JPH11160844A - Color developing treating liquid for silver halide color photographic sensitive material and its treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain good gradation stability and sensitivity stability even in rapid treatment and to obtain low development fog and bleach fog. SOLUTION: As for the treating liquid, a treating liquid for color development contains lithium ion by >=0.01 mol/l and <=0.5 mol/l and contains a color developing agent by 0.025 mol/l to 0.10 mol/l. Preferably, the color developing liquid above described contains iodine ion by 6.0×10<-7> mol/l to 7.0×10<-5> mol/l.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developing solution and a processing method for a silver halide color photographic light-sensitive material, and more particularly, it is possible to obtain good gradation stability and sensitivity stability even in rapid processing. And a color developing solution and a processing method for a silver halide color photographic light-sensitive material capable of simultaneously obtaining low development fog and bleaching fog.

[0002]

2. Description of the Related Art With the rapid increase of minilab shops in recent years, silver halide photographic materials (hereinafter simply referred to as photographic materials,
Sometimes referred to as sensible material. ), The demand for faster processing is increasing. Means for achieving rapid processing include increasing the concentration of a color developing agent (hereinafter sometimes simply referred to as "main agent") described in JP-A-4-67038 and the like, and described in JP-A-4-81848. Investigations have been made on speeding up processing by activating the color developing solution such as by raising the temperature. Also, a method of increasing the pH of the processing solution to increase the activity of the processing solution has been studied, and a technique for incorporating lithium hydroxide into the processing solution for color development is disclosed in JP-A-7-175175. Have been. However, in this technology, lithium hydroxide is added as a preferable alkali agent for improving the physical performance of the solid processing agent, and is not a technology relating to properties as a processing solution for rapid processing as in the present invention, and Even in the case of a processing solution for processing a silver halide photographic light-sensitive material, the concentration of lithium hydroxide is out of the range of the present invention, and is not technically related to the present invention.

[0003]

In the color developing process, the color developing agent and the alkaline agent react from the upper layer, so that the arrival of the agent and the alkaline agent to the lowermost layer is greatly delayed. In the case of performing rapid processing, since the main drug is not sufficiently supplied to the lowermost layer, improvement of the developability of the lowermost layer is the greatest problem in realizing rapid processing. Therefore, as mentioned above,
Investigations aimed at improving the developability of the lowermost layer even with a small amount of color developing agent by increasing the reactivity of the color developing agent by increasing the pH of the color developing solution have been repeated.

However, since the alkaline agent is consumed in the upper layer due to the neutralization reaction in the dye-forming reaction, even if the pH of the processing solution is increased, the immersion time is short in the case of rapid processing, so that the pH rises in the lowermost layer. Although the effect of (1) is weakened and the developability of the lowermost layer can be improved, after all, the layers other than the lowermost layer are greatly affected by the activation due to the increase in the pH of the processing liquid, and the color balance is improved. Was difficult.

Further, when the processing solution is activated by an increase in pH, the development reaction in the unexposed area is also activated at the same time, so that a so-called development fog is easily generated.

[0006] A further concern is the increase in bleaching fog. When the photosensitive material is immersed in the bleaching bath following the color developing process due to the increase in the pH of the color developing solution, the pH in the gelatin film of the light-sensitive material is unlikely to rapidly decrease. The so-called bleaching fog in which the main agent oxidized by the oxidizing agent therein reacts with the unreacted coupler in the light-sensitive material is liable to occur.

The present invention has been made in view of the above circumstances, and provides a good color balance and sensitivity by adjusting the concentration of lithium ions in the processing solution for color development to the above specific concentration. In addition, development fog and bleaching fog were reduced at the same time, and rapid processing of the photosensitive material was achieved. In addition, lithium ions have a smaller ionic radius than other alkali metals, and are likely to be taken into a high-boiling solvent in which a coupler or the like is held in the light-sensitive material,
It is presumed that the formation reaction of the dye is suppressed. For this reason, the present inventor has also found that by adding lithium ions to the developer, good image quality can be obtained in addition to the above effects.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to obtain good gradation stability and sensitivity stability even when rapid processing is performed.
Another object of the present invention is to provide a color developing solution and a processing method for a photosensitive material which can reduce development fog and bleach fog.

[0009]

Means for Solving the Problems (The objects of the present invention are as follows: 1. 0.01 mol of lithium ions in a color developing solution.
for a silver halide color photographic light-sensitive material, characterized in that it contains 1 to 0.5 mol / l or less and further contains a color developing agent in the range of 0.025 mol / l to 0.10 mol / l. Color developing solution.

[0010] 2. In the color developing solution, iodine ions are contained in an amount of 6.0 × 10 ⁻⁷ mol / L to 7.0 × 10 ⁷ mol / L.
^{2. The} color developing solution for silver halide color photographic light-sensitive materials as described in 1 above, which is contained in the range of ^-5 mol / l.

3. When the silver iodide content of the silver halide is 0.
A silver halide color photographic light-sensitive material in the range of 5 mol% to 15 mol% was prepared by adding
A method for processing a silver halide color photographic light-sensitive material, wherein the processing is performed with a color developing solution containing 1 / liter to 0.5 mol / liter.

4. Color development processing time is 30 seconds or more and 120
4. The method for processing a silver halide color photographic light-sensitive material according to the above item 3, wherein the processing time is not more than seconds.

5. 5. The method for processing a silver halide color photographic material as described in 3 or 4, wherein the color developing agent is contained in the range of 0.025 mol / l to 0.10 mol / l.

6. Processing temperature of color development process is 40 ° C
6. The method for processing a silver halide color photographic light-sensitive material according to any one of the above items 3 to 5, wherein the temperature is at least 55 ° C.

[0015] 7. Iodine ions in the color developing solution are from 6.0 × 10 ⁻⁷ mol / L to 7.0 × 1.
0 ^-5 method for processing a silver halide color photographic material according to any one of 3-6, characterized in that it contains in the range of ^mol / liter.

8. The silver halide color photographic light-sensitive material is a tabular silver halide having an aspect ratio of 5 or more and a thickness of 0.1 μm or more and 0.3 μm or less in 50% or more of the total projected area. 50% or more, the layer excluding the outermost layer has a maximum silver iodide content of less than 15 mol%, the outermost layer has a silver iodide content of 6 mol% or more, and 5 or more dislocation lines per grain. 8. A method for processing a silver halide color photographic light-sensitive material according to any one of the above items 3 to 7, wherein an emulsion containing silver halide grains having the formula (1) is contained in at least one photosensitive layer.

9. The weight ratio of the total lipophilic photographic material / the total gelatin in the silver halide color photographic light-sensitive material is 0.5.
The above-mentioned 3 to 8, which is 0 or more and 0.70 or less.
The method for processing a silver halide color photographic light-sensitive material according to any one of the above.

10. The silver halide color photographic light-sensitive material has a silver halide content of 3.0 g / m ² or more and 7.0 g / m ² or more.
^The method for processing a silver halide color photographic light-sensitive material according to any one of the above items 3 to 9, wherein the composition is applied in a range of ² or less. Is achieved by each of

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail for each item. (Color development processing step) The processing solution for color development of the present invention contains lithium ions, but in a range of 0.01 mol / liter to 0.5 mol / liter. Further, the concentration of lithium ion is more preferably in the range of 0.02 mol / l or more and 0.10 mol / l or less, from the viewpoint of improvement in gradation stability, development fog and bleaching fog.

The processing time of the color developing process of the present invention is 3
The time is preferably from 0 to 120 seconds, and more preferably from 60 to 100 seconds from the viewpoint of gradation stability and sensitivity stability.

