JPH11119399A - Treatment of silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make obtainable a good image even when rapid color development is carried out, by using a color developing liquid containing a specified amt. of potassium ion and developing it for a specified period. SOLUTION: A photographic material is developed by using a color developing liquid containing 0.65 to 1.5 mol/l potassium ion for 30 to 120 sec of color developing time. The density of potassium ion is preferably within the 0.81 to 1.0 mol/l range from the viewpoints of image density and a bleaching fog. The developing time is preferably controlled to 60 to 90 sec from the viewpoint of a developing fog. In the color developing liquid, a color developing agent is preferably used within the 0.02 to 0.01 mol/L range, more preferably within the 0.03 to 0.05 mol/L range. A treating temp. in a color developing process is preferably controlled to 40 to 55 deg.C. The color developing main agent is preferably a para-phenylene diamine compd. and for example, a compd. having water- soluble groups is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a method capable of obtaining a good image even during rapid processing, at the same time having low bleaching fog and good image storability. The present invention relates to a method for processing a silver halide color photographic light-sensitive material capable of obtaining the following.

[0002]

2. Description of the Related Art With the rapid increase of minilab shops in recent years, there is an increasing demand for faster processing of silver halide photographic light-sensitive materials (hereinafter also referred to as light-sensitive materials and light-sensitive materials for simplicity). Means for achieving rapid processing include increasing the concentration of a color developing agent (hereinafter, also simply referred to as "main agent") described in JP-A-4-67038 and the like.
No. 48 has been studied to speed up processing by activating a color developing solution such as raising the temperature.

[0003]

In the color developing step, the color developing agent and the alkaline agent react from the upper layer, so that the arrival of the main agent and the alkaline agent to the lowermost layer is greatly delayed. This delay in arrival is particularly serious for a main drug having a large molecular weight, and when rapid processing is performed, the main ingredient is not sufficiently supplied to the lowermost layer. Therefore, improvement of the developability of the lowermost layer is the greatest problem in realizing rapid processing. Therefore, as described above, studies aimed at shortening the time required for the main drug to reach the lowermost layer by increasing the concentration of the main drug and improving the developability of the lowermost layer have been repeated.

However, since the color photographic material is preliminarily hardened on the gelatin film of the photographic material, it is possible to sufficiently improve that the penetration of the color developing agent into the lowermost layer is largely delayed as compared with other layers. Can not. As a result, only the layers other than the lowermost layer are activated by increasing the concentration of the active ingredient, but do not improve the developability of the lowermost layer, and it is difficult to improve the color balance.

[0005] In addition, there is a great concern that an increase in the concentration of the main ingredient will cause development fogging, and an excessively high concentration cannot be put into practical use at present.

Further, as the concentration of the main agent increases, the concentration of the main agent in the gelatin film of the light-sensitive material does not decrease rapidly when the photosensitive material is immersed in the bleaching tank. So-called bleaching fog, in which the main drug oxidized by the oxidizing agent reacts with the unreacted coupler in the photographic material, is likely to occur. Furthermore, the concentration of the active substance present in the bleaching solution also increases, and bleaching fog is more likely to occur. Further, not only the color development processing step but also the subsequent steps are required to speed up the processing. Speeds up the processing after the color development process,
When the concentration of the main agent is increased in the color developing solution, the washing out of the color developing agent remaining in the light-sensitive material becomes insufficient. If a large amount of color developing agent remains in the light-sensitive material, the image after storage tends to deteriorate, causing a serious problem such as being unable to print on color paper when printing again at a later date. It has been found that it is difficult to achieve rapid processing by increasing the concentration of the active ingredient because the treatment becomes easy.

Accordingly, an object of the present invention is, firstly, to provide a method for processing a silver halide color photographic light-sensitive material capable of obtaining a good image even when rapid color development processing is performed. . Another object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material capable of obtaining low bleaching fog and good image storability even when rapid color development processing is performed.

[0008]

[Means for Solving the Problems]

1. A silver halide color photographic light-sensitive material which is developed using a processing solution for color development containing 0.65 to 1.5 mol / L of potassium ion for a color development processing time of 30 to 120 seconds. Processing method for color photographic light-sensitive materials.

[0009] 2. 2. The method for processing a silver halide color photographic light-sensitive material according to 1, wherein the processing solution for color development contains a color developing agent in a range of 0.020 to 0.10 mol / L.

[0010] 3. (1) The processing solution for color development contains a compound represented by the following general formula (1).
Or the method for processing a silver halide color photographic light-sensitive material according to item 2.

[0011]

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Wherein 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, and R represents a hydrogen atom. Or an alkyl group. Each of L, A, and R includes both linear and branched chains, and may be unsubstituted or substituted. L and R
May be linked to form a ring. ] 4. 4. The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 3, wherein the processing temperature of the color developing solution is 40 to 55 ° C.

5. The silver halide emulsion of the silver halide color photographic light-sensitive material has a silver halide iodine content in the range of 0.5 to 10 mol%.
5. The method for processing a silver halide color photographic light-sensitive material according to any one of items 1 to 4.

6. The silver halide color photographic light-sensitive material is tabular silver halide grains having an aspect ratio of 5 or more and a thickness of 0.1 to 0.3 [mu] m, wherein 50% or more of the total projected area is the tabular silver halide grains. Of the phase 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 dislocations per grain. 6. The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 5, wherein at least one layer contains a silver halide emulsion containing tabular silver halide grains having a line. .

[0015] 7. The weight ratio of the total lipophilic photographic material / the total gelatin in the silver halide color photographic light-sensitive material is 0.5.
7. The method for processing a silver halide color photographic light-sensitive material according to any one of 1 to 6, wherein the number is from 0 to 0.70.

8. The method for processing a silver halide color photographic material according to any one of 1 to 7, wherein the silver halide color photographic light-sensitive material is characterized in that it is 3000~7000mg / m ² coated with a silver halide.

That is, the present inventor has set the concentration of potassium ion in the color developing solution to 1 (that is, the invention described in claim 1).
By adjusting the density to a specific concentration, the degree of swelling of the gelatin film of the light-sensitive material is increased, and the penetration of the base agent is improved. It has been found that the improvement, the reduction of the bleaching fog and the improvement of the image storability can be performed at the same time, and the rapid processing of the color light-sensitive material can be realized.

