; Halogenated acid, periodic acid and the like can be used. 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 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
No. 5,593,110, JP-A-8-202002, JP-A-8-227131, and JP-A-8-234390, etc., can also be preferably used as the sulfonyl hydrazide and carbonyl hydrazide type color developing agents.

As an image forming method of the present invention, for example, a photographic processing solution containing an oxidizing agent for amplification development and an agent for imparting amplification development activity is supplied to a photosensitive material, and then a color developing agent is supplied to the photosensitive material. (P-1 below) or a method of supplying an oxidizing agent for amplification development to a photosensitive material, swelling the photosensitive material, supplying an amplification developing activity imparting agent, and further supplying a color developing agent to the photosensitive material ( The following P-2) can be used. Preferred embodiments of the image forming method of the present invention include: P-1) an oxidizing agent / activator → a color developing agent P-2) an oxidizing agent → an activator → a color developing agent P-3) an oxidizing agent / activator → color developing agent / activity imparting agent P-4) oxidizing agent / activity imparting agent → color developing agent / oxidizing agent P-5) activity imparting agent → oxidizing agent → color developing 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 according to the present invention, when the color developing agent is supplied to the photosensitive material, the amplification developing efficiency is increased by the diffusion of the components of the amplification developing solution, which have been supplied to the photosensitive material, out of the photosensitive material. In order to suppress the deterioration of the photographic processing solution, a photographic processing solution containing a color developing agent is directly supplied 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 reduced. It is preferable that the photosensitive material is supplied in a state of being held or circulated in a thin tank having a thickness of 100 times or less the thickness of the photosensitive material. Particularly preferred is a mode in which a photographic processing solution containing a color developing 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 color developing agent supplied to the photographic material after the oxidizing agent for amplification development and the activating agent for amplification development 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 an oxidizing agent for amplification development, an agent for imparting amplification development activity, an inhibitor, a preservative, and a chelating agent as long as the effect is not hindered. When an oxidizing agent for amplification development and an agent for imparting amplification development activity are added to a photographic processing solution containing a color developing agent, these are preferably used supplementarily. In this case, the amounts of the oxidizing agent for amplification development and the amplification development activator supplied to the photosensitive material from the photographic processing solution containing the color developing agent are determined before the color developing agent is supplied to the photosensitive material. The amount is preferably １ ／ or less, more preferably １ ／ or less of the amounts of the amplification developing agent and the amplification developing activity imparting agent supplied to the toner.

In the present invention, there is provided an image forming method in which a photographic processing solution containing an amplification developing activator or an oxidizing agent for amplification is not supplied to the photosensitive material after the color developing agent is supplied to the photosensitive material. This is a particularly preferred embodiment of the present invention, since it is possible to reduce the amount.

In the present invention, the preferred amount of the color developing agent in the photographic processing solution containing the color developing agent is 12 to 60.
Mmol / l, particularly preferably 25 to 60 mmol / l. When the amount of the color developing agent is in the above range, the decrease in the maximum density is small even when the amplification development time is shortened, and the deterioration of the processing solution for desilvering processing due to the carry-out of the color developing agent can be reduced. This is a preferred embodiment.

In the present invention, the pH of a photographic processing solution containing a color developing agent is adjusted to pH 1 from the viewpoint of storage stability.
It is preferably at most 0.0, more preferably at most pH 7.0.

In the present invention, when a photographic processing solution containing both an oxidizing agent for amplification development and an activator for amplification development is used, from the viewpoint of the stability of the processing solution, the concentration of the oxidizing agent for amplification development is: It is preferable that it is in the range of 0.05 to 0.3 mol / liter, and the pH is 10.0 or less.

In the present invention, the pH at the time of amplification development is preferably pH 9.0 to 12.5 from the viewpoint of rapid processing, and more preferably pH 10.5 to 12.0.