In the color developing solution of the present invention, the amount of the color developing agent is 0.025 mol / L or more and 0.10 mol / L.
It is preferably used in a range of not more than 1 liter, more preferably in a range of not less than 0.03 mol / l and not more than 0.05 mol / l.

The processing temperature of the color developing process of the present invention is 4
The temperature is preferably from 0 ° C. to 55 ° C.,
The temperature is more preferably 0 ° C or more and 45 ° C or less.

In the color developing solution of the present invention, iodine ions are contained in an amount of 6.0 × 10 ⁻⁷ mol / L to 7.0 × 10 ⁷ mol / L.
^The content is preferably in the range of ⁻⁵ mol / l, and more preferably from 5.0 × 10 ⁻⁶ mol / l to 2.
More preferably, it is in the range of 0 × 10 ⁻⁵ mol / liter.

The color development processing solution in the present invention is a processing solution in a processing tank for actually processing a photosensitive material, which means a so-called working solution, and does not include a replenisher.

The color developing agent used in the present invention is preferably a p-phenylenediamine compound having a water-soluble group. The water-soluble group has at least one amino group on a benzene nucleus or an amino group of a p-phenylenediamine compound.
Some specific water-soluble groups include-
_{(CH 2) n -CH 2 OH} , - (CH 2) m -NHSO
_{2 - (CH 2) n CH} 3, - (CH 2) m -O- (CH
_{2) n -CH 3, - (} CH 2 CH 2 O) n C m H
_{2m + 1 '(representing} the m and n are integers of 0 or more, respectively.) - COOH group, and as -SO ₃ H group and the like.

Examples of specific compounds preferably used in such a color developing agent include the following (C-1) to (C)
-16).

[0027]

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[0028]

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[0029]

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[0030]

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Among the color developing agents exemplified above, those preferred from the viewpoint of the effect of the present invention are (C-1) and (C-
2), (C-3), (C-4), (C-6), (C-
7) and (C-15), and particularly preferred is (C-
3).

The compound represented by the following general formula [D] is particularly preferably contained in a color developing solution.

[0033]

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(In the general formula [D], L represents an alkylene group, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, an amino group, an ammonium group, a carbamoyl group or a sulfamoyl group; R represents a hydrogen atom or an alkyl group, and L, A, and R each include a straight chain or a branched chain and may be unsubstituted or substituted. The compound represented by the formula [D] will be described in more detail. In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, groups such as methylene, ethylene, trimethylene, and propylene are preferred examples.
Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, and an ammonium group which may be alkyl-substituted, and preferred examples thereof include a carboxyl group, a sulfo group, a phosphono group, and a hydroxyl group. A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an amino group, an ammonium group, a carbamoyl group or a sulfamoyl group which may be alkyl-substituted, and a carboxyl group, a sulfo group, a hydroxyl group, a phosphono group And a carbamoyl group which may be alkyl-substituted. Preferred examples of -LA include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group. Groups, carboxyethyl groups, sulfoethyl groups, sulfopropyl groups, phosphonomethyl groups, and phosphonoethyl groups can be mentioned as particularly preferred examples. R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an amino group, an ammonium group, a carbamoyl group, or a sulfamoyl group which may be alkyl-substituted. There may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. Group, carboxyethyl group, sulfoethyl group, sulfopropyl group,
A phosphonomethyl group and a phosphonoethyl group are particularly preferable examples. L and R may combine to form a ring.

Next, typical examples of the compound represented by the formula [D] are shown below, but the present invention is not limited to these compounds.

[0036]

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In the color developing solution, a sulfite can be used as a preservative. As the sulfite, sodium sulfite, potassium sulfite, sodium bisulfite,
And potassium bisulfite.

Buffers can be used in the color developing solution, and the buffers include potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, and dibasic phosphate. Potassium, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-2-hydroxybenzoate Acid sodium (sodium 5-sulfosalicylate), 5-
Potassium sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) is preferred.

A development accelerator can be used in the color developing solution. Examples of the development accelerator include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, and amine compounds. , Polyalkylene oxides, 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles and the like can be added as necessary.

It is preferable that the color developing solution contains substantially no benzyl alcohol.

Chloride ions, bromine ions and iodides can be added to the color developing solution for the purpose of preventing fog and the like. When directly added to the color developing solution, the iodide ion-supplying material includes sodium, potassium, ammonium, nickel, magnesium, manganese, calcium or cadmium iodide, of which preferred are sodium iodide and iodide. Potassium. Further, it may be supplied in the form of a salt of a fluorescent whitening agent added to the color developing solution. Sodium, potassium, ammonium, lithium,
Calcium, magnesium, manganese, nickel, cadmium, cerium or thallium bromides are preferred, with potassium bromide and sodium bromide being preferred.

Further, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

(Steps after Color Developing Step) In carrying out the present invention, the steps after the color developing step, for example, steps having a bleaching ability, steps having a fixing ability, stabilizing steps, etc., are carried out in a usual manner. The configuration may be made in accordance with the following. For example, a process having a bleaching ability is described in JP-A-9-9057.
No. 9, Japanese Unexamined Patent Publication No.
-19971.

Preferred specific processing steps of the processing method according to the present invention are shown below. (1) Color development → bleaching → fixing → washing with water (2) Color developing → bleaching → fixing → washing → stable (3) Color developing → bleaching → fixing → stable (4) Color developing → bleaching → fixing → stable → second stable (5) Color development → bleach → bleach-fix → washing (6) Color development → bleach → bleach-fix → washing → stable (7) Color development → bleach → bleach-fix → stable (8) Color development → bleach → bleach-fix → (1) Color development → Bleaching → Bleaching and fixing → Fixing → Washing → Stable (10) Color development → Bleaching → Bleaching and fixing → Fixing → First stable →
Second stability (11) Color development → bleach-fix → stable (12) Color development → bleach → first fix → second fix → stable (13) Color development → bleach → fix → first stable → second stable →
Third stable Among these steps, (3), (4), (7), (1)
0), (12) and (13) are preferable, and particularly (3),
(4) and (13) are preferred.

(Silver halide photographic light-sensitive material) The light-sensitive material used in the present invention may be a silver halide photographic light-sensitive material containing a silver chloride emulsion, but contains silver bromide and silver iodobromide. It is preferably a high-sensitivity silver halide photographic material.

The silver halide coated with the light-sensitive material used in the present invention is from 3.0 g / m ^{2 to} 7.0 g / m ^2.
It is preferable to be within the following range. Furthermore, 4.0 g /
m and more preferably ² or more 6.0 g / ^{m 2} or less.

The tabular silver halide (hereinafter also referred to as tabular grain) in the present invention has two parallel main planes and an equivalent circle diameter of the main plane (having the same projected area as the main plane). A particle having an aspect ratio of 5 or more, i.e., the ratio of the diameter of a circle) to the distance between the main planes (i.e., the thickness of the particle).

In the rapid development processing, it is preferred that 50% or more of the total projected area of all the tabular grains of the present invention are tabular grains having an aspect ratio of 5 or more, more preferably 8 or more. If the aspect ratio is less than 5, a sufficient maximum density cannot be obtained.

The diameter of the tabular grains of the present invention is preferably from 0.3 to 10 μm, more preferably from 0.5 to 5.0 μm, still more preferably from 0.5 to 5.0 μm, in order to obtain a desired sensitivity.
2.0 μm. The particle thickness is preferably 0.05 to
0.8 μm, more preferably 0.1 to 0.3 μm
It is. It has been found that the surface area range according to the diameter and the particle thickness is suitable for rapid development processing.

The measurement of the particle diameter and the particle thickness in the present invention can be obtained by the method described in US Pat. No. 4,434,226.

