JPH11231451A - Image forming method for silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the stability of gradation and desilverization property without increasing fog or deteriorating sensitivity and graininess by incorporating a specified silver halide emulsion into a photosensitive layer and developing it with a specified color developing soln. SOLUTION: After a silver halide color photographic sensitive material contg. a silver halide emulsion (a) in a photosensitive layer is exposed, is developed with a color developing soln. for 30-120 sec color development time. In the silver halide emulsion, >=50% of the total projection area of silver halide particles consist of flat platelike silver halide particles having an aspect ration of >=2 and the particles has a part whose the silver iodide content is max. in the region of <=0.80 L for the distance L from the center of the particle to the outer surface. The color developing soln. A contains 0.025-0.100 mol/l color developing main agent, 6.0×10<-7> -7.0×10<-5> mol/l iodide ions, 8.0×10<-3> -3.0×10<-2> mol/l bromide ions and 0.01-50.0 g/l polyvinylpyrrolidone polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an image on a silver halide color photographic light-sensitive material, and more particularly, to a method having a high suitability for rapid development processing, that is, without deteriorating the sensitivity, graininess and sharpness. The present invention relates to a method for forming an image of a silver halide color photographic light-sensitive material capable of obtaining gradation stability and excellent desilvering characteristics.

[0002]

2. Description of the Related Art With the rapid increase in minilab shops in recent years, there has been an increasing demand for faster processing of silver halide color photographic light-sensitive materials (hereinafter, also referred to as light-sensitive materials and light-sensitive materials for simplicity). I have. Means for achieving rapid processing include increasing the concentration of a color developing agent (hereinafter also referred to as "main agent" for simplicity) described in JP-A-4-67038 and increasing the temperature described in JP-A-4-81848. Investigations have been made on speeding up the processing by activating the color developing solution.

[0003] Also, Japanese Patent Application Laid-Open Nos. 8-278611 and 9-
No. 5,962, No. 9-5951, etc., there is an attempt to achieve rapid development by adding a silver halide solvent to a color developing solution.

[0004]

However, all of these are inadequate performances for widespread market development as rapid development processing. In addition, it has been confirmed that the desilvering properties are insufficient due to the rapid development processing. A silver halide color photograph that is rich in rapid development suitability, that is, without increasing fog, without deteriorating sensitivity, granularity, and sharpness, and capable of obtaining better gradation stability and excellent desilvering characteristics. There is a need to provide an image forming method for photosensitive materials.

[0005]

The object of the present invention has been attained by the following.

[0006] 1. On one side of the support, a silver halide color photographic light-sensitive material having at least one photographic component layer consisting of a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer is developed. In the image forming method for obtaining an image by the method, at least one of the photosensitive layers in the photosensitive material is used.
The layer contains the following silver halide emulsion a, and after exposing the photosensitive material, using the following color developing solution A, performing a color developing process for a period of 30 seconds or more and 120 seconds or less. A method for forming an image of a silver halide color photographic light-sensitive material.

<Silver halide emulsion a> At least 50% of the total projected area of the silver halide grains is composed of tabular silver halide grains having two or more twin planes parallel to the main plane and having an aspect ratio of 2 or more, In addition, the grain has a portion having a maximum silver iodide content in a region of 0.80 L or less with respect to the distance L from the center of the grain to the outer surface, and the portion has the following (1) to
A silver halide emulsion satisfying (3).

(1) 5% or more of the silver content per grain 30
(2) The silver iodide content is 20 mol% or more and below the solid solution limit. (3) Reduction sensitization.

<Color developing solution A> Content of color developing agent 0.025 mol / L or more 0.1
00 mol / L or less Iodide ion content 6.0 × 10 ⁻⁷ mol / L or more 7.
0 × 10 ⁻⁵ mol / L or less Bromide ion content 8.0 × 10 ⁻³ mol / L or more
0 × 10 ⁻² mol / L or less Content of polyvinylpyrrolidone polymer or copolymer 0.01 g / L or more and 50.0 g / L or less On one side of the support, a silver halide color photographic light-sensitive material having at least one photographic component layer consisting of a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer is developed. In an image forming method for obtaining an image by the method, at least one of the photosensitive layers in the photosensitive material contains the following silver halide emulsion b, and after exposing the photosensitive material, using the color developing solution A, Color development processing time is 30
A method for forming an image of a silver halide color photographic light-sensitive material, wherein the development processing is performed for a period of not less than 120 seconds and not more than 120 seconds.

<Silver halide emulsion b> At least 50% of the total projected area of the silver halide grains is composed of tabular silver halide grains having two or more twin planes parallel to the main plane and having an aspect ratio of 2 or more, In addition, the grain has a portion having a maximum silver iodide content in a region other than the outermost layer, and
A silver halide emulsion satisfying (3).

(1) The silver iodide content of the outermost layer is 6 mol% or more. (2) The maximum silver iodide content is 6 to 15 mol%. (3) 5 or more dislocations per grain. With lines.

3. On one side of the support, a silver halide color photographic light-sensitive material having at least one photographic component layer consisting of a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer is developed. In the image forming method for obtaining an image by the method, at least one of the photosensitive layers in the photosensitive material is used.
The layer contains two or more tabular silver halide emulsions having an average aspect ratio of 2 or more and different in at least an average silver iodide content in the same layer. An image forming method for a silver halide color photographic light-sensitive material, wherein a developing process is performed using the liquid A for a color developing time of 30 seconds or more and 120 seconds or less.

4. A silver halide color photographic light-sensitive material having a photographic component layer comprising at least two red-sensitive layers, a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer on one side on a support is developed. In the image forming method of obtaining an image by performing the above process, the photosensitive layer in the photosensitive material is formed by mixing two or more tabular silver halide emulsions having an average aspect ratio of 2 or more and different in at least silver iodide content. It is contained in another layer of the color-sensitive layer, and after exposing the photosensitive material, the color development processing time is 30 seconds or more using the color development processing solution A.
An image forming method for a silver halide color photographic light-sensitive material, wherein a development process is performed for a period of 20 seconds or less.

5. A silver halide color photographic light-sensitive material having a photographic component layer comprising at least two red-sensitive layers, a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer on one side on a support is developed. In the image forming method for obtaining an image by performing a color development process, the photographic constituent layer of the photosensitive material contains a polyvinylpyrrolidone polymer or a copolymer, and after exposing the photosensitive material, the color development processing solution A is used. An image forming method for a silver halide color photographic light-sensitive material, wherein the development processing is performed for a time period of 30 seconds to 120 seconds.

6. Each of the two or more tabular silver halide emulsions having an average aspect ratio of 2 or more and different in silver iodide content has an average number of dislocation lines of 10 or more per grain. 5. The method for forming an image of a silver halide color photographic light-sensitive material as described in 3 or 4, wherein

Hereinafter, the present invention will be described in more detail.

First, the <silver halide emulsion a> will be described.

The silver halide grains contained in the silver halide emulsion of the present invention are tabular grains. Tabular grains are crystallographically classified as twins.

Twins are silver halide crystals having one or more twin planes in one grain, and the twin morphology is classified according to the report by Klein and Moiser in Photographi Corspondents.
Korespondenz) Vol. 99, p. 100,
Vol. 100, p. 57.

The tabular grains in the present invention have two twin planes parallel to the main plane. The twin plane can be observed with a transmission electron microscope. The specific method is as follows.