In the present invention, the pH at the time of amplification development is
Refers to the pH of a photographic processing solution in the presence of a color developing agent, an oxidizing agent for amplification development, and an agent for imparting amplification development activity, and the components of the amplification developing solution are divided into a plurality of photographic processing solutions, each of which is sprayed. When the solution is supplied directly to the photosensitive material using a method or a coating method, the amplification processing is performed by adjusting the pH of each photographic processing solution containing the components of the amplification developer in the ratio supplied to the photosensitive material. PH can be considered. 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, when the photosensitive material in a dry state is immersed in the processing bath. 2/3 of the saturated absorption amount of the above is used as the amount of processing solution supplied to the photosensitive material, and the pH of the solution obtained by previously mixing the respective photographic processing solutions containing the components of the amplification developing solution in the ratio supplied to the photosensitive material is obtained. It can be considered as the pH at the time of amplification development.

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.

In the present invention, a photographic processing solution containing an oxidizing agent for amplification development or an agent for imparting amplification development activity contains a development inhibitor such as chloride ion or benzotriazole as long as the effect of the present invention is not impaired. A preservative, a chelating agent and the like can be used together.

In the present invention, when a black-and-white developing agent is used in combination during amplification development, the amplification processing time can be shortened. When the photosensitive material has a plurality of color image forming layers, the development of other layers can be reduced. The presence or absence is preferable because the influence on the image forming speed of the own layer is reduced.

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 photosensitive 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 limited, and may be any of silver chloride, silver bromide, silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver chloroiodide and the like. Although a silver halide emulsion having a halogen composition may be used, when a silver halide emulsion having a silver chloride content of 80 mol% or more is used, the effect as a so-called catalyst poison that suppresses the amplification and development reaction is small, so that a high amplification is used. Although the development rate can be achieved, it was particularly difficult to achieve a low minimum density and a high maximum density at the same time with the softening of the leg gradation for high-intensity short-time exposure,
The effects of the present invention are particularly useful.

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.

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 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 grains before forming the silver halide grains, 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 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 kinds of 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 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.

Also, 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 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 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 graininess can be improved while maintaining high sensitivity, and is particularly preferred.

The silver halide emulsion used in the light-sensitive material of 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 fogging that occurs during the preparation of the light-sensitive material, reduces performance fluctuations during storage, and prevents fogging that occurs 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 within 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 layers, so-called inter-image 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.

As the coupler for use 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.

The cyan coupler preferably usable in the light-sensitive material of the present invention is 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 couplers and other organic compounds used in the light-sensitive material according to the present invention, they are 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.

As a compound preferable as a surfactant used for dispersing a photographic additive or adjusting the surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution 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 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-3-25184.
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.

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 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 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 known compounds can be used. As the blue-sensitive sensitizing dye, BS-1 to 8 described in JP-A-3-251840, page 28, can be used alone. Or in combination. As the green photosensitive sensitizing dye, the same publication 28
GS-1 to GS-5 described on the page are preferably used. As the red-sensitive sensitizing dye, RS described on page 29 of the same publication is used.
-1 to 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, other gelatins, 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.

Further, it is more preferable 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, because the effect of good gloss is obtained.
In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

The light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion of the support surface, antistatic property, 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.

In order to form a photographic image using the photosensitive material according to the present invention, it is preferable to convert the image information into digital information once and then expose the photosensitive material based on the digital information.

The types of light sources that can be used in the present invention include a xenon discharge tube, a cathode ray tube (CRT), a light emitting diode (LED), a tungsten halogen lamp, a mercury high pressure discharge tube, a gas laser, and a semiconductor laser (L
D) Any known light source such as a combination of an LD and a second harmonic generation element (a so-called SHG element) can be used. In particular, when performing exposure such that the exposure time per pixel is 10 ^-3 seconds or less, LEDs, LDs, and LEDs are used in consideration of image quality, compactness of the apparatus, and easy control of light quantity.
It is preferable to use a light source based on a combination of D and an SHG element.