The size distribution of the tabular grains of the present invention is obtained by dividing the standard deviation of the diameter distribution by the average diameter of the circle-converted diameter of the main plane (the diameter of a circle having the same projected area as the main plane). ) Is preferably 30% or less, and 20%
It is more preferred that:

The halogen composition of the silver halide grains is preferably silver iodobromide or silver chloroiodobromide, and the silver iodide content is preferably 0.5 to 15 mol%, More preferably, it is 10 mol%.

The intergranular distribution of the silver iodide content of the silver halide grains of the present invention is calculated by calculating the coefficient of variation of the silver iodide content (the standard deviation of the silver iodide content intergranular distribution is represented by the average silver iodide content). Is preferably 30% or less, and 20% or less.
% Is more preferable.

Although the tabular grains of the present invention have at least two or more phases having different halogen compositions inside the grains, the phase having the largest silver iodide content excluding the outermost layer has a silver iodide content of 3%. Mol% or more and less than 15 mol%, preferably 3 mol%.
Mol% or more and less than 10 mol%, more preferably 5 mol% or less.
It is at least 8 mol% and less than 8 mol%. Further, the volume fraction of the phase in the particles is preferably 30% or more and 90% or less, more preferably 30% or more and 60% or less.

The outermost layer of the tabular grains of the present invention preferably has a silver iodide content of 6 mol% or more and a solid solution limit or less. If it is less than 6 mol%, the storage stability of the adsorption of the sensitizing dye is undesirably reduced.

The outermost layer referred to in the present invention is a region including the surface area of the particles, but it is not always necessary to completely cover the inner phase. The outermost layer in the present invention refers to a region having a thickness of at least 10 atomic layers or more.

The silver iodide content on the grain surface in the present invention may be a numerical value measured by the XPS method or a numerical value measured by the ISS method.

The surface silver iodide content according to the XPS method of the present invention can be determined as follows. The sample is 1 × 10 ⁻⁸ torr
and cooled to −115 ° C. or less in an ultra-high vacuum of r or less, and irradiated with MgKα as an X-ray for a probe at an X-ray source voltage of 15 kV and an X-ray source current of 40 mA, and Ag3d5 / 2, Br3d,
It measures about I3d3 / 2 electron. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the halide composition on the surface is determined from the intensity ratio.

The structure relating to the halogen composition in the grains is represented by X
It can be examined by a line diffraction method, a composition analysis method using EPMA, or the like.

The maximum silver iodide-containing phase excluding the outermost layer referred to in the present invention does not include a high iodine localization region generated by an operation described later performed for forming dislocation lines.

As a method for producing tabular grains, methods known in the art can be appropriately combined. For example, Japanese Patent Application Laid-Open Nos. 61-6643, 61-146305, and 6
2-157024, 62-18556, 63-
No. 92942, No. 63-151618, No. 63-16
No. 3451, No. 63-220238, No. 63-311
A known method such as that described in Japanese Patent No. 244/244 can be referred to. For example, a double jet method, a double jet method, a control double jet method for maintaining a constant pAg in a liquid phase in which silver halide is formed, which is one type of the double jet method,
A trip jet method in which soluble silver halides having different compositions are separately added can also be used. A forward mixing method can be used, and a method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. If necessary, a silver halide solvent can be used. Silver halide solvents often used include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Pat.
No. 71,157, No. 3,790,387, No. 3,
No. 574,628 can be referred to. Also,
The mixing method is not particularly limited, and a neutral method using no ammonia, an ammonia method, an acidic method, or the like can be used. However, in order to reduce fog of silver halide grains, it is preferable to use a pH (hydrogen ion concentration). Logarithm of the reciprocal of
It is 5.5 or less, more preferably 4.5 or less.

The silver halide fine grains of the present invention contain iodide ions. In this case, the method of adding iodide ions in the grain growth is not particularly limited, and they may be added as an ion solution such as potassium iodide. Further, for example, it may be added as silver iodide fine particles.

The grain formation using silver halide fine grains is as follows.
Grain growth may be carried out using only silver halide fine grains as in the grains disclosed in JP-A-1-183417, JP-A-1-183644, JP-A-1-183645, etc.
What is necessary is just to supply at least one of the halogen elements by silver halide fine particles. In this case, the iodine ions are preferably supplied by silver halide fine particles. As claimed in Japanese Patent Application No. 3-218608, the number of silver halide fine grains used for grain growth is two or more, and at least one of them may consist of only one kind of halogen element. .

An emulsion containing silver halide grains grown in the presence of silver halide grains having a lower solubility than the growing silver halide grains, as in the claims of JP-A-2-16737. It is particularly desirable to use silver iodide as the silver halide grain having a small solubility product.

The dislocation of tabular grains is described, for example, in J. Am. Hami
lton, Photo. Sci. Eng. , 11 (19
67), 57 and T.I. Shiozawa, Jou. of
Photo. Sci. Japan, 35 (1972), 2
The observation can be performed by the method described in No. 13, that is, a direct method using a transmission electron microscope at a low temperature. That is,
The silver halide grains taken out so as not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for an electron microscope, and the sample is placed in a manner to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a cooled state. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, the use of a high-pressure electron microscope (200 kV for a thickness of 0.25 μm) enables more clear observation. From the grain photograph obtained by such a method, the position and number of dislocations for each grain when viewed from a direction perpendicular to the main plane can be determined.

The position of the dislocation of the grain of the present invention does not necessarily have to be at a specific position, but preferably exists at the fringe portion of the tabular grain. It may be present both in the fringe portion of the particle and inside the particle.

The fringe portion of the tabular grains referred to in the present invention refers to the outer periphery of the tabular grains. More specifically, the fringe portion is defined by a perpendicular drawn from the center of gravity of the tabular grain projection surface as viewed from the main plane to each side of the grains. Outside of 50% of the length of the perpendicular (side), preferably outside of 70%, more preferably 8
It means the area outside 0%.

The number of transitions in the tabular grains of the present invention is preferably such that grains containing 5 or more transitions account for at least 50% of the projected area of all silver halide grains in the emulsion.
It is particularly preferred that it is 0% or more. Further, the number of transitions is more preferably 10 or more. In the present invention, the presence of dislocation lines has an advantageous effect on high sensitivity, pressure resistance, and processing stability. When the number of dislocation lines is less than 5, the effect is small, and the number of dislocation lines is preferably large and there is no upper limit.

When dislocation lines exist between the inside of the grain and the fringe portion, it is preferable that five or more dislocation lines exist inside the grain, and it is more preferable that there are five or more dislocation lines both inside the fringe portion and inside the grain.

The method for introducing dislocation lines according to the present invention is not particularly limited, but a method of adding an aqueous solution of an iodide ion such as potassium iodide and a solution of a water-soluble silver salt by a double jet at the position where the transition is to be introduced, or The method can be carried out by a method of adding silver iodide fine particles, a method of adding only an iodine ion solution, a method using an iodide ion releasing agent as described in JP-A-6-11781, or the like. A method of adding an iodine ion aqueous solution and a water-soluble silver salt solution by double jet, a method of adding silver iodide fine particles, and a method of using an iodide ion releasing agent are preferable, and a method of using silver iodide fine particles is more preferable. The aqueous solution of iodine ion is preferably an aqueous solution of an alkali iodide, and the aqueous solution of a water-soluble silver salt is preferably an aqueous solution of silver nitrate.

The position where the dislocation is introduced is preferably performed after the formation of the maximum silver iodide-containing phase inside the grain, and more preferably after the formation of the phase and before the formation of the adjacent phase.

In relation to the position of the whole grain, it is preferable to introduce the silver in an amount corresponding to 50 to 95% of the silver amount of the whole grain, and it is more preferable to introduce the silver in an amount of less than 60 to 80%.