First, a silver halide photographic emulsion is coated on a support so that the contained tabular grains are substantially parallel to the main plane, thereby preparing a sample. This is cut using a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

The tabular grains of the present invention have an aspect ratio (length of long side of tabular grains / thickness of tabular grains) of 50% or more of the total projected area of silver halide grains. Preferably, 60% of the projected area has an aspect ratio of 4.0 or more, and 70% of the total projected area has an aspect ratio of 4.0 or more.
0 or less is more preferable.

In the present invention, the grain size of a silver halide grain is represented by a circle equivalent diameter of a projected area of the silver halide grain (diameter of a circle having the same projected area as the silver halide grain). It is preferably from 1 to 5.0 μm, more preferably from 0.2 to 2.0 μm. The particle diameter can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 70,000 and measuring the particle diameter or the area at the time of projection on the print (the number of measured particles is 1000 or more indiscriminately).

Here, the average particle size r is defined as the particle size ri when the product ni × ri ³ of the frequency ni and ri ³ of the particles having the particle size ri is maximum (three significant digits, minimum Digits are rounded off to the nearest 5).

The tabular grains of the present invention preferably comprise a monodispersed silver halide emulsion. Here, as the monodispersed silver halide emulsion, the one in which the weight of silver halide contained in a range of ± 20% of the particle size around the average particle size r is 60% or more of the total weight of silver halide particles. It is preferably at least 70%, more preferably at least 80%.

The highly monodispersed emulsion of the present invention has a distribution of 30% or less when the width of the distribution is defined by (standard deviation / average particle size) × 100 = particle size distribution (particle size variation coefficient) [%]. Is preferred, and more preferably 25% or less. Here, the average particle size and the standard deviation are the particle size ri defined above.
Shall be obtained from

In the present invention, the center of the tabular grain is defined as the abstract of the 1987 Spring Meeting of the Photographic Society of Japan, 46-4.
In the same manner as described in the summary of Inoue et al. On page 8, silver halide fine particles were dispersed in methacrylic resin and solidified, and ultrathin sections were obtained with a microtome. It is the center of a circle when drawing a minimum circumscribed circle with respect to the cross section by focusing on a slice sample having a cross-sectional area of at least%.

In the present invention, the distance L from the center of the tabular grain to the outer surface of the tabular grain is defined as the distance between the point intersecting the outer periphery of the grain when a straight line is drawn outward from the center of the circle and the center of the circle. Define. The method for detecting the point at which the silver iodide content is highest and the measurement of the distance L from the center are performed by using the XMA method (X-rayMic) on a straight line drawn from the center of the circle to the outer periphery.
It is determined by measuring the silver iodide content and position by a Ro Analyzer method.

In the present invention, the silver iodide content and the average silver iodide content of individual tabular grains and silver halide grains are as follows:
EPMA method (Electron Probe Micror)
oAnalyzer method).

According to this method, a sample in which emulsion grains are well dispersed so as not to be in contact with each other is prepared, and elemental analysis of a very small portion can be performed by X-ray analysis by electron beam excitation for irradiating an electron beam.

By determining the characteristic X-ray intensity of silver and iodine emitted from each grain by this method, the halogen composition of each grain can be determined. When the silver iodide content of at least 50 grains is determined by the EPMA method,
From these averages, the average silver iodide content is determined.

The tabular grains of the present invention preferably have a more uniform silver iodide content between grains. When the distribution of silver iodide content between grains is measured by the EPMA method, the relative standard deviation is 30% or less, more preferably 20% or less.

The surface of the tabular grain of the present invention is the outermost layer of the grain including the outermost surface of the tabular grain, and refers to a depth of up to 50 ° from the outermost surface of the grain. The halogen composition on the surface of the tabular grains of the present invention is determined by an XPS method (X-ray Photoele).
Cron Spectroscopy (X-ray photoelectron spectroscopy) as follows.

That is, the sample was cooled to −110 ° C. or less in an ultra-high vacuum of 1 × 10 E ^-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. Ag3d5 / 2, Br3d, I3
It measures about the electron of d3 / 2. The integrated intensity of the measured peak is referred to as a sensitivity factor (Sensitivity Fac).
tor), and the halide composition on the surface is determined from these intensity ratios.

The XPS method has hitherto been known as a method for determining the silver iodide content on the surface of silver halide grains as disclosed in JP-A-2-241.
No. 88 and the like. However, when the measurement was performed at room temperature, the sample was destroyed due to the X-ray irradiation, so that an accurate silver iodide content of the outermost layer could not be obtained. The present inventors succeeded in accurately determining the silver iodide content of the surface layer by cooling the sample to a temperature at which no destruction occurs.

As a result, in particular, for particles such as core / shell particles having different compositions between the surface and the inside or particles having a high iodine layer or a low iodine layer localized on the outermost surface, the measured values at room temperature are obtained. Is X
It became clear that the true composition was greatly different due to the decomposition of the silver halide by the radiation and the diffusion of the halide (particularly iodine).

The XPS method used here is specifically as follows.

Protease (pronase) was added to the emulsion.
A 05% by weight aqueous solution was added, and the mixture was stirred at 45 ° C. for 30 minutes to decompose gelatin. This is centrifuged to sediment the emulsion particles, and the supernatant is removed. Next, distilled water is added to disperse the emulsion particles in distilled water, centrifuged, and the supernatant is removed. The emulsion particles are re-dispersed in water and coated thinly on a mirror-polished silicon wafer to obtain a measurement sample. Using the sample thus prepared, the surface iodine was measured by XPS. To prevent the destruction of the sample by X-ray irradiation,
The sample was placed in a chamber for XPS measurement at -110 to -120.
Cooled to ° C.

As a probe X-ray, MgKα was irradiated at an X-ray source voltage of 15 kV and an X-ray source current of 40 mA, and Ag3d5
/ 2, Br3d and I3d3 / 2 electrons.
The integrated intensity of the measured peak is used as a sensitivity factor (Sensit
The surface halide composition was determined from these intensity ratios.

The region A in the tabular grain of the present invention is formed at a distance of 0.80 L or less in L defined above, but is preferably at a distance of 0.70 L or less, more preferably at a distance of 0.60 L or less. It is formed. This region A may be present at several places in the above range, but is preferably two places or less, and more preferably one place.

Region A in the tabular grains of the present invention is a region having the highest iodine content in the silver iodide content contained in the tabular grains of the present invention. And the area A
Is 30% in terms of silver content per particle
It refers to the following region, preferably 20% of the silver amount
And more preferably 10% to 3% of the silver amount.
Is a region formed by

The silver iodide content of region A in the tabular grains of the present invention is at least 20 mol%, preferably at least 25 mol%, more preferably from 30 mol% to the solid solution limit. In the region A, the silver iodide content may be constant or may change within the region A. Area A
When the silver iodide content changes within the range, the silver iodide content is preferably within the above-mentioned maximum silver iodide content -2 mol%, more preferably the above-mentioned maximum silver iodide content. -1 mol% or less.

In order to effectively bring out the effects of the present invention, the silver iodide content of the region A is preferably constant.

In the tabular grains of the present invention, the silver iodide content of the silver halide layers adjacent to both sides of the region A is monotonic until the silver iodide content of the region A is reduced to the maximum by half. Decrease. That is, it has a structure in which (1) it decreases linearly or (2) it follows a curve having neither a maximum nor a minimum from both ends of the region A where the silver iodide content is the highest. In order to effectively bring out the effects of the present invention, the embodiment (1) is preferable.

The silver iodide content of the silver halide layers adjacent to both sides of the region A is monotonously reduced by maximizing the silver iodide content of the region A. The silver iodide content of A is preferably 1/3 or less, more preferably 1/3 or less.
/ 5 or less.