In the image forming method of the present invention, when the exposure time per pixel is 10 ^-3 seconds or less, the effect of the present invention is remarkable and the present invention can be used effectively. The exposure time here is, in the case of flash exposure, the temporal change in light intensity,
The time from when the maximum value reaches 1/2 to the time when it attenuates to 1/2 of the maximum value. In the case of scanning exposure with laser light, the spatial intensity of the light flux When the light intensity becomes 1/2 of the maximum value, the outer edge of the light beam is defined as the outer edge of the light beam. Between the two points where the line that is parallel to the scanning line and passes through the point where the light intensity becomes the maximum and the outer edge of the light beam intersects Is the light beam diameter, the value obtained by dividing the light beam diameter by the scanning speed is defined as the exposure time. Scanning exposure using an array of light sources may be considered in the same manner as the above-described scanning exposure using laser light.

Examples of the exposure apparatus applicable to the image forming method of the present invention include, for example, JP-A-55-4071 and JP-A-55-4071.
9-11062, JP-B-56-14963, JP-B-56-40822, and European Patent 77410.
No., IEICE Technical Report Vol. 24
4 and Movie Television Technology 1984/6 (382), 34-
And those described on page 36 and the like.

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.

The processing apparatus used in the image forming method of the present invention may be a roller transport type in which the photosensitive material is transported between rollers disposed in a processing bath, or may be transported with the photosensitive material fixed to a belt. An endless belt method may be used, but a processing 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.

[0090]

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 addition of water (Solution B1) 10 g of silver nitrate 200 ml with addition of water 200 ml (Solution C1) 102.7 g of sodium chloride 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 µ
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1A was obtained. The above-mentioned EMP-1A was optimally subjected to chemical sensitization at 60 ° C. using the following compounds to give a blue-sensitive silver halide emulsion (Em-B
1) was obtained.

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

[0094]

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

The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) Second layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 First layer (blue 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

[0099]

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The light-sensitive material (10
In contrast to 1), an Ar laser (oscillation wavelength: 430 nm) is used as a light source, AOM is combined, and scanning exposure is performed based on image information so that the average exposure time per pixel is 6.4 × 10 ^-6 seconds. went. Note that the maximum value of the exposure amount was used in a region where the minimum density increase depending on the exposure did not occur in combination with the AOM. Next, the amplification and development processing was performed in any of the amplification and development processing steps 1 to 7, followed by the desilvering processing in the desilvering processing step. In each amplification / development process, the supply method of each photographic processing solution is as follows: processing bath: immersing and stirring the photographic material in 10 liter photographic processing solution in a 20 cm thick tank Spray: 1 m of the photographic material using either supplied by spraying a photographic processing solution of ² per 80 ml.

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 the maximum density (Dmax) were determined. The results are shown in Table 1.