The developer containing a high concentration of potassium ions is described in JP-A-9-212804, but is a developer for a monochrome photosensitive material. Are completely different. Further, the processing time is different from that of the present invention.
No. 804 does not suggest the present invention.

Hereinafter, the present invention will be described in detail.

(Color development processing step) The processing agent for color development of the present invention contains 0.65 to 1.5 mol /
L, but the concentration of potassium ion is 0.1.
The image density is in the range of 81 to 1.0 mol / L,
It is more preferable from the viewpoint of bleaching fog.

The processing time of the color developing process of the present invention is 3
The time is 0 to 120 seconds, and preferably 60 to 90 seconds from the viewpoint of development fog.

In the color developing agent of the present invention, the color developing agent is preferably used in the range of 0.020 to 0.10 mol / L, more preferably 0.03 to 0.05 mol / L.
/ L or less.

The processing temperature of the color developing process of the present invention is 4
The temperature is preferably from 0 to 55 ° C, more preferably from 40 to 45 ° C.
C. is more preferable.

The color developing agent preferably used in the present invention is preferably a paraphenylenediamine-based compound. As the paraphenylenediamine-based compound, a compound having a water-soluble group exhibits the desired effects of the present invention. It is preferably used because the occurrence of odor is small.

Further, the p-phenylenediamine compound having a water-soluble group has less contamination of the photosensitive material than a p-phenylenediamine compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. Not only does it have the advantage that the skin is not fogged and the skin is not easily fogged. In particular, the object of the present invention can be more efficiently achieved by combining it with the color developing solution of the present invention.

Examples of the paraphenylenediamine compound having a water-soluble group include those having at least one water-soluble group on the amino group or on the benzene nucleus of the paraphenylenediamine compound. Specific water-soluble _{group, - (CH 2) n-} CH 2 OH, - (CH 2) m-NH
_{SO 2 - (CH 2) nCH} 3, - (CH 2) m-O- (CH
_{2) n-CH 3, -} (CH 2 CH 2 O) nCmH2m + 1,
(M and n each represent an integer of 0 or more.)
H group, —SO ₃ H group and the like are mentioned as preferable ones.

Specific examples of the paraphenylenediamine compound preferably used in the present invention include the following.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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

The above-mentioned paraphenylenediamine compound is usually used in the form of hydrochloride, sulfate or p-toluenesulfonate.

Next, the compound represented by formula (1) will be described in more detail.

It is preferable that the processing agent for color development of the present invention does not substantially contain hydroxylamine. Further, it is preferable that the compound represented by the general formula (1) is contained.

Next, the compound represented by formula (1) will be described in more detail.

In the general formula (1), L represents 1 carbon atom.
Represents a linear or branched alkylene group 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 ammonio 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. Particularly preferred examples include a group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. R
Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted in a linear or branched chain, 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 ammonio 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. Groups, carboxyethyl groups, sulfoethyl groups, sulfopropyl groups, phosphonomethyl groups, and phosphonoethyl groups can be mentioned as particularly preferred examples. L and R may combine to form a ring.

The typical examples of the compounds represented by the formula (1) are shown below, but the present invention is not limited to these compounds.

[0040]

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[0041]

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[0042]

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[0043]

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The concentration of the compound represented by the general formula (1) is preferably from 0.001 to 0.2 mol / L, more preferably from 0.01 to 0.04 mol / L. The compounds represented by the general formula (1) may be used alone or in combination of two or more.

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. Sulfite concentration is 1
It is preferably from × 10 ^-4 to 1 × 10 ^-1 mol / l.

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 phosphoric acid. Dipotassium, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-2-hydroxy Sodium benzoate (sodium 5-sulfosalicylate),
Potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) is preferred.

An alkali agent is used in the processing solution for color development, and examples of the alkali agent include sodium hydroxide and potassium hydroxide in addition to the above-mentioned buffering agents.

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

It is preferable that the color developing solution does not substantially contain benzyl alcohol.

Iodine ions and bromine ions can be added to the color developing solution for the purpose of preventing fog and the like. When directly added to a color developing solution, sodium, potassium, ammonium,
Nickel, magnesium, manganese, calcium or cadmium chloride may be mentioned, and preferred are sodium iodide and potassium iodide. 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,
Mention may be made of magnesium, manganese, nickel, cadmium, cerium or thallium bromides, of which potassium bromide and sodium bromide are preferred. The content of these halogen ions is at most 0.02 mol / l, preferably 0.001 mol / l or less.

The processing solution for color development preferably contains a triazinylstilbene-based fluorescent whitening agent, and more specifically, a compound represented by the following general formula [E].

[0052]

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In the above formula, X ₂ , X ₃ , Y ₁ and Y ₂ each represent a hydroxyl group, a halogen atom such as chlorine or bromine, an alkyl group, an aryl group,

[0054]

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[0055] or represents a -OR _17. Where R ₁₃ and R ₁₄
Represents a hydrogen atom, an alkyl group (including a substituent) or an aryl group (including a substituent), R ₁₅ and R _{16 each} represent an alkylene group (including a substituent), and R ₁₇ represents a hydrogen atom, an alkyl group (including a substituent). Represents a substituent) or an aryl group (including a substituent), and M represents a cation.

Further, other 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, and stabilizing steps, are carried out in a usual manner. The configuration may be made according to. For example, a process having a bleaching ability is described in JP-A-9-9057.
No. 9, a process having a fixing ability and a stabilization process are described in JP-A-8-2.
01997.

Preferred specific processing steps of the processing method according to the present invention are shown below.

(1) Color development → bleaching → fixing → washing (2) Color developing → bleaching → fixing → washing → stable (3) Color developing → bleaching → fixing → stable (4) Color developing → bleaching → fixing → first 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 → Bleaching and fixing → First stable → Second stable (9) Color development → Bleaching → Bleaching and fixing → Fixing → Washing → Stable (10) Color developing → 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 silver halide photographic light-sensitive material referred to in the present invention is a material which forms an image with a dye, and has at least three layers of a blue light-sensitive layer, a green light-sensitive layer and a red light-sensitive layer. Refers to those composed of emulsion layers.