The proportion of the silver halide layer adjacent to both sides of the region A and having a monotonically decreasing silver iodide content per grain is preferably 60% or less, more preferably, in terms of silver amount. It is formed from 10% to 40% of the silver amount.

After the silver iodide content of the silver halide layers adjacent to both sides of the region A monotonously decreases to the above-mentioned predetermined silver iodide content, even if the silver iodide content remains constant, Alternatively, the silver iodide content may be increased within a range not exceeding the silver iodide content of the region A.

The tabular grains of the present invention are reduced sensitized in region A. The position where reduction sensitization is performed may be anywhere within the region A. That is, the surface may be an arbitrary surface in the region A or may cover the entire region in the region A. In order to effectively bring out the effects of the present invention, it is preferable that any surface in the region A is reduction-sensitized.

Reduction sensitization is carried out by adding a reducing agent to a silver halide emulsion or a mixed solution for grain growth. Alternatively, a silver halide emulsion or a mixed solution for grain growth is prepared under a low pAg of pAg7 or less, or at pH
It is carried out by ripening or growing particles under a high pH condition of 7 or more. A method performed by combining these methods is a preferred embodiment of the present invention.

Preferred reducing agents include thiourea dioxide, ascorbic acid and its derivatives, and stannous salts. Other suitable reducing agents include borane compounds,
Examples include hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines, and sulfites. The addition amount is 10 ^-2 per mol of silver halide.
Preferred is from 10 to 10 ^-8 mol.

For low pAg ripening, a silver salt can be added, but a water-soluble silver salt is preferred. Silver nitrate is preferred as the water-soluble silver salt. The pAg at ripening is suitably 7 or less, preferably 6 or less, more preferably 1 or less.
３3 (where pAg = −log [Ag ⁺ ]).

High pH ripening is carried out, for example, by adding an alkaline compound to a silver halide emulsion or a mixed solution for tabular grain growth. As the alkaline compound, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like can be used.

In the method of adding ammoniacal silver nitrate for silver halide formation, an alkaline compound other than ammonia is preferably used because the effect of ammonia is reduced.

The method of adding the silver salt and the alkaline compound for reduction sensitization may be rush addition or may be added over a certain period of time. In this case, the addition may be performed at a constant flow rate, or may be performed by changing the flow rate like a function. Further, the required amount may be added several times.

Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, it may be present in the reaction vessel, or may be mixed with the soluble halide solution and added together with the halide. Is also good. Further, it may be added separately from the soluble silver salt and the soluble halide.

In the preparation of the silver halide emulsion of the present invention, a method of growing from seed grains is preferably used.
Specifically, an aqueous solution containing a protective colloid and seed particles are pre-existing in a reaction vessel, and silver ions, halogen ions, or silver halide fine particles are supplied as necessary to grow the seed particles to obtain crystals. is there. Here, the seed particles can be prepared by a single jet method, a controlled double jet method, or the like well known in the art. The halogen composition of the seed grains is arbitrary, and silver bromide,
Any of silver iodide, silver chloride, silver iodobromide, silver chloroiodide, silver chlorobromide and silver chloroiodobromide may be used, but silver bromide and silver iodobromide are preferred, and iodobromide is preferred. In the case of silver, the average silver iodide content is preferably from 1 mol% to 20 mol%.

In the form of crystal growth from seed particles,
The low pAg ripening is preferably performed by adding silver nitrate after the formation of the seed emulsion, that is, during the process from immediately before desalting to after the desalting of the seed grains. In particular, it is preferable to add silver nitrate and ripen the seed particles after desalting, and the ripening temperature is preferably 40 ° C. or more and 50 ° C. to 80 ° C. The aging time is preferably 30 minutes or more and 50 to 150 minutes.

The most preferred form of the present invention is a method in which high pH ripening is performed during the growth of the region A in a form of growing from seed particles. That is, this is carried out by increasing the pH of the system to 7.0 or more at an arbitrary time during the growth of the region A. Preferably, it is carried out by raising it to 7.5 or more. At this time, the addition of the reaction solution for growing the region A may be continued, but it is preferable to temporarily stop the addition of the reaction solution and perform the high pH ripening for an arbitrary time.
Here, the arbitrary time for performing the high pH aging is preferably 1 minute or more, and more preferably 5 to 15 minutes.

Further, in the present invention, it is important to lower the pH of the system to 6.00 or less by adding an acid after aging at a high pH. Preferably from 5.00 to 3.00
Then, the crystal is grown at the same pH. Further, the pH of the system before high pH aging is preferably 6.00 or less.

An oxidizing agent can be used in the silver halide emulsion of the present invention. The following oxidizing agents can be used.

Hydrogen peroxide (water) and its adduct: H ₂ O ₂ ,
_{NaBO 2, H 2 O 2 -3H} 2 O 2, Na 4 P 2 O 7 -2H
Etc. _{2 O 2, 2Na 2 SO 4} -H 2 O 2 -2H 2 O. Peroxy acid salts: K ₂ S ₂ O ₃ , K ₂ C ₂ O ₃ , K ₄ P ₂ O ₃ , K ₂ [Ti
(O ₂₎ C ₂ O _{4]-3H 2} O, peracetic acid, ozone, iodine, bromine, and the like thiosulfonic acid compounds.

[0062] The amount of oxidizing agent used in the present invention, the kind of the reducing agent, reduction sensitization conditions, timing of addition of oxidizing agent, is influenced in an amount by adding conditions, the reducing agent per mole 10 using ^{- 2} to ^10-5 mol is preferred. The oxidizing agent may be added at any time during the silver halide emulsion manufacturing process. It can be added prior to the addition of the reducing agent.

Further, after the oxidizing agent is added, a reducing substance may be newly added to neutralize the excess oxidizing agent. These reducing substances are substances capable of reducing the oxidizing agent, and include sulfinic acids, di- and trihydroxybenzenes, chromans, hydrazines and hydrazides, p-phenylenediamines, aldehydes, aminophenols, Examples include enediols, oximes, reducing sugars, phenidones, sulfites, and ascorbic acid derivatives. The amount of the reducing substance is preferably an amount per mole ^10-3 to ³ moles of the oxidizing agent to be used is.

Although the tabular grains of the present invention are made of silver iodobromide, they can contain silver chloride as long as the effects of the present invention are not impaired.

The tabular grains of the present invention preferably comprise silver iodobromide having an average silver iodide content of 1 mol% to 20 mol%, more preferably 3 to 15 mol%.

As a means for forming the silver halide emulsion of the present invention, various methods well known in the art can be used.

That is, any combination of the single jet method, the controlled double jet method, the controlled triple jet method, etc. can be used. PAg in the liquid phase in which tabular grains are formed
It is important to control the value according to the growth rate of tabular grains. As the pAg value, a range of 7.0 to 10.5 is used, and preferably 7.5 to 10.0, 8.0 to 8.0.
It is particularly preferred to use a region of 9.5. In determining the addition rate, JP-A-54-48521 and JP-A-58-49938 can be referred to.

In the production of the tabular grains of the present invention, a known silver halide solvent such as ammonia, thioether, thiourea or the like may be present, or a silver halide solvent may not be used.

The tabular grains of the present invention may be grains in which a latent image is mainly formed on the surface or grains in which a latent image is mainly formed inside the grains.