Amplification development processing step 1 Processing time Supply method Amplification developer (CDA-1) 50 seconds Processing bath Amplification development processing step 2 Processing time Supply method Oxidizer liquid (OX-1) 20 seconds Processing bath activating liquid (AA) -1) 20 seconds Spray Color developing solution (CD-1) 45 seconds Spray Amplification development process 3 Processing time Supply method Oxidizing agent solution (OX-1) 20 seconds Processing bath activating solution (AA-1) 20 seconds Spray Coloring Developing solution (CD-2) 45 seconds Spray Amplification development processing step 4 Processing time Supply method Color developing solution (CD-2) 40 seconds Processing bath Oxidizing agent liquid (OX-1) 45 seconds Spray Amplification development processing step 5 Processing time Supply Method Oxidant solution (OX-2) 40 seconds Processing bath Color developing solution (CD-1) 45 seconds Spray Amplification development process 6 Processing time Supply method Oxidant solution (OX-2) 40 seconds Processing Bath Color developing solution (CD-2) 45 seconds Spray Amplification developing process 7 Processing time Supply method Oxidizing agent solution (OX-2) 40 seconds Processing bath Color developing solution (CD-3) 45 seconds Spray Desilvering process Process time Processing temperature Bleaching-fixing solution (BF-1) 45 seconds 30.0 ± 0.5 ° C. Stabilizing solution 60 seconds 30-34 ° C. Drying 30 seconds 60-80 ° C. The composition of the 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 13 0.0 mmol N, N-diethylhydroxylamine 4.7 g Hydroxylamine sulfate 1.0 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g 1-hydroxyethylidene-1,1'-diphosphonic acid 0.35 g Potassium carbonate 20 g Hydrogen peroxide (5.99%) 25 ml Adjust the pH to 10.3 with potassium hydroxide or sulfuric acid, and add water to make the total volume 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 13.0 mmol hydroxylamine sulfate 1.0 g Adjust the pH to 2.0 with potassium hydroxide or sulfuric acid, and add water to make the total volume 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 13.0 mmol hydroxylamine sulfate 1.0 g potassium carbonate 20 g Adjust the pH to 10.3 with potassium hydroxide or sulfuric acid, and add water to make the total volume 1 liter.

Color developing agent solution (CD-3) Pure water 800 ml Potassium bromide 0.001 g Potassium chloride 0.35 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 13.0 mmol hydroxylamine sulfate 1.0 g potassium carbonate 20 g Adjust the pH to 8.0 with potassium hydroxide or sulfuric acid, and add water to make the total volume 1 liter.

Oxidant solution (OX-1) Pure water 800 ml Diethylenetriaminepentaacetic acid sodium salt 2.0 g 1-hydroxyethylidene-1,1'-diphosphonic acid 0.35 g Hydrogen peroxide (5.99%) 25 ml Hydroxic acid Adjust the pH to 6.5 with potassium or sulfuric acid and add water to bring the total volume to 1 liter.

Oxidant liquid (OX-2) Pure water 800 ml Diethylenetriaminepentaacetic acid sodium salt 2.0 g 1-hydroxyethylidene-1,1'-diphosphonic acid 0.35 g Hydrogen peroxide (5.99%) 25 ml Potassium carbonate 20 g Adjust the pH to 11.0 with potassium hydroxide or sulfuric acid and add water to bring the total volume to 1 liter.

Activating solution (AA-1) (photographic processing solution containing the amplification developing activity-imparting agent of the present invention) (hereinafter also referred to as amplification developing activating solution) Pure water 800 ml Potassium carbonate 20 g pH with potassium hydroxide or sulfuric acid Is adjusted to 13.0 and water is added to bring the total volume to 1 liter.

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

Stabilizing solution Pure water 800 ml o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1 0.0 g fluorescent whitening agent (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g bismuth chloride (45% aqueous solution) 0.65 g magnesium sulfate heptahydrate 0.2 g PVP (polyvinylpyrrolidone) 1.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water. .

[0113]

[Table 1]

From the results shown in Table 1, it can be seen that, in the image forming method of the present invention, in the case of high illuminance short-time exposure by laser based on digital image information having a limited exposure area width,
It can be seen that both a low minimum concentration and a high maximum concentration can be achieved simultaneously.

Example 2 The photosensitive material (101) prepared in Example 1 was subjected to N-ethyl-N- (β methane) in the color developing solution (CD-1) in the amplification and development step 5 of Example 1. Sulfonamidoethyl)
Processing and evaluation were performed in the same manner except that the amount of -3-methyl-4-aminoaniline sulfate (color developing agent) was changed as shown in Table 2. The results are shown in Table 2.