The lipophilic photographic material in the present invention refers to a substantially water-insoluble material, and specifically includes a so-called high-boiling solvent and a so-called high-boiling solvent to be added to a photographic light-sensitive material. At the same time or at the same time. For example, an emulsified dispersion to be added to a hydrophilic colloid binder such as an ultraviolet absorber, an anti-turbidity agent, an antioxidant, an anti-stain agent, and an oil-soluble coupler or a DIR coupler is also included.

As the organic high-boiling compounds, those having a boiling point at normal pressure of 180 ° C. or more and less than 350 ° C. are generally used.

In the present invention, any known method can be used to add the lipophilic photographic material. Typical methods include, for example, one or more of the above-mentioned organic high-boiling compounds and the like. If necessary, a compound capable of forming oil droplets is dissolved with a photographic additive as described below, and if necessary, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, dimethylene are added. Dissolve in low-boiling solvents such as glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, ethyl alcohol, propyl alcohol, fluorinated alcohol, acetonitrile, dimethylformamide, dioxane, acetone, methyl ethyl ketone, and methyl isobutyl ketone. ( The boiling point solvent may be used alone or in combination.) Anionic surfactants such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid and / or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate Is mixed with an aqueous solution containing a hydrophilic colloid substance such as gelatin containing, and emulsified and dispersed by a high-speed mixer, a colloid mill or an ultrasonic dispersing device, and the resulting dispersion is added to a coating liquid containing a hydrophilic colloid substance. Then, it may be coated on a support or on a silver halide emulsion or the like provided on the support. The compound capable of forming a certain kind of oil droplet may be dissolved, for example, in the above-mentioned low-boiling organic solvent, and the solution may be directly added to a coating liquid containing a hydrophilic colloid substance.

The low-boiling organic solvent used at this time evaporates after coating and drying, and hardly exists in the binder.

As the oil-soluble coupler, there are a yellow coupler, a magenta coupler and a cyan coupler which form a color image by color development.

As the couplers that can be used in the present invention, the compounds described in the following patents are representatively included.

Among them, yellow couplers include benzoylacetanilide type, bivaloylacetanilide type,
Alternatively, it is a 2-equivalent yellow coupler in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction (a so-called split-off group). As the magenta coupler, 5-pyrazolone,
A pyrazolotriazole-based, pyrazolino-benzimidazole-based, indazolone-based, or 2-equivalent magenta coupler having a split-off group.

The cyan coupler is a phenol-based, naphthol-based, or 2-equivalent cyan coupler having a split-off group.

Further, as a preferable example of the coupler to be contained in the oil droplet in the present invention, a so-called Weiss coupler which is oil-soluble and does not form a colored dye by reacting with an oxidized form of the developing agent is also mentioned.

The lipophilic photographic material in the non-photosensitive layer preferably contains a color turbidity inhibitor. Examples of the color turbidity preventing agent include compounds described in Japanese Patent Application No. 4-19048, which react with an oxidized form of a color developing agent and do not impart an image density. Nos. 4-19048 H-1 to H18), pyrogallol-based and catechol-based compounds (Japanese Patent Application No. 4-194048)
Nos. P1 to P16), sulfonylamino compounds (Japanese Patent Application No. 4-19048, S-1 to S-19), coupling compounds (CP-1 to CP-23), and hydrazine compounds (HZ-1 to HZ) -14).

In the present invention, the weight ratio of total lipophilic photographic material / gelatin is preferably 0.50 to 0.70, more preferably 0.50 to 0.65. 0.7
When it is larger than 0, the storage stability is poor, and when it is smaller than 0.50, the effect of stabilizing the rapid development processing of the present invention is small. In addition, the coated amount of gelatin is 14.0 to 18.0 g / m ² , and more preferably 15.0 to 17.0 g / m ² . 1
When the amount is less than 4.0 g / m ² , the pressure resistance is insufficient, and the sweating phenomenon (the oily photographic material in the photosensitive material oozes on the surface of the photosensitive material and becomes sweaty) is likely to occur. If it is more than 18.0 g / m ² , the development processing time will be long.

The non-photosensitive layer of the present invention is a layer containing no photosensitive silver halide, but may contain a non-photosensitive silver halide. The non-light-sensitive intermediate layer located between the light-sensitive layers may be the same color-sensitive layer or a different color-sensitive layer, and the weight ratio of at least one lipophilic photographic material / gelatin weight of the non-light-sensitive intermediate layer Is 0.30 or more and 0.90 or less, more preferably 0.35 or more.
70 or less. In the present invention, the weight ratio of the lipophilic photographic material / gelatin in the non-photosensitive intermediate layer is 0.30.
It is not less than 0.90 and more preferably not less than 0.35 and not more than 0.70. If it is more than 0.90, the adhesion of the coating film will decrease and sweating will occur, and if it is less than 0.30, the effect of improving the pressure resistance of the present invention will be small.

In the present invention, the photosensitive layer and the non-photosensitive layer adjacent to each other may be above or below the photosensitive layer as viewed from the support, and all the parent layers of the adjacent photosensitive layer and non-photosensitive layer may be used. Oil-based photographic material weight / gelatin weight ratio difference between 0 and 0.5
0 or less, more preferably 0 or more and 0.40 or less. If it is larger than 0.50, the adhesiveness of the coating film is inferior and the stability over time is also reduced. Further, all the layers adjacent to each other may be photosensitive layers, non-photosensitive layers, or a photosensitive layer and a non-photosensitive layer. The difference in gelatin weight ratio is 0 or more and 0.60 or less, more preferably 0 or more and 0.50 or less.
It is as follows.

The photographic constituent layer of the photographic material of the present invention preferably has a calcium content of 50 ppm or less, and particularly preferably 4 ppm or less.
It is preferably at most 0 ppm, more preferably at most 30 ppm. If the calcium content is too high, the film will peel off or devitrify during rapid development, making it impractical.

The calcium in the gelatin forming the photographic constituent layer is derived from the raw materials. To obtain the gelatin having the calcium content of the present invention, the selection of the raw materials, the selection of the production conditions, the ion exchange treatment, etc. May be appropriately combined.

In the ion exchange treatment, gelatin may be extracted from raw materials such as beef bone and pig skin and then ion exchanged using an ion exchange resin (for example, IRA type manufactured by Rohm Hand Haas Co.).

The calcium ion content after the ion exchange treatment may be determined according to the method described in the sixth edition of the photographic gelatin test method (abbreviation: the Bagii method) established by the Joint Committee for the Test Methods for Gelatin.

[0090]

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

Example 1 Automatic developing machine CL-Kp50QA for color negative film
Konica Color Negative Film LV10, which was subjected to wedge exposure by a normal method using an automatic developing machine modified so as to increase the transport speed of photosensitive material (manufactured by Konica) to 2.16 times.
0 (24 shots) at a rate of 20 shots a day under the following conditions:
Continuous treatment was performed for 5 days. In the present invention, the processing of the following processing steps is referred to as rapid processing.

(Processing step (rapid processing)) Processing time Processing temperature Replenishment amount Color development 90 seconds 42 ° C. 550 ml / m ² Bleaching 21 seconds 38 ° C. 100 ml / m ² Fixing-1 21 seconds 38 ° C. Fixing-2 21 seconds 38 ° C. 550 ml / ^{m 2} stabilized -1 9.2 sec 38 ° C. stable -2 9.2 sec 38 ° C. stable -3 9.2 sec 38 ° C. 860 ml / ^{m 2} drying 40 sec 65 ° C. the fixing treatment step from 2 1, The stabilization process was a countercurrent system from 3 to 2, 2 to 1, and replenishment was performed in the final tank.