The tabular grains of the present invention are produced in the presence of a dispersion medium, that is, in an aqueous solution containing the dispersion medium. Here, the aqueous solution containing the dispersion medium refers to an aqueous solution in which a protective colloid is formed in an aqueous solution by a substance capable of forming a hydrophilic colloid (e.g., a substance that can serve as a binder), and preferably a colloidal protective substance. It is an aqueous solution containing gelatin.

In the practice of the present invention, when gelatin is used as the above protective colloid, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in Arthur Guice's, The Macromolecular Chemistry of Gelatin, (Academic Press, 1964).

Examples of hydrophilic colloids other than gelatin that can be used as protective colloids include, for example, gelatin derivatives, graft polymers of gelatin and other polymers,
Proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
There are various kinds of synthetic hydrophilic polymer substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole.

In the case of gelatin, it is preferable to use those having a jelly strength of 200 or more in the puggy method.

The tabular grains of the present invention can be used in the step of forming and / or growing the grains, in the course of cadmium salt, zinc salt, lead salt, thallium salt, iron salt, rhodium salt, iridium salt, indium salt (including complex salt). )), Metal ions can be added using at least one selected from the group consisting of these metal elements inside and / or on the surface of the particles.

The tabular grains of the present invention may be those from which unnecessary soluble salts have been removed after the growth of the tabular grains, or may be those containing them.

It is also possible to desalinate at any point during silver halide growth, as in the method described in JP-A-60-138538. When removing the salts, use Research Disclosure (Research Disc).
Closure (hereinafter abbreviated as RD) 17643 No. II.

More specifically, in order to remove the soluble salt from the emulsion after the formation of the precipitate or after the physical ripening, a Nudel washing method performed by gelling gelatin may be used. A precipitation method (flocculation) using an activator, an anionic polymer (eg, polystyrene sulfonic acid), or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used.

The tabular grains of the present invention can be chemically sensitized by a conventional method. That is, sulfur sensitization, selenium sensitization,
A noble metal sensitization method using gold or another noble metal compound can be used alone or in combination.

The tabular grains of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye which has no spectral sensitizing effect by itself together with the sensitizing dye or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. May be.

Next, <Silver halide emulsion b> will be described.

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 2 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 preferable 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 coefficient of variation of the circle-converted diameter of the main plane (the diameter of a circle having the same projected area as the main plane) by dividing the standard deviation of the diameter distribution by the average diameter. ) 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 1 to 15 mol%,
More preferably, it is 3 to 12 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 calculated by calculating the coefficient of variation of the silver iodide content (the standard deviation of the silver iodide content intergranular distribution is expressed 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 largest 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 silver iodide content of the outermost layer of the tabular grains of the present invention is preferably at least 6 mol% and no more than the solid solution limit. If it is less than 6 mol%, the storage stability of the adsorption of the sensitizing dye is undesirably reduced.

The outermost layer as 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 as referred to in the present invention may be a value measured by an XPS method or an ISS method (Ion Scattering Spectrosc).
Either value may be used as the numerical value measured by the optics 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.

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 later 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 dislocation lines in the tabular grains of the present invention is preferably such that the number of dislocation lines containing 5 or more dislocation lines accounts for at least 50% of the projected area of all silver halide grains in the emulsion, but 80%. It is particularly preferable that the above is satisfied. Further, the number of dislocation lines 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 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 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 position at which dislocations are introduced is preferably 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 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%.

Next, the use of a combination of tabular silver halide emulsions will be described.

In the present invention, in at least one of the light-sensitive layers in the light-sensitive material, two or more kinds of tabular silver halide emulsions having an average aspect ratio of 2 or more and different in at least an average silver iodide content are used. Are used in combination in the same layer to exhibit the effect of the present invention.

Here, the difference in the average silver iodide content means that
The difference in silver iodide content of two or more tabular silver halide emulsions is different from each other by 0.2 mol% or more, preferably 0.3 mol% to 8 mol%, particularly preferably 0.1 mol% to 8 mol%. Different from 5 mol% to 5 mol%. If the difference is too small, the effect of the present invention is small. Conversely, if the difference is too large, the characteristic curve will undulate during rapid development, which is not preferable.

The addition ratio of two or more tabular silver halide emulsions used in combination in the same layer is not particularly limited and can be appropriately adjusted depending on the kind of the tabular silver halide emulsion to be used. The silver halide emulsion is
In terms of silver amount, the content is preferably 5% by weight or more and 95% by weight or less,
Particularly preferred is 10% by weight or more and 90% by weight or less.

The layer used in combination of two or more tabular silver halide emulsions is not particularly limited, and may be any of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. Also,
Even if it is composed of a plurality of layers having the same color sensitivity and different sensitivities, any of the highest sensitivity layer, the lowest sensitivity layer and the intermediate sensitivity layer may be used, but the effect of the present invention can be applied to the lowest sensitivity layer and the intermediate sensitivity layer. Can be sufficiently exhibited.

The light-sensitive layer in the light-sensitive material has an average aspect ratio of 2 or more and at least different silver iodide contents.
The effect of the present invention is exhibited by using a combination of two or more kinds of tabular silver halide emulsions in different layers within the same color-sensitive layer.

The difference in the average silver iodide content is the same as described above.

The addition ratio of two or more tabular silver halide emulsions used in combination in different layers in the same color-sensitive layer is as follows:
There is no particular limitation, and it can be appropriately adjusted depending on the kind of the tabular silver halide emulsion to be used. However, each tabular silver halide emulsion is preferably 5% by weight or more and 95% by weight or less, and more preferably 10% by weight or more in terms of silver amount. 90% by weight or less is particularly preferred.

The other layers in the same color-sensitive layer, which are used in combination of two or more tabular silver halide emulsions, are not particularly limited, and may be any of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. Either is acceptable. Further, among a plurality of layers having the same color sensitivity and different sensitivities, any of the highest sensitivity layer and the lowest sensitivity layer, the lowest sensitivity layer and the intermediate sensitivity layer, and the highest sensitivity layer and the intermediate sensitivity layer may be used.
When the light-sensitive layer is composed of a minimum sensitivity layer and an intermediate sensitivity layer adjacent to each other, a maximum sensitivity layer and an intermediate sensitivity layer, or two layers having the same color sensitivity and different sensitivities, the maximum sensitivity layer and the minimum sensitivity layer can sufficiently provide the effects of the present invention. It is preferable because it can be demonstrated. It is particularly preferable to apply to all layers having the same color sensitivity and different sensitivities.

In the present invention, two or more tabular silver halide emulsions having an average aspect ratio of 2 or more and different in silver iodide content each have an average number of dislocation lines per grain. When the number is 10 or more, preferably 30 or more and 50 or less, the effect of the present invention is emphasized. If the number is 50 or more, it is impossible to confirm the number of the lines, and the effect will level off.

In the present invention, the silver halide emulsion may be prepared according to Research Disclosure No. 308119 (hereinafter R
D308119) can be used.

The following shows the places to be described.

[Items] [Page of RD308119] Manufacturing method 993 IA and 994 E Iodine composition 993 IA Crystal habit Normal crystal, twin 993 IA Epitaxial 993 IA Halogen composition Uniform, non-uniform 993 I-B Halogen conversion 994 I-C Halogen substitution 994 I-C Metal-containing 994 I-D Mono-dispersion 995-I F Solvent addition 999 I-F Latent image formation position Surface and interior Section 995I-G Applicable photosensitive material Negative 995I-H Section Emulsion mixed and used 995I-J Section Desalting 995II-A In the present invention, the silver halide emulsion is physically ripened or chemically ripened. And those subjected to spectral sensitization. Additives used in such a process are described in Research Disclosure No. 17643, No. 1 18716 and no. 3
08119 (hereinafter referred to as RD17643 and RD18, respectively)
716 and RD308119). The following shows the places to be described.