[0116]

[Table 2]

In Example 2, amplification development was performed by changing the concentration of the color developing agent in the photographic processing solution containing the color developing agent. From the results in Table 2, when the concentration of the color developing agent in the photographic processing solution containing the color developing agent is 12 mmol / L or more, a higher maximum concentration can be obtained, and the spray time of the color developing solution can be obtained. It can be seen that even when is shortened to 30 seconds, it has a high maximum density. In addition, No. 3 having a color developing agent concentration of 60 mmol / L or more. In No. 206, adhesion of sludge was observed on the tank wall surface of the bleach-fix solution (BF-1) used in the desilvering process. From the above, it can be seen that a case where the concentration of the color developing agent in the photographic processing solution containing the color developing agent is 12 mmol / L or more and 60 mmol / L or less is a particularly preferred embodiment of the present invention.

Example 3 With respect to the photosensitive material (101) prepared in Example 1, the pH of the color developing solution (CD-1) in the amplification and development processing step 5 of Example 1 was changed as shown in Table 3. , Color developer (CD-
The treatment and evaluation were performed in the same manner as in Example 1 for each of the case where 1) was prepared on the day of the treatment and the case where it was left at room temperature for 3 weeks after the preparation. Table 3 also shows the results.

[0119]

[Table 3]

In Example 3, the pH of a photographic processing solution containing a color developing agent was changed, and after a lapse of time, an amplification development process was performed. From the results in Table 3, it can be seen that when the pH of the photographic processing solution containing the color developing agent is 10.0 or less, a high maximum density and a low minimum density are achieved even when the photographic processing solution is aged. It can be seen that this is a preferred embodiment of the present invention.

Example 4 To the photosensitive material (101) produced in Example 1, the supply method of the color developing solution in the amplification and development processing step 5 of Example 1 was changed in the same manner as described below. Processing and evaluation were performed. Table 4 shows the results.

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

[0123]

[Table 4]

In Example 4, the processing was performed by changing the method of supplying the color developing solution to the photosensitive material. From the results shown in Table 4, among the image forming methods of the present invention, a photographic processing solution containing a color developing agent was circulated in a thin tank in which the thickness inside the tank was 100 times or less the thickness of the photosensitive material. It can be seen that the method of directly supplying the color developing solution to the photosensitive material, such as the spray method and the coating method, has a large effect of the present invention and is preferable.

Example 5 (Preparation of silver halide emulsions (Em-B2) and (Em-B3)) (Solution A1) and (Solution C1) used for the preparation of silver halide emulsion EMP-1A in Example 1 To each (A2 solution),
(C2 liquid) except that the average particle diameter was 0.1.
A monodisperse cubic emulsion (EMP-2A) having a grain size of 57 μm and a silver chloride content of 85 mol% was prepared, subjected to the same spectral chemical sensitization as in the preparation of (Em-B1), and subjected to a blue-sensitive silver halide emulsion (Em-B1). B2) was prepared. In addition, (A1 liquid), (C1
Solution) was changed to (A3 solution) and (C3 solution), respectively, to prepare a monodispersed cubic emulsion (EMP-3A) having an average particle size of 0.57 μm and a silver chloride content of 75 mol%,
The same spectral sensitization as in the preparation of (Em-B1) was performed to prepare a blue-sensitive silver halide emulsion (Em-B3).

(A2 solution) Sodium chloride 2.92 g Potassium bromide 1.05 g Water was added to 200 ml (C2 solution) Sodium chloride 87.7 g 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 Water was added to 600 ml (Preparation of photosensitive materials (501) and (502)) In the preparation of the photosensitive material (101), the types of the photosensitive silver halide emulsions were (Em-B2) and (Em-B2). Photosensitive material in the same manner except for changing the -B3) (501), and (502) was prepared.

The photosensitive material (50
For Nos. 1) and (502), No. 1 of the first embodiment. 10
The same processing and evaluation as in 1, 104 and 105 were performed. Table 5 shows the results.