(Prescription of Processing Solution) (Starting solution for color development) Sodium sulfite 5.5 g Potassium carbonate 42.0 g Hydroxylamine sulfate 3.0 g Diethylenetriaminepentaacetic acid pentasodium 4.0 g Potassium bromide 1.33 g Polyvinylpyrrolidone K- 17 4.0 g Potassium iodide 2.0 mg Lithium hydroxide Described in Table 1 4-Amino-3-methyl-N-ethyl-N (β-hydroxyethyl) aniline sulfate (Exemplified Compound C-3) Described in Table 1 Add water to make up to 1 liter and adjust the pH to 10.3 with potassium hydroxide or 50% sulfuric acid.

(Replenisher for color development) Sodium sulfite 7.0 g Potassium carbonate 42.0 g Hydroxylamine sulfate 3.8 g Diethylenetriaminepentasodium pentasodium 4.0 g Potassium bromide 0.4 g Polyvinylpyrrolidone K-17 4.0 g Hydroxide Lithium Same amount as the above start amount 4-amino-3-methyl-N-ethyl-N (β-hydroxyethyl) aniline sulfate (Exemplified compound C-3) 1.18 times the above start solution And adjust the pH to 10.55 with potassium hydroxide or 50% sulfuric acid.

(Bleaching start liquid) Ferric ammonium 1,3-propylenediaminetetraacetate 140 g 1,3-propylenediaminetetraacetic acid 7 g Ammonium bromide 60 g Maleic acid 60 g Water was added to make 1 liter, and ammonia water or 50% Adjust the pH to 3.0 with sulfuric acid.

(Bleaching replenisher) Ferric ammonium 1,3-propylenediaminetetraacetate 190 g 1,3-propylenediaminetetraacetic acid 10 g Ammonium bromide 90 g Maleic acid 90 g Water was added to make 1 liter, and ammonia water or 50% Adjust the pH to 2.0 with sulfuric acid.

(Fixing Start Solution, Fixing Replenisher) Ammonium thiosulfate 225 g Sodium thiosulfate 25 g Sodium sulfite 20 g Potassium carbonate 2 g Ethylenediaminetetraacetic acid disodium 2 g Add water to make up to 1 liter, and use ammonia water or 50% sulfuric acid. Adjust the pH to 6.5.

(Stable start solution, stable replenisher) m-hydroxybenzaldehyde 1.0 g disodium ethylenediaminetetraacetate 0.2 g potassium carbonate 0.2 g β-cyclodextrin 0.2 g potassium hydroxide 0.03 g Finish to liter.

Also, CL-KP50QA (manufactured by Konica Corporation)
The above-mentioned photosensitive material is processed (normal processing) under the processing conditions of the same process using a replenisher for the CNK-4-52 process and a starter (manufactured by Konica) as a processing agent. At the end of the continuous processing experiment, evaluation was performed using the method described below.

(Evaluation of Gradation Stability) In the D-logE characteristic curve, a point of density of minimum density + 0.3 and minimum density +
With respect to the gradient γ of the straight line connecting the points having the density of 1.3, the ratio of the rapid processing γR to the normal processing γN and γR / γN were obtained for the magenta image.

Further, the transmission density (Dmin (B)) at 440 nm of the unexposed portion of the processed photosensitive material at the start and end of the rapid processing continuous processing experiment was measured, and the scale of development fog and bleach fog were measured. did. The results are summarized in Table 1. In this embodiment, it is assumed that the smaller the change in gradation stability from 1.00 and the smaller the change in Dmin (B) from 0.90, the better the performance.

[0102]

[Table 1]

As is clear from the results shown in Table 1, the color developing solution contains lithium ions in the range of 0.01 mol / l to 0.5 mol / l and the color developing agent in the range of 0.025 mol / l to 0.1 mol / l. 10mol
It can be seen that when the content is within the range, good tone stability can be obtained and development fog and bleaching fog can be reduced.

Example 2 Experiment No. 1 of Example 1 1-7, except that the concentration of the color developing agent (exemplified compound C-3) was fixed and the concentration of lithium ion and the concentration of potassium iodide were changed as shown in Table 2. The same processing of the light-sensitive material as in Example 1 was performed using the starting solution for the process. For the sensitized material after the processing, the minimum density +0.
The rapid processing γ with respect to the normal processing γN with respect to the slope γ of the straight line connecting the density point of 3
The ratio of R and γR / γN were obtained for the magenta image, and the gradation stability was evaluated. Further, development fog and bleaching fog were evaluated in the same manner as in Example 1. The results are summarized in Table 2.

[0105]

[Table 2]

As is clear from Table 2, when the color developing solution contains iodine ions in the range of 6.0 × 10 ⁻⁷ mol / L to 7.0 × 10 ⁻⁵ mol / L, It can be seen that the effects of the present invention can be further exhibited.

Example 3 Photosensitive materials having different silver iodide contents as shown in Table 3 were prepared in the same manner as in the method of preparing a light-sensitive material described in JP-A-1-261640. The grain size of the silver halide applied was adjusted so that each photosensitive material had the same D-logE characteristic curve when the normal processing in the present invention was performed. The amount of silver applied was 5.0 for all photosensitive materials.
g / m ² . Next, Experiment No. 1 of Example 1 was performed. The starting solution of each step used in Example 1 was used except that the concentration of the color developing agent (exemplified compound C-3) was fixed at 1-7 and the concentration of lithium ion was changed as shown in Table 3. Then, the processing of the photosensitive materials 1 to 7 subjected to the usual wedge exposure was performed. For the light-sensitive material after processing, D-lo
In the gE characteristic curve, the ratio of the rapid processing γR to the normal processing γN, γR /, for the slope γ of the straight line connecting the point of the minimum density +0.3 and the point of the minimum density +1.0.
γN was determined for the magenta image of each photosensitive material, and the gradation stability was evaluated. In addition, sensitivity stability was evaluated by the following method.

(Sensitivity stability) In the D-logE characteristic curve, for the reciprocal S of the exposure amount with respect to the point of the density of minimum density +0.5, the ratio of the rapid processing SR to the normal processing SN and the ratio SR / SN to each photosensitive material For the yellow image.

[0109]

[Table 3]

As is clear from the results shown in Table 3, the color developing solution contains lithium ions in the range of 0.01 mol / l to 0.5 mol / l, and the halogenation of the silver halide color photographic light-sensitive material. It can be seen that when the silver iodide content of silver is in the range of 0.5 mol% to 15 mol%, good gradation stability and sensitivity stability can be obtained.

Example 4 Experiment No. 1 of Example 1 The concentration of the color developing agent (exemplified compound C-3) was fixed at 1-7, and the lithium ion concentration and the color development processing time were adjusted by adjusting the transport speed of the automatic developing machine.
The processing of the photosensitive material was performed in the same manner as in Example 1 except that the starting solution in each step used in Example 1 was changed as shown in (1). The processed photosensitive material was evaluated for gradation stability for a yellow image and for sensitivity stability for a cyan image in the same manner as in Example 3. Table 4 shows the results.

[0112]

[Table 4]

As is clear from the results shown in Table 4, the effect of the present invention can be further exhibited when the color development processing time is from 30 seconds to 120 seconds.

Example 5 Experiment No. 1 of Example 1 1-7, except that the concentration of the color developing agent (exemplified compound C-3) was fixed, and the concentration of the lithium ion and the color developing temperature were changed as shown in Table 5.
Example 1 Using the starting solution for each step used in Example 1
The same photosensitive material processing was performed. The processed photosensitive material was evaluated for sensitivity stability in the same manner as in Example 3 for magenta images.