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[Table 1]

Known photographic additives that can be used in the present invention are also described in Research Disclosure below.

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[Table 2]

Various couplers can be used in the present invention, and specific examples thereof are described in the following Research Disclosure.

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[Table 3]

The additive used in the present invention is RD3081
It can be added by the dispersion method described in 19XIV.

In the present invention, page 28 of RD17643, page 647 to page 8 of RD18716, and RD308
The support described in 119 XVII can be used.

The light-sensitive material of the present invention includes RD3081 described above.
An auxiliary layer such as a filter layer or an intermediate layer described in the item 19 VII-K can be provided.

Next, the <color developing solution A> of the present invention will be described.

The polyvinylpyrrolidone polymer or copolymer used in the present invention refers to a polymer or copolymer having a pyrrolidone nucleus in its molecular structure. Polymer having a pyrrolidone nucleus in the molecular structure added to the color developing solution of the present invention (hereinafter also referred to as vinylpyrrolidone polymer)
Is a homopolymer of vinylpyrrolidone alone,
It may be a copolymer with another monomer.

Other monomers that can be copolymerized with vinylpyrrolidone include vinyl esters (vinyl acetate, vinyl propionate, vinyl butyrate, etc.) and acrylate esters (methyl acrylate, ethyl acrylate, butyl acrylate, and the like).
Acrylic acid-2-ethylhexyl, etc.), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid-2-ethylhexyl), acrylic acid, methacrylic acid, styrene and the like. Is 5-1 to vinylpyrrolidone
It is preferably used in the range of 00 mol%.

In the present invention, the weight average molecular weight (Mw) of the vinylpyrrolidone polymer added to the color developer is usually in the range of 500 to 800,000, preferably 2,000.
４００400,000. Polymeric substances such as the polymers or copolymers of the present invention generally have a molecular weight distribution because they consist of a mixture of homologs having different molecular weights.
Therefore, the molecular weight value gives a different average molecular weight depending on the measurement method, and the value differs. As a method for measuring the average molecular weight, for example, published by the Society of Polymer Science, published by Corona (1973)
The polymer can be measured by the method described in the Handbook of Polymer Materials (Year), but in the examples of the present invention, it was measured according to the viscosity method.

The polymer or copolymer of the present invention may be used alone or in combination of two or more. The amount of the polymer or copolymer is from 0.01 g / L to 50.50 g in a color developing solution. 0g
/ L, and further 0.05 g / L to 10 g / L.
It is more preferable that the ratio is in the range of L from the viewpoints of good gradation and storage stability of the processing solution.

In the present invention, specific examples of the vinylpyrrolidone polymer to be added to the color developing solution include the following.

(P-1) Polyvinylpyrrolidone (Mw to 40,000) (P-2) Polyvinylpyrrolidone (Mw to 9,000) (P-3) Polyvinylpyrrolidone (Mw to 16,000) (P-4) Vinylpyrrolidone-vinyl acetate copolymer (copolymer molar ratio = 7: 3, Mwｗ4,000) (P-5) Vinylpyrrolidone-methyl acrylate copolymer (copolymer molar ratio = 7: 3, Mw〜1) , 000) (P-6) vinylpyrrolidone-ethyl acrylate copolymer (copolymer molar ratio = 7: 3, Mw-25,000) (P-7) vinylpyrrolidone-butyl acrylate copolymer (copolymer molar ratio = 7: 3, Mw ~ 7,000) (P-8) vinylpyrrolidone-2-ethylhexyl acrylate copolymer (copolymerization molar ratio = 7: 3, Mw ~ 18,000) (P-9) vinylpyrrolidone - styrene copolymer (copolymerization molar ratio = 1: 3, Mw~20,000)) is in the color developing processing solution of the present invention is iodide ion 6.
It is contained in the range of 0 × 10 ⁻⁷ mol / L to 7.0 × 10 ⁻⁵ mol / L, and further 5.0 × 10 ⁻⁶ mol / L.
To 2.0 × 10 ⁻⁵ mol / L is more preferable in order to obtain good gradation. The iodide ions may be added to the replenisher or may be eluted from the photosensitive material to be processed. When directly added to the color developing solution, sodium, potassium, ammonium, nickel, magnesium, manganese or calcium iodide may be used as an iodide ion supply, and among them, preferred are sodium iodide and iodide. Potassium.

The processing solution for color development of the present invention contains bromide ions in an amount of from 0.80 × 10 ^-2 mol / L to 3.0 × 10 ^-2.
mol / L, but preferably from 0.85 × 10 ^-2 mol / L to 1.7 × 10 ^-2 mo.
It is more preferable that the ratio be in the range of 1 / L in order to obtain good gradation. The bromide ions may be added to the replenisher or may be eluted from the photosensitive material to be processed. When directly added to the color developing solution, sodium, potassium, ammonium, nickel, magnesium, manganese or calcium bromide may be mentioned as the bromide ion supply, with sodium bromide and potassium bromide being preferred. is there.

The processing time of the color developing process of the present invention is 3
The range is from 0 to 120 seconds, and more preferably from 60 to 105 seconds.

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

The color developing agent used in the present invention is preferably a p-phenylenediamine compound having a water-soluble group. Wherein the water-soluble group is at least one preferably being on amino group or benzene nucleus of p- phenylenediamine compound, as a specific water-soluble group _{- (CH 2) n -CH 2} OH, - ( CH ₂ ) _m —NHSO ₂ —
_{(CH 2) n -CH 3,} - (CH 2) m -O- (CH 2) n -C
_{H 3, - (CH 2 CH} 2 O) n -C m H 2m + 1 (m and n each represents an integer of 0 or _{more.), - COOH, -SO 3} H
And the like are preferred.

Examples of specific compounds preferably used in such color developing agents include the following (C-1)
To (C-16). Among them, preferred from the viewpoint of the effect of the present invention are (C-1), (C-2),
(C-3), (C-4), (C-6), (C-7),
(C-15), and particularly preferred is (C-3).

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In the color developing solution of the present invention, the color developing agent is preferably used in the range of 0.025 mol / L or more and 0.100 mol / L or less, more preferably 0.03 mol / L or less.
It is more preferable that it is in the range of not less than mol / L and not more than 0.05 mol / L from the viewpoint of low-temperature precipitation resistance and storage stability of the processing solution.

In the present invention, it is particularly preferable that a compound represented by the following general formula [D] is contained in a color developer.

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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,
Represents a phosphine 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. L, A, R
Includes both linear and branched chains, and may be unsubstituted or substituted. L and R may combine to form a ring.

The compound represented by 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, a methylene group,
Preferred examples include an ethylene group, a trimethylene group, and a propylene group. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, an ammonium group which may be substituted with alkyl, and the like, and a carboxyl group, a sulfo group, a phosphono group, and a hydroxyl group are preferable. A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, an amino group which may be alkyl-substituted, an ammonium group, a carbamoyl group, or a sulfamoyl group, 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 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. . 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, an amino group which may be substituted with an alkyl, an ammonium group, a carbamoyl group, and a sulfamoyl group. 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 hydroxylethyl group. A hydrogen atom, a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group are particularly preferred. L and R may combine to form a ring.

The typical examples of the compounds represented by the formula [D] are shown below.

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In the color developing solution of the present invention, a sulfite can be used as a preservative. Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

A buffer can be used in the color developing solution of the present invention. Examples of the buffer include potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, and the like. Dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, potassium 5-sulfo-2-hydroxybenzoate (Potassium 5-sulfosalicylate)
Is preferred.