The light-sensitive material used in the present invention may be a silver halide photographic light-sensitive material containing a silver chloride emulsion, but a high-sensitivity silver halide photographic light-sensitive material containing silver bromide or silver iodobromide. Preferably, it is a material.

The amount of silver halide applied in the present invention refers to the amount of silver applied on a support before the light-sensitive material is processed.

The silver halide coated with the light-sensitive material used in the present invention is preferably in the range of 3000 to 7000 mg / m ² . In addition, 4000-6000
More preferably, it is mg / m ² .

The tabular silver halide (hereinafter also referred to as “tabular grain”) in the present invention has two parallel main planes and a circle-equivalent 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 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 grains of 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 coefficient of variation (diameter of the diameter of a circle having the same projected area as the main plane) of the principal plane by the standard deviation of the diameter distribution. ) 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.
The silver iodide content is preferably from 0.5 to 10 mol%, more preferably from 3 to 8 mol%. If the silver iodide content is too high, the development progress will be reduced, and if it is too low, the processing stability will be degraded.

The intergranular distribution of the silver iodide content of the silver halide grains of the present invention is determined 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 more preferably 20% or less.

The tabular grains of the present invention have at least two or more phases having different halogen compositions inside the grains, and the phase having the highest silver iodide content excluding the outermost layer has a silver iodide content of 3%. It is from mol% to less than 15 mol%, preferably from 3 mol% to less than 10 mol%, more preferably from 5 mol% to less than 8 mol%. 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.

In the present invention, the silver iodide content on the grain surface may be either 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 is determined as follows. The sample was cooled to −115 ° C. or less in an ultra-high vacuum of 1 × 10 ⁻⁸ torr or less, and irradiated with MgKα as a probe X-ray at an X-ray source voltage of 15 kV and an X-ray source current of 40 mA, and Ag3d5 / 2 and Br3d. , I3
It measures about d3 / 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.

Further, the maximum silver iodide-containing phase excluding the outermost layer in the present invention does not include a high iodine-localized region generated by an operation described below 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 244 can be referred to.
For example, a double jet method, a double jet method, a so-called controlled double jet method which maintains a constant pAg in a liquid phase in which silver halide is formed, which is a type of the double jet method, and a soluble silver halide having a different composition, respectively. A triple jet method, which is added independently, 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. For thioethers, reference can be made to U.S. Pat. Nos. 3,271,157, 3,790,387, 3,574,628 and the like.
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, from the viewpoint of reducing fogging of silver halide grains, it is preferable to use pH (hydrogen). The logarithmic value of the reciprocal of the ion concentration) is 5.5 or less, more preferably 4.5 or less.

The silver halide 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.
As with the grains disclosed in JP-A-1-183417, JP-A-1-183644, JP-A-1-183645 and the like, grain growth may be performed using only silver halide fine grains. May be supplied by silver halide fine particles. In this case, the iodide 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 even if at least one of them is composed of only one kind of halogen element, Good.

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 preferable 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. F. Ha
Milton, Photo. Sci. Eng. , 11
(1967), 57; Shiozawa, Jou.
ofPhoto. Sci. Japan, 35 (197
2) Observation can be performed by the method described in 213, that is, a direct method using a transmission electron microscope at a low temperature. That is, silver halide grains taken out so as not to apply enough pressure from the emulsion to generate dislocations on the grains are placed on a mesh for an electron microscope to prevent damage (printout, etc.) by an electron beam. Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particle, the more difficult it is for the electron beam to pass therethrough.
The use of an electron microscope (200 kV) for a thickness of 5 μm allows 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 dislocation position of the grains of the present invention does not necessarily have to be at a specific location, but preferably exists at the fringe portion of the tabular grains. 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 projected 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 70%, more preferably 80%
% Means the area outside.

The number of dislocations in the tabular grains of the present invention is preferably such that grains containing 5 or more dislocations 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 dislocations 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.

In the case where dislocation lines are present inside 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 of 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 water-soluble silver salt solution by a double jet at the position where the dislocation is to be introduced, or A method of adding silver halide fine particles, a method of adding only an iodine ion solution,
The method can be carried out by a method using an iodide ion releasing agent as described in No. 11781. A method of adding an aqueous iodide ion solution and a water-soluble silver salt solution by a 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 iodide ions 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 dislocation is preferably introduced 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.

Further, in relation to the position of the whole grain, it is preferable that the silver is introduced in an amount corresponding to 50 to 95% of the silver amount of the whole grain, and it is more preferable that the silver is introduced in a proportion 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 material. Similarly or simultaneously, it refers to one that is dissolved, emulsified and dispersed. 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 DIR coupler is also included.

As the organic high-boiling compound, 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 for adding the lipophilic photographic material. Typical examples of the method include one or more of the above-mentioned organic high-boiling compounds and the like. A compound capable of forming an oil droplet is dissolved with a photographic additive as described below, if necessary, and further, if necessary, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, dimethylene glycol Dissolved in low boiling solvents such as monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, ethyl alcohol, propyl alcohol, fluorinated alcohol, acetonitrile, dimethylformamide, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone The low 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. An aqueous solution containing a hydrophilic colloid substance such as gelatin containing an activator is mixed and emulsified and dispersed with a high-speed rotating mixer, a colloid mill or an ultrasonic dispersing device, and the obtained dispersion is applied to a coating liquid containing a hydrophilic colloid substance. And coated on a support or on a silver halide emulsion layer 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.

The oil-soluble couplers include a yellow coupler, a magenta coupler, and a cyan coupler which form a color image by color development.

As the couplers usable in the present invention, the compounds described in the following patents are representatively included.

Among them, yellow couplers include benzoylacetanilide type, pivaloylacetoanilide type,
Alternatively, it is a 2-equivalent yellow coupler in which the carbon atom at the coupling position is substituted with a substituent (so-called split-off group) capable of leaving during the coupling reaction. Examples of magenta couplers include 5-pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, indazolone and split-off groups.
It is an equivalent magenta coupler.