Further, with respect to the sample after the rapid processing, the granularity (RMS value) was evaluated at a place where the transmission density at 550 nm was 1.2. The RMS value is obtained by measuring the density of the portion to be measured of the sample with the aperture scanning area of 1600 μm ² (slit width 1).
The sample was scanned with a microdensitometer (0 μm, slit length 160 μm) (using a Watten filter W-99 manufactured by Eastman Kodak Co.), and the concentration measurement sampling number was 1
The standard deviation of the variation of the concentration value of 000 or more was determined as 1000 times, and the value of Experiment No. The RMS value of 5-1 was shown as a relative value with 1.00. The smaller the RMS value, the better the performance.

Table 5 shows the results.

[0117]

[Table 5]

As is clear from the results in Table 5, when the processing temperature in the color development processing step is 40 ° C. or more and 55 ° C. or less, good sensitivity stability and granularity are obtained, and the effects of the present invention are further exhibited. We can see that we can do it.

Example 6 A photosensitive material having a different amount of silver applied as shown in Table 6 was prepared in the same manner as in the method of preparing a photosensitive material described in JP-A-1-261640. The silver iodide content was adjusted to be 7.0 mol% for all the photographic materials. Further, the particle size of the silver halide particles applied was adjusted in the same manner as in Example 3. Next, Experiment No. 1 of Example 1 was performed. 1-
7, except that the concentration of the color developing agent (Exemplified Compound C-3) was fixed and the concentration of lithium ion was changed as shown in Table 6, and the starting solution of each step used in Example 1 was used. Photosensitive materials 11 to 17 subjected to normal wedge exposure
Was performed. For each of the processed photosensitive materials, the gradation stability of the yellow image and the sensitivity stability of the cyan image were evaluated in the same manner as in Example 3. Table 6 shows the results.

[0120]

[Table 6]

As is clear from the results shown in Table 6, the silver halide color photographic light-sensitive material contained 3.0 g / m 2 of silver halide.
^It can be seen that good gradation stability and sensitivity stability can be obtained by coating in the range of ^{2 to} 7.0 g / m ² .

Example 7 A silver halide photographic material was prepared by the following method. Preparation of Seed Emulsion-1 A seed crystal emulsion was prepared as follows.

JP-B-58-58288, 58-58
No. 289, a silver nitrate aqueous solution (1.161 mol) was added to the following solution A1 adjusted to 35 ° C.
And a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV. For 2 minutes to form nuclei. Subsequently, it takes 60 minutes to adjust the liquid temperature to 60 minutes.
° C and the pH was adjusted to 5.0 with an aqueous solution of sodium carbonate, and then an aqueous solution of silver nitrate (5.902 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (2 mol% of potassium iodide) were added to silver. While the potential was maintained at 9 mV, the mixture was added in 42 minutes by the simultaneous mixing method. 40 ° C after completion of addition
While the temperature was lowered, desalting and washing with water were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and 90% or more of the total projected area of the silver halide grains had a maximum side ratio of 1.0.
~ 2.0 hexagonal tabular grains. This emulsion is referred to as seed emulsion-1. [Solution A1] Ossein gelatin 24.2 g Potassium bromide 10.8 g HO (CH ₂ CH ₂ O) m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) nH (m + n = 9.77) (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml Preparation of silver iodide fine grain emulsion SMC-1 6.0% by weight gelatin aqueous solution containing 0.06 mol of potassium iodide 5 While stirring the liter vigorously, 7.0
A 6 mol silver nitrate aqueous solution and a 7.06 mol potassium iodide aqueous solution, 2 liters each, were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are prepared, p is added using an aqueous solution of sodium carbonate.
H was adjusted to 5.0. The average particle diameter of the obtained silver iodide fine particles was 0.05 μm. This emulsion is designated as SMC-1.

Preparation of Emulsion Em-1 0.178 mol of seed crystal emulsion-1 and HO (CH ₂ CH
_{2 O) m (CH (CH} 3) CH 2 O) 19.8 (CH 2
700 ml of a 4.5% by weight aqueous solution of inert gelatin containing 0.5 ml of a 10% ethanol solution of (CH ₂ O) nH (m + n = 9.77) was kept at 75 ° C., and the pAg was 8.9.
After adjusting the pH to 5.0, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure. 1) 2.1 mol of silver nitrate aqueous solution and 0.195 mol of SM
C-1 and an aqueous potassium bromide solution with a pAg of 8.9,
It was added while maintaining the pH at 5.0. 2) Subsequently, a 1.028 mol aqueous silver nitrate solution and 0.03 mol
Two moles of SMC-1 and an aqueous solution of potassium bromide were added to pA
g was maintained at 8.9 and the pH was maintained at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the above addition, a water washing treatment was performed at 40 ° C. by using a normal flocculation method, and gelatin was added to redisperse, and the pAg was adjusted to 8.1 and the pH was adjusted to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was a tabular grain having a halogen composition shown in Table 7 having a side length of 0.65 μm and an average aspect ratio of 7.2.

When the content of silver iodide on the surface was measured by the method described in this specification, the content of silver iodide on the surface was 4.5 mol%.

Preparation of Emulsion Em-2 In the preparation of Emulsion Em-1, after the completion of the step 2).
Em-2 was prepared in the same manner as Em-1, except that 004 mol of SMC-1 was added and aged for 15 minutes.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was a tabular grain having a halogen composition shown in Table 4 having a side length of 0.65 μm and an average aspect ratio of 7.2. The surface silver iodide content was 13.1 mol%.

Preparation of Emulsion Em-3 0.178 mol of seed crystal emulsion-1 and HO (CH ₂ CH
_{2 O) m (CH (CH} 3) CH 2 O) 19.8 (CH 2
700 ml of a 4.5% by weight aqueous solution of inert gelatin containing 0.5 ml of a 10% ethanol solution of (CH ₂ O) nH (m + n = 9.77) was kept at 75 ° C., and the pAg was 8.9.
After adjusting the pH to 5.0, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure. 1) 2.1 mol of silver nitrate aqueous solution and 0.195 mol of SM
C-1 and an aqueous potassium bromide solution with a pAg of 8.9,
It was added while maintaining the pH at 5.0. 2) Subsequently, the temperature of the solution was lowered to 60 ° C., and the pAg was adjusted to 9.8. Thereafter, 0.071 mol of SMC-1 was added and aging was performed for 2 minutes (introduction of dislocation lines). 3) pAg of 0.959 mol of silver nitrate aqueous solution, 0.030 mol of SMC-1 and potassium bromide aqueous solution was adjusted to 9.
8. It was added while maintaining the pH at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the above addition, a water washing treatment was performed at 40 ° C. by using a normal flocculation method, and gelatin was added to redisperse, and the pAg was adjusted to 8.1 and the pH was adjusted to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was a tabular grain having a halogen composition shown in Table 7 having a side length of 0.65 μm and an average aspect ratio of 7.0. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 6.7 mol%.

Preparation of Emulsion Em-4 Em-3 was prepared except that the amount of silver nitrate added in step 2) was 0.92 mol and the amount of SMC-1 was 0.069 mol in the preparation of emulsion Em-3. Emulsion Em-4 was prepared in the same manner as described above.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was a tabular grain having a halogen composition shown in Table 7 having a side length of 0.65 μm and an average aspect ratio of 6.7. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 11.9 mol%.