A development accelerator can be used in the color developing solution of the present invention. Examples of the development accelerator include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, Amine compound, polyalkylene oxide, 1-phenyl-3-
Pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles and the like can be added as needed.

The color developing solution preferably does not substantially contain benzyl alcohol.

In the color developing solution of the present invention, other various additives other than those mentioned above, such as a stain inhibitor, an anti-sludge agent, and a layering effect accelerator, can be used.

In practicing the present invention, the steps after the color developing step, for example, the step having the bleaching ability, the step having the fixing ability, the stabilizing step, etc., may be constituted according to a usual method. For example, the step having bleaching ability is described in JP-A-9-90579, the step having fixing ability is described in JP-A-8-201997, and the stabilizing step is described in JP-A-8-201997.

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 Among these steps, (3), (4), (7), ( 1
0) and (12) are preferable, and (3) and (4) are particularly preferable.

The method for forming an image of a silver halide color photographic light-sensitive material of the present invention is characterized in that the light-sensitive material is rapidly developed with a color developing solution containing a polyvinylpyrrolidone polymer or copolymer. It is also preferable to incorporate a polyvinylpyrrolidone polymer or copolymer in the photographic constituent layer of the light-sensitive material and to carry out rapid development processing with the color developing solution in order to further exert the effects of the present invention. The polyvinylpyrrolidone polymer or copolymer added to the photographic component layer may be the same as the one added to the color developing solution, and is preferably the same.

The amount of the polyvinylpyrrolidone polymer or copolymer added during the photographic construction was 0.005 g /
preferably ^{m 2 ~1.0g / m 2, 0.01g} / m 2 ~
0.5 g / m ² is particularly preferred. The layer to be added can be added to any of the photosensitive layer and the non-photosensitive layer in the photographic constituent layer, and is preferably added to the photosensitive layer, particularly preferably to all layers.

[0162]

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 A multilayer color photographic light-sensitive material sample 101 was prepared by sequentially forming layers having the following compositions on a triacetyl cellulose film support provided with an undercoat layer from the support side.

The amount of addition is expressed in grams per m ² .
However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.123 CC-1 0.044 OIL-1 0.167 Gelatin 1.33 Second Layer (Intermediate) Layer) AS-1 0.160 OIL-1 0.20 Gelatin 0.69 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.20 Silver iodobromide b 0.29 SD-1 37 × 10 ^-5 SD-2 1.2 × 10 ^-4 SD-3 2.4 × 10 ^-4 SD-4 2.4 × 10 ^-6 C-1 0.32 CC-1 0.038 OIL-2 0.28 AS-2 0.002 Gelatin 0.73 Fourth layer (medium-sensitivity red-sensitive layer) Silver iodobromide c 0.10 Silver iodobromide d 0.86 SD-1 4.5 × 10 ^{-5 SD-2 2.3 × 10 -4 SD} -3 4.5 × 10 -4 C-2 0.52 CC-1 0.06 DI-1 0.047 O L-2 0.46 AS-2 0.004 Gelatin 1.30 Fifth Layer (high sensitivity red-sensitive layer) Silver iodobromide d 1.31 SD-1 3.0 × 10 -5 SD-2 1. 5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-2 0.047 C-3 0.09 CC-1 0.036 DI-1 0.024 OIL-2 0.27 AS-20 006 Gelatin 1.28 6th layer (intermediate layer) OIL-1 0.29 AS-1 0.23 Gelatin 1.00 7th layer (low sensitivity green photosensitive layer) Silver iodobromide a 0.19 Iodobromide Silver b 0.062 SD-4 3.6 × 10 ^-4 SD-5 3.6 × 10 ^-4 M-1 0.18 CM-1 0.033 OIL-1 0.22 AS-2 0.002 AS -3 0.05 gelatin 0.61 8th layer (intermediate layer) OIL-1 0.26 AS-1 0.054 gelatin 0.80 9th layer ( Medium-speed green photosensitive layer) Silver iodobromide e 0.54 Silver iodobromide f 0.54 SD-6 3.7 × 10 ^-4 SD-7 7.4 × 10 ^-5 SD-8 5.0 × ^10-5 M-1 0.17 M-2 0.33 CM-1 0.024 CM-2 0.029 DI-2 0.024 DI-3 0.005 OIL-1 0.73 AS-30 035 AS-2 0.003 Gelatin 1.80 10th layer (high-sensitivity green photosensitive layer) Silver iodobromide f 1.19 SD-6 4.0 × 10 ^-4 SD-7 8.0 × 10 ^-5 SD-8 5.0 × 10 ^-5 M-1 0.065 CM-2 0.026 CM-1 0.022 DI-3 0.003 DI-2 0.003 OIL-1 0.19 OIL-20 .43 AS-3 0.017 AS-2 0.014 Gelatin 1.23 11th layer (yellow filter layer) Yellow colloidal silver 0.05 OIL-1 0.18 AS-1 0.16 Gelatin 1.00 12th layer (low-sensitivity blue-sensitive layer) Silver iodobromide a 0.30 Silver iodobromide h 0.09 SD-96 0.5 × 10 ^-4 SD-10 2.5 × 10 ^-4 YA 0.77 DI-4 0.017 OIL-1 0.31 AS-2 0.002 Gelatin 1.29 13th layer (high sensitivity Blue photosensitive layer) Silver iodobromide i 1.02 SD-9 4.4 × 10 ^-4 SD-10 1.5 × 10 ^-4 YA 0.23 OIL-1 0.10 AS-20 004 Gelatin 1.20 14th layer (first protective layer) Silver iodobromide j 0.30 UV-1 0.055 UV-2 0.110 OIL-2 0.30 Gelatin 1.32 15th layer (2nd Protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 Gelatin 0.55 Displaying the characteristics of the silver iodobromide below (one side length of a cube having the same volume as the average particle diameter).

Emulsion No. Average particle size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 b 0.40 8.0 1.4 c 0.60 7.0 3.0. 1d 0.65 7.0 7.2 e 0.60 7.0 4.1 f 0.65 7.0 6.5 h 0.65 8.0 1.4 i 1.43 8.0 2.0. 3 j 0.05 2.0 1.0 Each silver iodobromide emulsion had a structure in which the halogen composition in the grains was uniform.

After the above-mentioned sensitizing dyes were added to each of the above emulsions and ripened, triphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate were added, and the fog and the sensitivity were optimized according to a conventional method. Chemical sensitization was applied to obtain.

Incidentally, in addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersion aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, inhibitor AF-
3, AF-4, AF-5, hardeners H-1, H-2 and preservative Ase-1 were added.

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

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[0178]

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For sample 101, EM-1, 4, 7, 8, and 9 of Examples of JP-A-9-203983 were replaced with silver iodobromide emulsion i of the thirteenth layer by the same silver amount. Samples 102 to 106 shown in Table 4 were similarly prepared except that they were used.
It was created.

[0180]

[Table 4]

However, the amount of silver in the maximum AgI region was EM-
1, 4, 7, 8, 9: 7 to 11.5% per particle
Met.

Automatic developing machine CL-K for color negative film
The transfer speed of P-50QA (manufactured by Konica Corporation) is 1.95.
Samples 101 to 10 which were subjected to sensitometric exposure by a normal method using an automatic developing machine modified so as to be doubled
No. 6 was treated under the following conditions while changing the polymer or copolymer of the present invention, its concentration and the concentration of potassium iodide (KI) as shown in Table 5. In the present invention, the processing of the following processing steps is referred to as “rapid development processing”.