Further, 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 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 a developing agent is also mentioned.

The lipophilic photographic material in the non-photosensitive layer preferably contains an anti-turbidity agent. 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. H4-1 to H-18), pyrogallol-based compounds, catechol-based compounds (Japanese Patent Application No. 4-19048)
Nos. P1 to P16), sulfonylamino compounds (Japanese Patent Application No. 4-19048, S-1 to S-19), coupling type compounds (CP-1 to CP23) and hydrazine compounds (HZ-1 to HZ-14) ) And the like.

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) tends 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.
90 or less, more preferably 0.35 or more and 0.70 or more
It is as follows. In the present invention, the weight ratio of all lipophilic photographic materials / gelatin in the non-photosensitive intermediate layer is from 0.30 to 0.90, more preferably from 0.35 to 0.9.
70 or less. 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 layers adjacent to each other may be photosensitive layers, non-photosensitive layers, or both a photosensitive layer and a non-photosensitive layer. The weight of the lipophilic photographic material between all adjacent layers / The difference in gelatin weight ratio is 0 or more and 0.60 or less, and more preferably 0 or more and 0.50 or less.

The photographic constituent layer of the light-sensitive material of the present invention preferably has a calcium content of 50 ppm or less, 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 bovine bone and pig skin, and then subjected to ion exchange using an ion exchange resin (for example, IRA type manufactured by Rohm and Haas Company).

The calcium ion content after the ion-exchange treatment can 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.

[0107]

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

Example 1 This example was carried out as follows using an automatic developing machine having a processing tank as shown in FIG. 1 (hereinafter also referred to as an automatic developing machine).

The structure of the processing tank shown in FIG. 1 is shown below.

In the photosensitive material processing tank 1Y, a lower member 13Y which defines the shape of the lower side of the processing tank in a shape along the transport path and also serves as a transport guide for the silver halide photographic photosensitive material, The upper side of the processing tank, which is shaped along the transport path, defines the shape, and is on the transport path between the upper member 12Y, which also serves as a transport guide for the silver halide photographic material, and the lower member 13Y and the upper member 12Y. , And transport rollers 16Y, 17Y, and 18Y for transporting the silver halide photographic light-sensitive material. And
Only the insertion port 14Y and the discharge port 15Y of the transport path defined between the lower member 13Y and the upper member 12Y are gas-liquid interfaces of the processing liquid in the processing tank 1Y. Further, although not shown, a transfer guide 28Y provided in close contact with the lower member 13Y on the downstream side of the transfer path of the discharge port 15Y, and an opposing roller for transferring the silver halide photographic material along the transfer guide 28Y. A certain transfer roller pair 29Y is provided.

On the side of the photosensitive material processing tank 1Y, the processing tank 1
Y has an auxiliary tank 2Y provided separately. Then, a circulation pipe 21Y is formed from the processing tank 1Y to a lower portion of the auxiliary tank 2Y so that the processing liquid flows.

The rod-shaped heater 26Y is provided so as to penetrate the upper wall of the auxiliary tank 2Y and to be immersed in the processing liquid in the auxiliary tank 2Y. The heater 26Y is connected to a processing liquid circulation path and a processing tank 1 based on a temperature detected by a thermometer (not shown) provided in the auxiliary tank 2Y.
The processing solution in Y is heated, in other words, the processing solution in the processing tank 1Y is heated to a temperature range suitable for processing (for example, 20 ° C.).
To 55 ° C.).

[0113] The plate-like filter 22Y is
Y and a circulation pipe 29Y to the processing liquid storage tank 4Y
The auxiliary tank 2Y is provided so as to be replaceable, and has a function of removing insolubles, for example, precipitates and the like in the processing liquid. The circulation pipe 29Y communicates with the lower part of the auxiliary tank 2Y and the upper part of the processing liquid storage tank 4Y. The lower part of the processing liquid storage tank 4Y is connected to the suction side of a circulation pump 24Y (circulation means) via a circulation pipe 23Y provided through the lower wall of the processing liquid storage tank 4Y.

The circulation system includes the auxiliary tank 2Y and the circulation pipe 2
The processing tank 1Y includes the processing liquid circulation path formed by 9Y, the processing liquid storage tank 4Y, the circulation pipe 23Y, the circulation pump 24Y, and the circulation pipe 25Y. The other end of the circulation pipe 25Y communicating with the discharge side of the circulation pump 24Y penetrates the lower wall of the processing tank 1Y, and is connected to a nozzle 27Y that uniformly discharges the processing liquid in the width direction toward the transport path of the processing tank 1Y. Communicating. With such a configuration, when the circulation pump 24Y operates, the processing liquid is sucked from the auxiliary tank 2Y, discharged into the processing tank 1Y, and circulated again into the auxiliary tank 2Y.

FIG. 2 is a schematic cross-sectional view showing a partial schematic configuration of the automatic processing machine connected to the processing tank shown in FIG. The processing tank is a color developing tank C from the left along the transport direction of the silver halide photographic material P.
D, bleaching tank BL, fixing tank Fix (first fixing tank Fix1,
Second fixing tank Fix2) ・ Stabilizing tanks STB1, STB2,
STB3 is arranged in the horizontal direction. Each of the tanks is filled with a color developing solution, a bleaching solution, a fixing solution, and a stabilizing solution. The photosensitive material P is configured to be transported by a transport roller. In this embodiment, the processing liquid in each processing tank is filled to almost the same height. The time when the photosensitive material is moved between the processing tanks and is not immersed in the processing solution is 5 minutes each.
Seconds.

The processing tank is formed in a single tank unit, and is extremely thin compared to a conventional automatic developing machine. Thereby, the opening area is remarkably reduced, and the tank capacity is also reduced. These upper surface members define the upper shape of the processing tank along the transport path, and also serve as the transport path of the silver halide photographic light-sensitive material. In this example, processing tanks having the same size were used for all processing tanks except for the color developing processing tank.

FIG. 3 is a diagram showing a specific configuration of the processing tank 1Y. FIG. 3A is a diagram showing the shape of the processing tank 1Y. FIG. 3B is a diagram showing the arrangement of holes as viewed from the ejection direction of the nozzle 27Y. The nozzles 27Y are distributed in the width direction longer than the width of the photosensitive material to be conveyed in order to uniformly discharge the processing liquid in the width direction, and a plurality of nozzle examples having uniform intervals are provided in the conveyance direction. Have been. These nozzles make an angle of 90 ° with the transport direction.
Further, as shown in FIG. 3B, the nozzles 27Y are provided at equal intervals, and the nozzles are similarly provided in the adjacent nozzle rows at a half pitch from the nozzles of the nozzle rows.
The nozzles are arranged in a zigzag as a whole. These nozzles 27Y spray a pressurized processing solution from a hole having a spray angle of 90 ° and a diameter of 2.0 mm.

Konica Color Negative Film L which has been subjected to wedge exposure by a usual method using the above automatic developing machine
V400 (24 shots) was continuously processed for 15 days at a rate of 20 a day under the following conditions.

(Processing step) Processing time Processing temperature Replenishment amount Color development Developed Table 42.5 ° C. 520 ml / m ² Bleaching 22 seconds 38 ° C. 100 ml / m ² Fixing-1 22 seconds 38 ° C. Fixing-2 22 seconds 38 ° C. 550 ml / m ² Stable-1 22 seconds 38 ° C. Stable-2 22 seconds 38 ° C. Stable-3 22 seconds 38 ° C. 860 ml / m ² Drying 40 seconds 65 ° C. The fixing process is 2 to 1 and the stabilization process is 3 It was a countercurrent system from 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 29.0 g Potassium bicarbonate 2.9 g Diethylenetriaminepentaacetic acid pentasodium 2.6 g Exemplified compound 1-7 4.25 g Hydroxide Sodium 1.36 g Potassium bromide 1.33 g 2-Methylbenzimidazole 0.05 g Polyvinylpyrrolidone K-17 4.0 g Potassium iodide 2.0 mg Potassium nitrate Listed in Table 1 4-amino-3-methyl-N-ethyl-N -(Β-hydroxyethyl) aniline sulfate (Exemplified Compound C-3) 10.5 g Water was added to make 1 L, and the pH was adjusted to 10.1 with potassium hydroxide or 50% sulfuric acid. Adjusted to 3.

(Replenisher for color development) Sodium sulfite 7.0 g Potassium carbonate 29.0 g Potassium bicarbonate 2.9 g Diethylenetriaminepentasodium pentasodium 4.0 g Exemplified compound 1-7 5.10 g Sodium hydroxide 1.63 g Bromide Potassium 0.4 g 2-Methylbenzimidazole 0.05 g Polyvinylpyrrolidone K-17 4.0 g Potassium nitrate The same amount as the starting solution 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate ( Exemplified compound C-3) 12.0 g Water was added to make 1 L, and the pH was adjusted to 10.1 with potassium hydroxide or 50% sulfuric acid. Adjusted to 5.

(Bleaching start solution) Ferric ammonium 1,3-propylenediaminetetraacetate 140 g 1,3-propylenediaminetetraacetic acid 7 g Ammonium bromide 60 g Succinic acid 30 g Maleic acid 30 g Add water to make 1 L, and add ammonia water or Adjust the pH to 3.0 using 20% sulfuric acid.

(Bleaching replenisher) Ferric ammonium 1,3-propylenediaminetetraacetate 190 g 1,3-propylenediaminetetraacetic acid 10 g Ammonium bromide 90 g Succinic acid 45 g Maleic acid 45 g Add water to make 1 L, and add ammonia water or Adjust the pH to 2.0 using 20% sulfuric acid.

(Fixing Start Solution, Fixing Replenisher) Ammonium thiosulfate 250 g Sodium sulfite 18 g Potassium carbonate 2 g Ethylenediaminetetraacetate 2 g 2 g Water was added to make up to 1 L, and pH = 6 using ammonia water or 20% sulfuric acid. Adjust to 5.

(Stabilizing Solution, Stabilizing Replenishing Solution) m-hydroxybenzaldehyde 1.5 g disodium ethylenediaminetetraacetate 0.2 g potassium carbonate 0.2 g potassium hydroxide 0.03 g Water is added to make up to 1 L.

The processing time in the color development processing step was changed as shown in Table 1, and the amount of potassium nitrate added was changed so that the concentration of potassium ion became as shown in Table 1, and the above conditions were continuously applied. After the processing, the Konica Color Negative Film LV400 that has been subjected to wedge exposure by the above-described normal method is processed, and the unexposed portion 440 of the processed photosensitive material is processed.
The transmission density in nm (Dmin (B)) was measured. Also,
Dmin (B) at start and 660n of maximum density part
The transmission density (Dmax (R)) of m was also measured.

Table 1 summarizes the results.

In this embodiment, from the viewpoint of printing efficiency when printing on color paper, Dmin
It is preferable that (B) does not change from 0.91.

[0129]

[Table 1]

As is clear from the results in Table 1, potassium ions are contained in the range of 0.65 mol / L to 1.5 mol / L, and the color development processing time is 30 seconds to 12 mol / L.
It can be seen that a sufficient image density can be obtained and the bleaching fog can be suppressed to a low level by setting the time to 0 second or less (the configuration of the invention described in claim 1).

Example 2 Illustrative compound 1-7 of the processing agent for color development used in Example 1
And the hydroxylamine sulfate were changed to the compounds and addition amounts shown in Table 2, and the treatment was carried out continuously for 20 days at a ratio of 15 per day for 20 days. A continuous processing experiment similar to 1-9 was performed, and D at the start and end of the continuous processing was determined.
The max (R) and Dmin (B) were measured.

Further, the compound 1-7 of the replenishing color-developing agent used in Example 1 was changed to the compounds shown in Table 2 and the added amount thereof, and the opening area ratio was 100 cm ² / L.
Leave at 50 ° C for 2 weeks in the container of
Was measured.

The above results are summarized in Table 2.

The HAS in the table indicates a sulfate of hydroxylamine.