Preparation of Emulsion Em-5 0.178 mol of seed crystal emulsion-1 and polyisoprene
4.5% by weight containing 0.5 ml of a 10% ethanol solution of polyethylene oxydisuccinate sodium salt
Of inert gelatin aqueous solution at 75 ° C.
After adjusting the Ag to 8.9 and the pH to 5.0, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure. 1) A pAg of a 0.692 mol silver nitrate aqueous solution, 0.297 mol SMC-1 and potassium bromide aqueous solution was set to 8.
9. Added while keeping the pH at 5.0. 2) Subsequently, a 2.295 mol silver nitrate aqueous solution and 0.07 mol
1 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g was maintained at 8.9 and the pH was maintained at 5.0. 3) After the step 2), 0.004 mol of SMC-1
Was added and aged for 15 minutes.

Each solution was added at an optimum rate throughout the particle formation so that the formation of new nuclei and the Ostwald ripening between particles did not proceed. After the above step 3), after performing a water washing treatment at 40 ° C. using a normal flocculation method,
Gelatin was added for redispersion, and the pAg was adjusted to 8.1 and the pH was adjusted to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
This emulsion was composed of tabular grains having a halogen composition shown in Table 7 having a side length of 0.65 μm and an average aspect ratio of 4.3. Observation of this emulsion with an electron microscope revealed that there were no grains having dislocation lines. The surface silver iodide content is 1
2.0 mol%.

Preparation of Emulsion Em-6 Em-6 described in Examples of JP-A-7-92594
In accordance with the production method of Comparative Example 4, Comparative Emulsion Em-6 was prepared.

Emulsions Em-1 to Em-1 prepared as described above
Table 7 shows the contents of No. 6.

[0141]

[Table 7]

1) The silver iodide content (mol%) of each phase is shown. X indicates a dislocation line introduction position. 2) Aspect ratio at 50% of the total projected area of silver halide grains in each emulsion. 3) → indicates that the iodine composition was continuously changed in the formulation.

To each of the above emulsions Em-1 to Em-6, sensitizing dyes SD-5, SD-6 and SD-7 were added, and sodium thiosulfate, chloroauric acid, potassium thiocyanate, selenium sensitizer b -1 was added, and chemical sensitization was performed according to a conventional method so as to optimize the fog-sensitivity relationship.

After completion of the chemical sensitization, a stabilizer ST-1 was added to each emulsion.
And an antifoggant AF-1. The amount of ST-1 added was 1 g per mol of silver halide, and the amount of AF-1 was 15 mg per mol of silver halide.

Thus, chemically sensitized emulsions Em-A to Em-F corresponding to Em-1 to Em-6 were prepared.

[0146]

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{Preparation of multilayer color photographic light-sensitive material sample} On a triacetyl cellulose film support provided with an undercoat layer, layers having the following compositions are sequentially formed from the support side, and a multilayer color photographic light-sensitive material sample 101 is formed. Was prepared.
In the fifth, tenth and fourteenth layers, the emulsion Em-
A was used.

[0148] The addition amount is particularly shows the number of grams per 1 m ² unless otherwise noted. Further, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in moles per mole of silver.

First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling organic solvent (Oil-1) 0.07 Gelatin 1.53

Second layer: Intermediate layer Color stain inhibitor (SC-1) 0.06 High boiling organic solvent (Oil-2) 0.08 Gelatin 0.80

Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size: 0.38 μm, silver iodide content: 8.0 mol%) 0.41 Silver iodobromide emulsion (average grain diameter: 0.1%) 27 μm, silver iodide content: 2.0 mol%) 0.15 sensitizing dye (SD-1) 2.8 × 10 ⁻⁴ sensitizing dye (SD-2) 1.9 × 10 ⁻⁴ sensitizing dye ( 1.9 × 10 ^-4 sensitizing dye (SD-4) 1.0 × 10 ^-4 cyan coupler (C-1) 0.53 colored cyan coupler (CC-1) 0.021 DIR compound (SD-3) D-1) 0.025 High boiling solvent (Oil-1) 0.49 Gelatin 1.12

Fourth layer: middle-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size: 0.52 μm, silver iodide content: 8.0 mol%) 0.87 Silver iodobromide emulsion (average grain size: 0.02%) 38 μm, silver iodide content: 8.0 mol%) 0.21 sensitizing dye (SD-1) 2.3 × 10 ^-4 sensitizing dye (SD-2) 1.2 × 10 ^-4 sensitizing dye ( SD-3) 1.6 × 10 ^-4 Cyan coupler (C-1) 0.44 Colored cyan coupler (CC-1) 0.040 DIR compound (D-1) 0.017 High boiling solvent (Oil-1) 0.39 gelatin 1.01

Fifth layer: high-sensitivity red-sensitive layer Em-A 1.25 sensitizing dye (SD-1) 1.3 × 10 ^-4 sensitizing dye (SD-2) 1.3 × 10 ^-4 sensitization Dye (SD-3) 1.6 × 10 ^-4 Cyan coupler (C-2) 0.19 Colored cyan coupler (CC-1) 0.034 DIR compound (D-3) 0.001 High boiling solvent (Oil- 1) 0.37 gelatin 1.05

Sixth layer: Intermediate layer Color stain inhibitor (SC-1) 0.075 High boiling organic solvent (Oil-2) 0.095 Gelatin 1.00

Seventh layer: Intermediate layer Gelatin 0.45

Eighth layer: low-sensitivity green-sensitive layer Silver iodobromide emulsion (average grain size: 0.39 μm, silver iodide content: 8.0 mol%) 0.64 Silver iodobromide emulsion (average grain size: 0. 29 μm, silver iodide content 2.0 mol%) 0.21 sensitizing dye (SD-4) 7.4 × 10 ^-4 sensitizing dye (SD-5) 6.6 × 10 ^-4 magenta coupler (M -1) 0.19 Magenta coupler (M-2) 0.49 Colored magenta coupler (CM-1) 0.12 High boiling solvent (Oil-2) 0.31 Gelatin 1.89

Ninth layer: middle-sensitivity green-sensitive layer Silver iodobromide emulsion (average grain size: 0.59 μm, silver iodide content: 8.0 mol%) 0.74 Sensitizing dye (SD-6) 1.5 × 10 ^-4 sensitizing dye (SD-7) 1.6 × 10 ^-4 sensitizing dye (SD-8) 1.5 × 10 ^-4 magenta coupler (M-1) 0.041 Magenta coupler (M-2) ) 0.095 Colored magenta coupler (CM-2) 0.039 DIR compound (D-2) 0.021 DIR compound (D-3) 0.002 High boiling solvent (Oil-2) 0.17 Gelatin 0.76

Tenth layer: High-sensitivity green-sensitive layer Em-A 1.46 Magenta coupler (M-1) 0.08 Magenta coupler (M-2) 0.130 Colored magenta coupler (CM-2) 0.014 High Boiling solvent (Oil-1) 0.15 High boiling solvent (Oil-2) 0.22 Gelatin 1.08

Eleventh layer: Yellow filter layer Yellow colloidal silver 0.07 Color stain inhibitor (SC-1) 0.18 Formalin scavenger (HS-1) 0.14 High boiling solvent (Oil-2) 0.11 Gelatin 0.73

Twelfth layer: Intermediate layer Formalin Scavenger (HS-1) 0.18 Gelatin 0.60

Thirteenth layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average particle size: 0.60 μm, silver iodide content: 8.0 mol%) 0.07 Silver iodobromide emulsion (average particle size: 0. 37 μm, silver iodide content: 3.0 mol%) 0.16 Silver iodobromide emulsion (average grain size: 0.25 μm, silver iodide content: 2.0 mol%) 0.20 sensitizing dye (SD-9) 2.1 × 10 ⁻⁴ sensitizing dye (SD-10) 2.8 × 10 ⁻⁴ Yellow coupler (Y-1) 0.89 DIR compound (D-4) 0.008 High boiling point solvent (Oil-2) ) 0.27 gelatin 1.51

Fourteenth layer: high-sensitivity blue-sensitive layer Em-A 0.95 sensitizing dye (SD-9) 7.3 × 10 ^-4 sensitizing dye (SD-10) 2.8 × 10 ^-4 yellow coupler (Y-1) 0.16 High boiling point solvent (Oil-2) 0.093 Gelatin 0.80

Fifteenth layer: First protective layer Silver iodobromide emulsion (average particle size 0.05 μm, silver iodide content 3.0 mol%) 0.28 UV absorber (UV-1) 0.094 UV Absorbent (UV-2) 0.10 Formalin scavenger (HS-1) 0.38 High boiling solvent (Oil-1) 0.05 Gelatin 1.41

Sixteenth layer: Second protective layer Alkali-soluble matting agent PM-1 (average particle size 2 μm) 0.15 Polymethyl methacrylate (average particle size 3 μm) 0.04 Slip agent (WAX-1) 0.02 Gelatin 0.55 In addition to the above composition, coating aids SU-1 and SU-
2, SU-3, dispersing aid SU-4, viscosity modifier V-1,
Stabilizer ST-1, dyes AI-1, AI-2, antifoggant AF-1, two kinds of polyvinylpyrrolidone (AF-2) having a weight average molecular weight of 10,000 and a weight average molecular weight of 100,000, Membrane agents H-1, H-2 and preservative DI
-1 was added. The amount of DI-1 added was 9.4 mg / m ^2.
Met.

The structures of the compounds used in the above samples are shown below.

[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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Emulsion E of the fifth, tenth and fourteenth layers of Sample 101
mA was replaced with Em-B to F-F,
106 was created.

Next, Experiment No. 1 of Example 1 was performed. 1-7, except that the concentration of the color developing agent (exemplified compound C-3) was fixed and the concentration of lithium ions was changed as shown in Table 8.
The processing of the photosensitive materials 101 to 106 subjected to the usual wedge exposure was performed using the starting solution of each step used in Example 1. 440n of the maximum density part of each photosensitive material after processing
m transmission density (DR (B)), 550 nm of maximum density part
And the transmission density (DR (R)) at 660 nm of the maximum density part were measured. The normal processing in Example 1 is performed on the photosensitive materials 101 to 106 that have been subjected to normal wedge exposure, and the transmission density (DN (B)) at 440 nm of the maximum density part of each photosensitive material after processing, and the maximum density part Was measured at a transmission density of 550 nm (DN (G)) and a transmission density at 660 nm (DN (R)) of the maximum density part. Next, △ DB, △ DG, △ obtained by the following equations
DR was calculated and used as a measure of suitability for rapid processing. Note that △ D
The smaller B, ΔDG and ΔDR are, the quicker the process.

ΔDB = DR (B) −DN (B) ΔDG = DR (G) −DN (G) ΔDR = DR (R) −DN (R) The results are shown in Table 8.

[0178]

[Table 8]

As is clear from the results in Table 8, the silver halide color photographic light-sensitive material has a tabular silver halide having an aspect ratio of 5 or more and a thickness of 0.1 μm to 0.3 μm in at least 50% of the total projected area. Wherein at least 50% of the tabular silver halide has a maximum silver iodide content of the layer excluding the outermost layer of less than 15 mol% and a silver iodide content of the outermost layer of 6 mol% or more. It can be seen that when at least one silver halide emulsion having 5 or more dislocation lines per grain is contained in at least one layer, rapid processing suitability can be obtained.

Example 8 In the light-sensitive material 101 of Example 7, the amounts of the high-boiling solvents Oil-1 and Oil-1 in each layer were increased at the same ratio, and the total lipophilic photographic material weight / The total amount of gelatin (O / G ratio) was adjusted as shown in Table 9 and subjected to wedge exposure, followed by the same treatment as in Example 7. ΔDG was calculated for the processed photosensitive material in the same manner as in Example 7, and rapid processing suitability was evaluated. Further, the transmission density (DRmin (B)) of the unexposed portion of the sensitized material after the rapid processing was measured at 440 nm, and the 440 nm of the unexposed portion of the sensitized material after the normal processing was measured. The transmission density (DNmin (B)) is measured, and the following equation ΔDmin (B) = DRmin (B) −DNm
ΔDmin (B) from in (B) was used as a measure of development fog and bleaching fog. The O / G ratio of the sample 101 of Example 5 was 0.4
It was 5.

Table 9 summarizes the results.

[0182]

[Table 9]

As is clear from the results in Table 9, rapid processing suitability was obtained when the weight ratio of total lipophilic photographic material / weight of total gelatin in the silver halide color photographic light-sensitive material was 0.50 or more and 0.70 or less. It can be seen that good fog is maintained and development fog and bleaching fog can be reduced.

[0184]

According to the present invention, color development for a silver halide color photographic light-sensitive material is capable of obtaining good image performance even during rapid processing and at the same time obtaining low development fog and bleaching fog. A developing solution and a processing method can be provided.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 7/20 G03C 7/20

Claims (10)

[Claims] (1) Lithium ion is added to a color developing solution in an amount of 0.1 to 0.1%.
It is contained in the range of from 0.1 mol / L to 0.5 mol / L, and further contains 0.025 mol of a color developing agent.
A color developing solution for silver halide color photographic light-sensitive materials, characterized in that it is contained in an amount of 0.10 mol / liter to 0.10 mol / liter. 2. The color developing solution contains 6.0 × 10 ⁻⁷ mol / liter of iodine ion to 7.0 × 10 ⁷ mol / l.
^{2. The} color developing solution for a silver halide color photographic light-sensitive material according to claim 1, which is contained in the range of ^-5 mol / l. 3. A silver halide having a silver iodide content of 0.5 m
ol% to 15 mol% of a silver halide color photographic light-sensitive material, and lithium ions of 0.01 mol /
A method for processing a silver halide color photographic light-sensitive material, wherein the processing is performed with a color developing solution having a content of from 1 liter to 0.5 mol / liter. 4. A method for processing a silver halide color photographic material according to claim 3, wherein the color development processing time is 30 seconds or more and 120 seconds or less. 5. The method for processing a silver halide color photographic material according to claim 3, wherein the color developing agent is contained in the range of 0.025 mol / l to 0.10 mol / l. 6. The method for processing a silver halide color photographic light-sensitive material according to claim 3, wherein the processing temperature in the color development processing step is 40 ° C. or more and 55 ° C. or less. 7. The processing solution for color development contains iodine ions in an amount of from 6.0 × 10 ⁻⁷ mol / L to 7.0 × 10 ⁷ mol / L.
7. The method for processing a silver halide color photographic light-sensitive material according to claim 3, wherein the content is in the range of ^-5 mol / l. 8. The silver halide color photographic light-sensitive material according to claim 1, wherein 50% or more of the total projected area is a tabular silver halide having an aspect ratio of 5 or more and a thickness of 0.1 μm to 0.3 μm. The maximum silver iodide content of the layer excluding the outermost layer is less than 15 mol%, the silver iodide content of the outermost layer is 6 mol% or more, and 5% or more per grain The silver halide color photographic light-sensitive material according to any one of claims 3 to 7, wherein an emulsion containing silver halide grains having at least one dislocation line is contained in at least one photosensitive layer. Processing method. 9. The method according to claim 3, wherein the weight ratio of total lipophilic photographic material to total gelatin in the silver halide color photographic light-sensitive material is 0.50 or more and 0.70 or less. The method for processing a silver halide color photographic light-sensitive material described in 1 above. 10. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide has a silver halide content of 3.0 g / m ² or more and 7.0 g / m ^2.
The method for processing a silver halide color photographic material according to any one of claims 3 to 9, wherein the composition is applied in the following range.