(Processing Step: Rapid Development Processing) Step Processing Time Processing Temperature Color Development 90 seconds 42 ° C. Bleaching 20 seconds 38 ° C. Fixing-1 20 seconds 38 ° C. Fixing-2 20 seconds 38 ° C. Stable-1 10 seconds 38 ° C. Stable 2 10 seconds 38 ° C Stable -3 10 seconds 38 ° C Total 3 minutes (Formulation of processing solution) [Color developing solution] Sodium sulfite 6.0 g Potassium carbonate 35.0 g N, N-bis (sulfoethyl) hydroxylamine disodium 8 5.0 g diethylenetriaminepentaacetic acid pentasodium 5.0 g potassium bromide 1.1 × 10 ⁻² mol / L polyvinylpyrrolidone polymer or copolymer described in Table 5 Potassium iodide described in Table 5 4-amino-3-methyl- N-ethyl-N- (β-hydroxyethyl) aniline sulfate (Exemplified Compound C-3) 0.035 mol / L Water was added to make 1 L. PH was adjusted to 10 using potassium hydroxide or 50% sulfuric acid. Adjusted to 3.

[Bleaching Treatment Solution] Ferric ammonium 1,3-propylenediaminetetraacetate 160 g 1,3-propylenediaminetetraacetic acid 7 g Ammonium bromide 60 g maleic acid 90 g Water was added to make 1 L, and ammonia water or 50% sulfuric acid was added. The pH was adjusted to 3.0 using.

[Fixing treatment solution] Ammonium thiosulfate 180 g Sodium thioosulfate 20 g Sodium sulfite 10 g Potassium carbonate 2 g Ethylenediaminetetraacetate 2 g Add water to make 1 L, and adjust the pH to 6.5 using aqueous ammonia or 50% sulfuric acid. It was adjusted.

[Stabilizing Solution] m-hydroxybenzaldehyde 1.5 g disodium ethylenediaminetetraacetate 0.2 g potassium carbonate 0.2 g β-cyclodextrin 0.2 g potassium hydroxide 0.03 g Water was added to make 1 L.

A commercially available CL-KP-50QA (manufactured by Konica Corporation) is used as a supplement for the CNK-4-52 process.
And a starter (manufactured by Konica Corporation) as a processing agent, and the above-described photosensitive material is processed under the standard processing conditions of the same process.
The gradation stability was evaluated using the method described below. In the present invention, the processing of the CNK-4-52 process is referred to as "normal development processing".

[0188]

[Table 5]

(Evaluation of Gradation Stability) A straight line connecting the density point of minimum density + 0.3 and the density point of minimum density + 1.3 in the D-logE characteristic curve of the photosensitive material after each development processing. Was determined for the yellow image (by blue light measurement), ie, the ratio of the rapid development processing γQ to the normal development processing γN and γQ / γN. Note that this γQ /
The closer the γN is to 1.00, the more compatible with the normal developing process, that is, the faster the developing process is, the better the performance is. The results are summarized in Table 6.

(Evaluation of Desilvering Characteristics) The amount of residual silver was analyzed for the maximum density portion of the photosensitive material after each development processing. If the amount of residual silver is 8 μg / cm ² or less, there is no practical problem. If the amount of silver is 5 μg / cm ² or less, excellent performance comparable to normal development is obtained as rapid development. To indicate that

[0191] The results are summarized in Table 6.

[0192]

[Table 6]

As is evident from the results in Table 6, the color developer contains at least 0.01 g / L of a polymer or copolymer having a pyrrolidone nucleus in its molecular structure.
0 g / L or less, and iodide ions were added to 6.0 × 10 ^−7.
Mol / L or more and 7.0 × 10 ⁻⁵ mol / L and a bromide ion content of 8.0 × 10 ⁻³ mol / L or more and 3.0 ×
10 ^-2 mol / L or less, the content of the color developing agent is 0.025 mol / L or more and 0.100 mol / L or less, and the predetermined conditions in the silver halide color photographic light-sensitive material. It can be seen that the use of the silver halide emulsion described above makes it possible to provide an image forming method having good gradation and excellent desilvering properties even in a rapid development process.

Example 2 Sample No. 1 of Example 1 In the combination of No. 102 and Process No. 8, the developing process was performed under the same conditions except that the concentration of potassium bromide (KBr) in the color developing solution was changed as shown in Table 7 from 8A to 8E. The gradation stability was evaluated using the same method as in Example 1.

The transmission density (DQ (Y)) at 440 nm of the unexposed portion of the photosensitive material which has been subjected to the rapid development processing is measured, and the 440 nm of the unexposed portion of the photosensitive material which has been subjected to the normal development process is measured.
The transmission density in nm (DN (Y)) was measured. Further, ΔDmin (Y) was obtained by the following equation. Note that this ΔDm
The closer the in (Y) is to 0.00, the smaller the increase in fog even in rapid development processing, that is, the higher the suitability for rapid development processing.

ΔDmin (Y) = DQ (Y) −DN (Y) The results are shown in Table 7.

[0197]

[Table 7]

As is clear from the results in Table 7, when the bromide ion is contained in the color developing solution in the range of 8.0 × 10 ⁻³ mol / L to 3.0 × 10 ⁻² mol / L. It can be seen that good gradation stability and rapid development suitability can be obtained.

Example 3 For the sample 101 of Example 1 described above, Em-1, 4 and 9 of Examples of JP-A-9-160151 were replaced with the silver iodobromide emulsion d of the fifth layer, respectively. Samples 302 to 304 shown in Table 8 were prepared in the same manner except that an equivalent silver amount was used.

[0200]

[Table 8]

In the same manner as in Example 1, evaluation of gradation stability (measured with a red light for the cyan image) and evaluation of desilvering characteristics were performed.

The results are summarized in Table 9.

[0203]

[Table 9]

As apparent from the results shown in Table 9, the color developer contains at least 0.01 g / L of a polymer or copolymer having a pyrrolidone nucleus in its molecular structure.
0 g / L or less, and iodide ions were added to 6.0 × 10 ^−7.
Mol / L or more and 7.0 × 10 ⁻⁵ mol / L and a bromide ion content of 8.0 × 10 ⁻³ mol / L or more and 3.0 ×
10 ^-2 mol / L or less, the content of the color developing agent is 0.025 mol / L or more and 0.100 mol / L or less, and the predetermined conditions in the silver halide color photographic light-sensitive material. It can be seen that the use of the silver halide emulsion described above makes it possible to provide an image forming method having good gradation and excellent desilvering properties even in a rapid development process.

Example 4 In the same manner as in Example 2, the sample No. 30
For Nos. 1 to 304, processing was performed in combination with Process Nos. 8 and 8A to 8D in which the concentration of potassium bromide (KBr) was changed, and the gradation stability of the cyan image and ΔDmin (C) at 650 nm were measured. As a result, the same relationship as in Example 2 was recognized, and the effect of the present invention was confirmed.

Example 5 Sample No. 1 of Example 1 In the ninth layer of No. 101, silver iodobromide emulsion f was replaced with emulsion fx having an average silver iodide content of 8.7 mol%.
Sample 502 was prepared in the same manner except that the silver
Was prepared. In addition, the sample No. Sample No. 101 was prepared in the same manner except that the silver iodobromide emulsion f of the tenth layer was replaced with the silver iodobromide emulsion fx. 503 were produced. Table 1
0 is shown.