[0135]

[Table 2]

As is clear from Table 2, by containing the compound represented by the general formula (1) (the constitution of the invention according to claim 3), continuous treatment with high stability can be realized. It can also be seen that the stability of the processing solution is also improved.

Further, it is clear that the effect can be further exerted when the compound represented by the general formula (1) is contained in the range of 0.001 mol / L to 0.2 mol / L.

Example 3 The concentration of the color developing agent (exemplified compound C-3) in the starting solution for color development used in Example 1 was changed as shown in Table 3, and the color developing time was fixed at 90 seconds. And the amount of potassium nitrate added was fixed to 0 g / L or 40 g / L (Table 3).
Under the same conditions as in Example 1 except that the unexposed Konica Color Negative Film LV400 was only treated with the respective starting solutions. 55 of photosensitive material after processing
The transmission density (Dmin (G)) of 0 nm was measured and 60
Stored in a dark place at 50 ° C. and 50% RH for 10 days, and the amount of increase in transmission density at 550 nm after storage (ΔDmin (G))
Was measured.

Each starting solution was left in a container having an opening area ratio of 100 cm ² / L at 50 ° C. for 2 weeks, and the state of the treated solution after storage was visually evaluated according to the following criteria.

Table 3 summarizes the results.

In this embodiment, from the viewpoint of printing efficiency when printing on color paper, Dmin
It is preferable that (G) does not change from 0.75.

<< State of treatment liquid after storage >> ：: No generation of tar is observed at all △: The degree of generation of tar on the surface of the liquid is at a level that does not cause any problem ×: Tar is generated

[0143]

[Table 3]

As is clear from Table 3, the color developing processing agent contained 0.020 mol / L to 0.10 m of the color developing agent.
It is clear that by containing the compound in the range of ol / L (the structure of the invention described in claim 2), high printing efficiency can be maintained and good image storability can be obtained.

Example 4 CNK-4 was prepared using CL-KP-50QA (manufactured by Konica Corporation).
When a treatment is performed under the same process conditions using a replenisher for the -52 process and a starter (manufactured by Konica Corporation) under the same process conditions, the bombardment exposure is performed so that the transmission density at 440 nm becomes 1.00. Experiment No. 1 of Example 1 except that the processed Konica Color Negative Film LV400 was processed at the processing temperature described in Table 4. The processing was performed under the same conditions as in 1-9, and the transmission density of 440 nm and 550 nm was measured at arbitrary six locations of the exposed portions,
The average value (DB) of the transmission density at 40 nm, the density difference (ΔDB) between the maximum value and the minimum value, and the average value (DG-1) of the transmission density at 550 nm were determined. In this embodiment, ΔDB is used as a measure of development unevenness.

In addition, CL-KP50QA (Konica Corporation)
And a starter (manufactured by Konica Corporation) as a processing agent, and the above-mentioned photosensitive material is processed under the same processing conditions as above, and the transmission density at 550 nm is measured in the same manner. And the average value of transmission density at 550 nm (DG-2) was determined. Further, color turbidity (ΔD) was evaluated using the following equation.

ΔD = (DG-1) − (DG-2) Average density value (DB), uneven development (ΔDB), turbidity (Δ
The results of D) are summarized in Table 4.

[0148]

[Table 4]

As is clear from the results shown in Table 4, when the processing temperature in the color development processing step is 40 ° C. to 55 ° C. (the structure of the invention described in claim 4), an appropriate density can be obtained. It can be seen that development unevenness and color turbidity can be suppressed low.

Example 5 Preparation of seed crystal emulsion-1 A seed crystal emulsion was prepared as follows.

Japanese Patent Publication Nos. 58-58288 and 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, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, 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), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% of potassium iodide) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing 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) n H (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 While vigorously stirring 5 l, 2 l each of a 7.06 mol aqueous silver nitrate solution and a 7.06 mol aqueous potassium iodide solution 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 preparation of the particles, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The average particle size of the obtained silver iodide fine particles is 0.05 μm.
Met. This emulsion is designated as SMC-1.

Preparation of Emulsion Em-1 0.178 moles of seed crystal emulsion-1 and HO (CH ₂ CH _{2
O) m (CH (CH 3} ) CH 2 O) 19.8 (CH 2 CH 2 O)
10% ethanol solution of nH (m + n = 9.77)
4.5% by weight of an inert gelatin aqueous solution containing 5 ml 7
The solution was kept at 75 ° C., the pAg was 8.9, and the pH was 5.
After adjusting to 0, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure.

1) A 2.1 mol aqueous solution of silver nitrate and 0.19
5 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.

2) Subsequently, a 1.028 mol aqueous solution of silver nitrate, 0.032 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining the pAg at 8.9 and the pH at 5.0.

[0157] 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 completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH 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 4 having a side length of 0.65 μm and an average aspect ratio of 7.2.

When the surface silver iodide content was measured by the method described in this specification, the surface silver iodide content was found to be:
It was 4.5 mol%.

Preparation of Emulsion Em-2 In the preparation of Emulsion Em-1, after the completion of the step 2), the emulsion was dried.
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 emulsion obtained 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 moles of seed crystal emulsion-1 and HO (CH ₂ CH _{2
O) m (CH (CH 3} ) CH 2 O) 19.8 (CH 2 CH 2 O)
10% ethanol solution of nH (m + n = 9.77)
4.5% by weight of an inert gelatin aqueous solution containing 5 ml 7
The solution was kept at 75 ° C., the pAg was 8.9, and the pH was 5.
After adjusting to 0, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure.

1) 2.1 mol silver nitrate aqueous solution and 0.19
5 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.

2) Subsequently, the solution was cooled to 60 ° C.
Was adjusted to 9.8. Then, 0.071 mol of SMC
-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) 0.959 mol silver nitrate aqueous solution and 0.1 mol
030 mol of SMC-1 and an aqueous solution of potassium bromide,
The pAg was added while maintaining the pH at 9.8 and 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 addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH 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 4 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).
This emulsion was composed of tabular grains having a side composition of 0.65 μm and an average aspect ratio of 6.7 and having a halogen composition shown in Table 4. 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% solution of polyethylene oxy-disuccinate sodium salt in ethanol
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) 0.692 mol of silver nitrate aqueous solution and 0.1 mol
297 moles of SMC-1 and potassium bromide aqueous solution
The pAg was added while keeping the pH at 8.9 and the pH at 5.0.

2) Subsequently, an aqueous solution of 2.295 mol of silver nitrate, 0.071 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining the pAg at 8.9 and the pH at 5.0.

3) After completion of the step 2), 0.004 mol of SMC-1 was added and the mixture was 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).
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 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 E prepared as described above
Table 5 shows the content of m-6.

[0178]

[Table 5]

Sensitizing dyes SD-5, SD-6 and SD-7 were added to the above emulsions Em-1 to Em-6, and sodium thiosulfate, chloroauric acid, potassium thiocyanate and 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 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.

[0182]

Embedded image

<< Preparation of Multilayer Color Photographic Material Sample >> On a triacetylcellulose film support provided with an undercoat layer, each layer having the following composition was sequentially formed from the support side to prepare a multilayer color photographic material sample 101 Was prepared. In the fifth, tenth and fourteenth layers, the emulsion Em-
A was used.

[0184] The addition amount is particularly shows the number of grams per 1 m ² unless otherwise noted. Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed 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 Antifouling agent (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 particle size 0.38 μm, iodine Silver iodide emulsion (average grain size: 0.27 μm, silver iodide content: 2.0 mol%) 0.13 Sensitizing dye (SD-1) 8 × 10 ^-4 sensitizing dye (SD-2) 1.9 × 10 ^-4 sensitizing dye (SD-3) 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 (D-1) 0.025 High boiling point solvent (Oil-1) 0.49 Gelatin 1.14 Fourth layer: middle-sensitivity red-sensitive layer Silver iodobromide emulsion (average particle size 0.52 μm, silver iodide content 8.0 mol%) 89 silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.22 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) 0.45 colored cyan coupler (CC-1) 0.038 DIR compound (D-1) 0.017 High-boiling-point solvent (Oil-1) 0.39 Gelatin 1.01 Fifth layer: High-sensitivity red-sensitive layer Emulsion Em-A 1.17 Sensitizing dye (SD-1) 1.3 × 10 ^-4 Sensitizing dye (SD-2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-4 Cyan coupler (C-2) 0.18 Color Dosian coupler (CC-1) 0.034 DIR compound (D-3) 0.001 High boiling solvent (Oil-1) 0.37 Gelatin 1.10 6th 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 38 μm, silver iodide content 8.0 mol%) 0.60 silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.19 sensitizing dye (SD-4) ) 7.4 × 10 ^-4 sensitizing dye (SD-5) 6.6 × 10 ^-4 magenta coupler (M-1) 0.17 Magenta coupler (M-2) 0.49 Colored magenta coupler (CM-1) ) 0.12 High boiling solvent (Oil-2) 0.31 Gelatin 1.89 9th : Medium Sensitivity Green-Sensitive Layer Silver iodobromide emulsion (average grain size 0.59 .mu.m, a silver iodide content of 8.0 mol%) 0.76 Sensitizing dye (SD-6) 1.5 × 10 -4 sensitization Dye (SD-7) 1.6 × 10 ^-4 Sensitizing dye (SD-8) 1.5 × 10 ^-4 Magenta coupler (M-1) 0.043 Magenta coupler (M-2) 0.10 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 10th layer: High sensitivity Green-sensitive layer Emulsion Em-A 1.40 Magenta coupler (M-1) 0.08 Magenta coupler (M-2) 0.120 Colored magenta coupler (CM-2) 0.014 High boiling solvent (Oil-1) 0 .15 High boiling solvent (Oil-2) 0.22 Zera 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 12th layer: Intermediate layer Formalin Scavenger (HS-1) 0.18 Gelatin 0.60 13th layer: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, containing silver iodide 0.069) Silver iodobromide emulsion (average grain size: 0.38 μm, silver iodide content: 3.0 mol%) 0.16 Silver iodobromide emulsion (average grain size: 0.27 μm, Silver iodide content 2.0 mol%) 0.18 Sensitizing dye (SD-9) 2.1 × 10 ^-4 Sensitizing dye (SD-10) 2.8 × 10 ^-4 Yellow coupler (Y-1) ) 0.83 DIR compound (D-4) 0.008 High boiling point solvent ( il-2) 0.27 Gelatin 1.51 14th layer: high sensitivity blue-sensitive layer Emulsion Em-A 0.90 Sensitizing dye ^{(SD-9) 7.3 × 10} -4 Sensitizing dye (SD-10) 2.8 × 10 ^-4 Yellow coupler (Y-1) 0.16 High boiling solvent (Oil-2) 0.093 Gelatin 0.80 15th layer: 1st protective layer Silver iodobromide emulsion (average particle size 0) 0.05 μm, silver iodide content 3.0 mol%) 0.28 UV absorber (UV-1) 0.094 UV absorber (UV-2) 0.12 Formalin scavenger (HS-1) 0.38 high Boiling point solvent (Oil-1) 0.05 Gelatin 1.44 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 Zera Down 0.55 Note that in addition to, coating aids SU-1 of the above-described compositions, 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.

[0187]

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[0188]

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[0189]

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[0190]

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[0191]

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[0192]

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[0193]

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[0194]

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[0195]

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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.

The samples 101 to 106 were subjected to ordinary wedge exposure, and the samples of Experiment No. 1 of Example 1 were exposed. 1-5 or 1-
The same processing (rapid processing) as in No. 9 was performed.

Further, CL-KP50QA (Konica Corporation)
And the starter (manufactured by Konica Corporation) as a processing agent, and the above-mentioned photographic material was processed (normal processing) under the same processing conditions as described below. The gradation stability was evaluated. In addition,
The evaluation of the gradation stability was performed on the sample at the start of the continuous processing.

(Evaluation of Tone Stability) In the D-logE characteristic curve, a point of minimum density +0.3 and a minimum density of +1.8.
The ratio of the rapid processing γR to the normal processing γN, γR / γN, for the gradient γ of the straight line connecting the points, and γR / γN were obtained for the magenta image.

Further, the transmission density (Dmax (R)) of the maximum density part at 660 nm was measured for each sample at the end of the continuous processing when the rapid processing was performed.

The results are summarized in Table 6.

[0202]

[Table 6]

As is clear from Table 6, the photosensitive material to be processed is 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 for 50% or more of the total projected area. 50% or more of the tabular silver halide has a maximum silver iodide content of the phase excluding the outermost layer of 15 mol.
less than 1%, and the silver iodide content of the outermost layer is 6 mol%
The gradation stability is improved by containing at least one silver halide emulsion having at least one dislocation line per grain as described above (the constitution of the invention according to claim 6). I understand.

Example 6 In the sample 101 prepared in Example 5, the amount of the high-boiling solvents Oil-1 and Oil-2 in each layer was increased at the same ratio, and the total weight of the lipophilic photographic material in the silver halide photographic light-sensitive material was increased. / The total gelatin amount (O / G ratio) was adjusted as shown in Table 7, and the gradation stability of the cyan image was evaluated in the same manner as in Example 5. Also, in Experiment No. 1 of Example 1, 1-5 or 1
With respect to the sample after the same treatment as in -9, the physical properties of the coating film were visually evaluated according to the following criteria. Example 5
The sample 101 had an O / G ratio of 0.45.

<< Evaluation of Physical Properties of Coating Film >> ：: No devitrification at all Δ: Degree of slight devitrification confirmed X: Clearly devitrified

[0206]

[Table 7]

As is clear from the results in Table 7, the weight ratio of total lipophilic photographic material / total gelatin in the silver halide photographic light-sensitive material processed in the present invention is 0.50 or more and 0.70 or less. It can be seen that the (gradation stability) and the physical properties of the coating film are improved by the (structure of the invention described in claim 7).

Example 7 The silver iodide content of the emulsions Em-1 to Em-6 prepared in Example 5 was adjusted to change the silver iodide ratio of the whole photographic material as shown in Table 8, and the sensitization was carried out. The same rapid processing and normal processing as in Example 5 were performed by changing the amount of silver applied to the material as shown in Table 8, and then the gradation stability of the cyan image was evaluated as in Example 5. In addition, the sample after the rapid treatment was evaluated for granularity (RMS value) at a place where the transmission density at 440 nm (using a Watten filter W-98 manufactured by Eastman Kodak Co.) was 0.8 by the following method. Was done. The RMS value is obtained by measuring the density of the portion to be measured of the sample by an aperture scanning area of 1.
250 μm ² (slit width 5 μm, slit length 250 μm
m), the sample was scanned with a microdensitometer, and the standard deviation of the fluctuation of the density value for the number of density measurement samplings of 1000 or more was determined to be 1000 times the standard deviation. The RMS value of 7-1 was expressed as a relative value with 1.00. The smaller the RMS value, the better the performance.

Table 8 shows the above results.

[0210]

[Table 8]

As is clear from Table 8, the content of silver halide in the light-sensitive material was 0.5 mol% to 10 mol%.
1% (structure of the invention described in claim 5), or the photosensitive material contains 3000 mg of silver halide.
/ M ^{2 to} 7000 mg / m ² (the constitution of the invention according to claim 8), it can be seen that good gradation stability and good granularity can be obtained.

[0212]

According to the present invention, firstly, a processing method of a silver halide color photographic light-sensitive material capable of obtaining a good image even when rapid color development processing is performed can be provided. Secondly, a processing method of a silver halide color photographic light-sensitive material capable of obtaining low bleaching fog and good image storability even when rapid color development processing is performed can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic view of a processing tank of an automatic developing machine used in Example 1.

FIG. 2 is a schematic cross-sectional view of the automatic developing machine used in Example 1.

FIG. 3 is a specific configuration diagram of the processing tank of FIG. 1;

[Explanation of symbols]

 Reference Signs List 1Y processing tank 2Y auxiliary tank 4Y processing liquid storage tank 12Y upper member 13Y lower member 16Y transport roller 24Y circulation pump 25Y circulation pipe 27Y nozzle for discharging processing liquid P silver halide photographic photosensitive material CD color developing tank BL bleach tank Fix fixing Tank

Claims (8)

[Claims] 1. A silver halide color photographic material is developed using a color developing solution containing 0.65 to 1.5 mol / L of potassium ion for a color developing time of 30 to 120 seconds. A method for processing a silver halide color photographic light-sensitive material. 2. The processing of a silver halide color photographic light-sensitive material according to claim 1, wherein the color developing solution contains a color developing agent in a range of 0.020 to 0.10 mol / L. Method. 3. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the processing solution for color development contains a compound represented by the following general formula (1). Embedded image [Wherein 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 ammonio group, a carbamoyl group or a sulfamoyl group, and R represents a hydrogen atom or an alkyl group. Represents L, A, and R all include both linear and branched chains;
It may be unsubstituted or substituted. L and R may combine to form a ring. ] 4. The processing temperature of the color developing solution is 40 to 40.
4. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the temperature is 55 [deg.] C. 5. The silver halide emulsion according to claim 1, wherein the silver halide has an iodine content of 0.5 to 10 mol% in the silver halide emulsion. 4. The method for processing a silver halide color photographic light-sensitive material according to claim 1. 6. The silver halide color photographic light-sensitive material is tabular silver halide grains having an aspect ratio of 5 or more and a thickness of 0.1 to 0.3 μm in at least 50% of the total projected area. The maximum silver iodide content of the phase excluding the outermost layer is less than 15 mol%, the silver iodide content of the outermost layer is 6 mol% or more, and The silver halide according to any one of claims 1 to 5, wherein the silver halide emulsion contains tabular silver halide grains having five or more dislocation lines in at least one layer. Processing method for color photographic light-sensitive materials. 7. The weight ratio of total lipophilic photographic material / total gelatin in the silver halide color photographic light-sensitive material is 0.50.
The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 6, wherein 8. The silver halide color according to claim 1, wherein the silver halide color photographic light-sensitive material is coated with 3000 to 7000 mg / m ^{2 of} silver halide. Processing method of photographic photosensitive material.