[0128]

[Table 5]

In Example 5, processing was performed by changing the halogen composition of the photosensitive silver halide in the photosensitive material. From the results in Table 5, among the image forming methods of the present invention,
When a photosensitive silver halide having a silver chloride content of 80 mol% or more is used, a higher maximum density can be obtained,
It turns out 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 the silver halide emulsion EMP-1A of Example 1, the addition time of (A1 solution) and (B1 solution) and (C1 liquid)
A monodispersed cubic emulsion EMP-11A having an average particle size of 0.30 μm and a silver chloride content of 99.5 mol% was obtained in the same manner as above except that the addition time of the solution (D1) was changed. The above EMP-1
1A was optimally chemically sensitized at 60 ° C. using the following compound to obtain a green light-sensitive silver halide emulsion (Em-G1).

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

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

[0133]

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

[0138]

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[0139]

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[0140]

Embedded image

The light-sensitive material (60
For 1), based on the digitized image data,
AO independently from each of the three laser light sources
M and the average exposure time per pixel is 6.4
Scanning exposure was performed while controlling to be × 10 ⁻⁶ seconds.
The exposure was performed using an Ar laser (oscillation wavelength: 430 nm), He
A -Ne laser (oscillation wavelength 544 nm) and a semiconductor laser (oscillation wavelength 670 nm) were used as light sources. Next, after performing the processing in any one of the amplification and development processing steps 1 to 7 in the same manner as in Example 1, the desilvering processing in the desilvering processing step was performed. For the obtained sample, PDA-65
Blue light, green light,
Measure the reflection density by red light, yellow, magenta,
The minimum and maximum densities were determined for each cyan image. Table 6 shows the results.

[0142]

[Table 6]

In Example 6, processing was performed on a full-color photosensitive material having a plurality of color image forming layers having different hues on a support. From the results shown in Table 6, it can be seen that even when the image forming method of the present invention is used for a full-color photosensitive material, a low minimum density and a high maximum density can be simultaneously achieved in each color image forming layer.

[0144]

According to the present invention, in the amplification development processing,
It was possible to provide an image forming method capable of simultaneously achieving high maximum density and low minimum density even when exposed to high illuminance for a short time.

Claims (10)

[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 in which amplification development processing is performed in the presence of an amplification development activator, an amplification oxidizing agent and an amplification development activator are supplied to a silver halide photographic material, and then a color developing agent is supplied to the photosensitive material. An image forming method. 2. The image forming method according to claim 1, wherein the color developing agent is supplied as a photographic processing solution having a pH of 10.0 or less. 3. The concentration of a color developing agent in a photographic processing solution containing a color developing agent of 12 mmol / L or more,
3. The image forming method according to claim 1, wherein the amount is not more than millimol / liter. 4. The concentration of a color developing agent in a photographic processing solution containing a color developing agent of 25 mmol / L or more,
The image forming method according to claim 3, wherein the amount is not more than millimol / liter. 5. A photographic processing solution containing a color developing agent is supplied directly to a silver halide photographic light-sensitive material or is contained in a thin tank in which the thickness inside the tank is 100 times or less the thickness of the light-sensitive material. The image forming method according to claim 1, wherein the image forming apparatus is supplied in a held or circulated manner. 6. The photosensitive silver halide contained in the silver halide photographic material has an average silver chloride content of 80 mol%.
The image forming method according to claim 1, wherein: 7. The method according to claim 1, wherein the oxidizing agent for amplification and development is hydrogen peroxide or a compound that gives hydrogen peroxide such as a salt of hydrogen peroxide and an addition compound of hydrogen peroxide.
7. The image forming method according to any one of 6. 8. The method according to claim 1, wherein the amplification development processing is performed in the presence of a black-and-white developing agent.
Item. 9. An amount of a photosensitive silver halide contained in a silver halide photographic light-sensitive material of 0.001 g / m ² or more,
2. The composition according to claim 1, wherein the weight is 0.3 g / m ² or less.
The image forming method according to any one of claims 1 to 8, wherein 10. The image forming method according to claim 1, wherein the exposure is performed such that the exposure time per pixel of the silver halide photographic material is 10 ^-3 seconds or less. Method.