[0207]

[Table 10]

As in Example 1, evaluation of gradation stability (measured with green light for magenta image) and evaluation of desilvering characteristics were performed.

The results are summarized in Table 11.

[0210]

[Table 11]

As is clear from the results shown in Table 11, the use of the combination of silver halide emulsions under the predetermined conditions described in Claims 3 and 4 of the present invention makes it possible to perform rapid development processing.
It can be seen that an image forming method having good gradation and excellent desilvering characteristics can be provided.

Example 6 Sample No. 1 of Example 1 In the fourth layer of No. 101, silver iodobromide emulsion d was replaced with emulsion dx having an average silver iodide content of 6.5 mol%.
In the same manner as in Sample 602, except that
Was prepared. In addition, the sample No. Sample No. 101 was prepared in the same manner except that the silver iodobromide emulsion d of the fifth layer was replaced with the silver iodobromide emulsion dx. 603 was produced. Table 12
Shown in

[0213]

[Table 12]

(However, the content in parentheses indicates the silver iodide content; mol%) In the same manner as in Example 1, the gradation stability was evaluated (measured with a red light for the cyan image) and the desilvering property was evaluated. Was.

The results are summarized in Table 13.

[0216]

[Table 13]

As is clear from the results shown in Table 13, the use of the combination of silver halide emulsions under the predetermined conditions described in Claims 3 and 4 of the present invention makes it possible to achieve rapid development processing.
It can be seen that an image forming method having good gradation and excellent desilvering characteristics can be provided.

Example 7 The sample No. of Example 1 was used. At 101, P-1
Was added as shown in Table 14 to prepare Samples 702 and 703.

[0219]

[Table 14]

In the same manner as in Example 1, the evaluation of gradation stability (measured with red light for the cyan image) and the evaluation of the desilvering property were performed.

The results are summarized in Table 15.

[0222]

[Table 15]

As is clear from the results in Table 15, the polyvinyl pyrrolidone polymer or copolymer shown in claim 5 of the present application was added to a silver halide color photographic light-sensitive material and to a color developing solution. It can be seen that the use of the combination can provide an image forming method having good gradation and excellent desilvering properties even in a rapid development process.

Example 8 Sample No. 5 of Example 5 Emulsions E and FX were the same as emulsions e and fx used for the ninth and tenth layers in 502 and 503 except that 30 or more dislocation lines were introduced into the fringe portion during grain formation. Was prepared, and Sample No. 802 and 803 were produced.

Similarly, the sample No. 60
Emulsions C and DX were prepared in the same manner as in Emulsions c and dx used for the fourth and fifth layers in 2,603 except that 30 or more dislocation lines were introduced into the fringe portion during the grain formation. Was prepared, and Sample No. 804,805
Was prepared.

The contents are shown in Table 16.

[0227]

[Table 16]

(However, the content in parentheses indicates the silver iodide content; mol%) As in Example 1, evaluation of gradation stability (measured for magenta and cyan images) and evaluation of desilvering properties were performed. .

The results are summarized in Table 17.

[0230]

[Table 17]

As is clear from the results shown in Table 17, the use of the combination of silver halide emulsions under the predetermined conditions described in claim 6 of the present application makes it possible to obtain excellent gradation and excellent even in rapid development processing. It can be seen that an image forming method having desilvering characteristics can be provided.

[0232]

According to the present invention, even when rapid development processing is performed, fog is not increased, and sensitivity, granularity, and sharpness are not deteriorated.
Further, good gradation stability and excellent desilvering characteristics were obtained.

Claims (6)

[Claims] 1. A silver halide color photographic light-sensitive material having, on one side on a support, at least one photographic constituent layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In an image forming method for obtaining an image by developing a material, at least one of the photosensitive layers in the photosensitive material contains the following silver halide emulsion a, and after exposing the photosensitive material, the following color developing solution A. A method for forming an image of a silver halide color photographic light-sensitive material, wherein a developing process is performed using A in a color developing time of 30 seconds or more and 120 seconds or less. <Silver halide emulsion a> At least 50% of the total projected area of the silver halide grains is composed of tabular silver halide grains having two or more twin planes parallel to the main plane and having an aspect ratio of 2 or more,
Further, the grain has a portion having a maximum silver iodide content in a region of 0.80 L or less with respect to a distance L from the center of the grain to the outer surface, and the portion has the following (1) to (3) A silver halide emulsion satisfying (3). (1) 5% or more and 30% or less of the silver amount per particle. (2) The silver iodide content is not less than 20 mol% and not more than the solid solution limit. (3) Reduction sensitization. <Color developing solution A> Content of color developing agent 0.025 mol / L or more 0.1
00 mol / L or less Iodide ion content 6.0 × 10 ⁻⁷ mol / L or more 7.
0 × 10 ⁻⁵ mol / L or less Bromide ion content 8.0 × 10 ⁻³ mol / L or more
0 × 10 ^-2 mol / L or less Content of polyvinylpyrrolidone polymer or copolymer 0.01 g / L or more and 50.0 g / L or less 2. A silver halide color photographic light-sensitive material having, on one side on a support, at least one photographic constituent layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In an image forming method for developing an image by developing a material, at least one of the photosensitive layers in the photosensitive material contains the following silver halide emulsion b, and after exposing the photosensitive material, the color developing solution A. A method for forming an image of a silver halide color photographic light-sensitive material, wherein a developing process is performed using A in a color developing time of 30 seconds or more and 120 seconds or less. <Silver halide emulsion b> At least 50% of the total projected area of the silver halide grains is composed of tabular silver halide grains having two or more twin planes parallel to the main plane and having an aspect ratio of 2 or more,
And a silver halide emulsion in which the grains have a portion having a maximum silver iodide content in a region other than the outermost layer and satisfy the following (1) to (3). (1) The silver iodide content of the outermost layer is 6 mol% or more. (2) The maximum silver iodide content is 6 to 15 mol%. (3) 5 or more dislocation lines per particle. 3. A silver halide color photographic light-sensitive material having, on one side on a support, at least one photographic constituent layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In an image forming method for obtaining an image by developing a material, at least one of the photosensitive layers in the photosensitive material has an average aspect ratio of 2 or more and at least two or more kinds having different average silver iodide contents. A tabular silver halide emulsion is contained in the same layer, and after the photosensitive material is exposed, development processing is performed using the color development processing solution A for a color development processing time of 30 seconds or more and 120 seconds or less. An image forming method for a silver halide color photographic light-sensitive material, characterized in that: 4. A silver halide color photograph having on one side on a support at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In an image forming method for developing a photosensitive material to obtain an image, the photosensitive layer in the photosensitive material has an average aspect ratio of 2 or more and at least two or more tabular halides having different silver iodide contents. A silver emulsion is contained in another layer within the same color-sensitive layer, and after the photosensitive material is exposed, the color development processing time is 30 seconds or more and 12
A method for forming an image of a silver halide color photographic light-sensitive material, wherein the development processing is performed in a range of 0 second or less. 5. A silver halide color photographic having, on one side on a support, at least two photographic constituent layers each comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer. In an image forming method for obtaining an image by developing a photosensitive material, a photographic constituent layer of the photosensitive material contains a polyvinylpyrrolidone polymer or copolymer, and after exposing the photosensitive material, using the color developing solution A Wherein the color developing time is from 30 seconds to 120 seconds. 6. The two or more tabular silver halide emulsions having an average aspect ratio of 2 or more and different in silver iodide content each having an average number of dislocation lines per grain of 10 5. The method for forming an image on a silver halide color photographic light-sensitive material according to claim 3, wherein: