JPH0792633A - Image forming method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a color image forming method for silver halide color photographic sensitive material improved in sharpness without deteriorating photographic performance. CONSTITUTION:This photosensitive material has photographic constituent layers comprising at least each one of red-, green-, and blue-sensitive layers and nonphotosensitive layers on one side of a transparent support, and it is characterized by that it is color developed with a color developing solution containing a color developing agent represented by the formula in which each of R<1> and R<2> is, independently, an optional substituent; R<3> is an alkyl; and R<4> is an alkylene; and R<5> is an alkyl or the like, and it has a specified photographic sensitivity of 25-320 and contains silver in the total coating amount of 3.0-5.0g/m<2> in terms of metallic silver in the photographic constituent layers.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an image forming method for a silver halide color photographic light-sensitive material, and more particularly to a color image forming method with improved sharpness.

[0002]

2. Description of the Related Art Recent technological advances relating to silver halide color photographic light-sensitive materials (hereinafter sometimes abbreviated as "color light-sensitive materials" or simply "light-sensitive materials") have been remarkable, but have been remarkable. In addition to the demand for improvement in photographic performance such as sensitivity and image quality, recently, it has been recently demanded that the product be one in which resource saving, energy saving and environmental issues are taken into consideration.

From the viewpoint of resource saving, since a valuable silver resource, which is a raw material of silver halide grains used in a light-sensitive material, is effectively used, a light-sensitive material having a low silver amount and a coated silver amount as small as possible is desired. There is. However, if the amount of silver is simply reduced, a development inhibitor releasing coupler (DIR coupler) and a silver halide which are added for the purpose of inter-image effect, gradation adjustment, and sharpness improvement of a color light-sensitive material are combined. The balance is lost, and a failure occurs in color image formation. For this reason, it is necessary to reduce the amount of DIR couplers and the like as the amount of silver is reduced, which causes a new problem that sharpness, graininess and the like deteriorate.

As a general measure for improving sharpness deterioration, for example, as described in US Pat. No. 3,409,433,
There is a method in which the film is colored with a water-soluble dye to prevent a decrease in image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called "irradiation"). However, most dyes used for coloring, when added to the photographic emulsion layer for improving sharpness, have little effect on the photographic emulsion itself, but are unnecessary for the spectrally sensitized emulsion. There is the drawback of causing a decrease in sensitivity which may be due to spectral sensitization or desorption of the sensitizing dye in the region.

As another measure for improving sharpness, there is a method of reducing the diffused reflection by reducing the coating amount of gelatin on the light-sensitive material to prevent irradiation, but fog due to physical pressure on the light-sensitive material increases. Under the present circumstances, it is not easy to improve the sharpness of a light-sensitive material.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming a color image of a silver halide color light-sensitive material having a low silver content and improved sharpness without deteriorating photographic performance. Is.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to comprise, on one side of a transparent support, at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer. A silver halide color light-sensitive material having a photographic constituent layer,
In the color image forming method for obtaining a color image by developing with a color developing solution containing a color developing agent, the specific photographic sensitivity of the silver halide color light-sensitive material is 25 or more 320
And the coating amount of silver in terms of metallic silver in the photographic constituent layer is 3.0 g / m ² or more and 5.0 g / m ² or less, and the color developing agent is represented by the following general formula (1). And a method of forming an image of a silver halide color photographic light-sensitive material.

[0008]

[Chemical 2]

In the formula, R ₁ and R ₂ may be the same or different and each represents an arbitrary substituent. R ₃ represents an alkyl group, R ₄
Represents an alkylene group. R ₅ represents an alkyl group, an aryl group, or a heterocyclic group linked by carbon atoms.

More preferably, at least one of the silver halide emulsions in the light-sensitive layer is spectrally sensitized by adding a substantially water-insoluble spectral sensitizing dye for photographic use in the solid state without using an organic solvent. The method for forming an image of a silver halide color photographic light-sensitive material as described above, and more preferably, the bleaching treatment time is 1 in the method for forming an image of a silver halide color photographic material in which a bleaching treatment step is performed after the color development processing step. It was achieved by a method of forming an image of a silver halide color photographic light-sensitive material which is within a minute.

The inventors of the present application have judged that there is a limit to the improvement of the sharpness from the constituents of the silver halide color photographic light-sensitive material, and control the image formation.
The processing step, which is one of the factors, is examined, and among them, attention is paid to the color developing agent, and the silver halide color light-sensitive material is processed with the color developing solution containing the compound represented by the general formula (1) as the color developing agent. However, although the mechanism is not clear, it was found that the sharpness was improved more than expected, and the present invention was completed.

Processing a low silver content silver halide color light-sensitive material with a specific color developing agent is disclosed in JP-A-3-246543.
No. 4-11255, No. 4-337727, etc., but it is completely different from the object of the present invention, and no improvement in sharpness is disclosed.

Further, the effect of the image forming method of the present invention is hardly exerted even when applied to the conventional silver halide color photographic light-sensitive material of the related art, and is exhibited only in the silver halide color photographic light-sensitive material of the present invention. I have found what to do.

The present invention will be described in more detail below.

In the present invention, the total coated silver amount coated on the support can be measured by a fluorescent X-ray method. The total amount of coated silver also includes silver halide and colloidal silver which have substantially no photosensitivity. The total coated silver amount of the silver halide color light-sensitive material in the present invention is 3.0 g / m ² or more 5.0
It is characterized in that it is not more than g / m ² .

In order to effectively use valuable silver resources, studies have been conducted to reduce the coated silver amount in silver halide color photographic light-sensitive materials as much as possible.

In the light-sensitive material of the present invention, the total coated silver amount is preferably 3.0 to 4.5 g / m ² , and more preferably 3.5 to 4.0 g / m ² .

The silver halide grains useful in the present invention have a silver halide content of 3 mol% or more as an average halogen composition in all silver halide emulsion layers constituting a light-sensitive material. Good. Therefore, the silver iodide content of the light-sensitive material as a whole is sufficient, and the silver halide grains contained in a certain layer may be out of this range.

The present invention is characterized by having at least one layer of red-sensitivity, green-sensitivity and blue-sensitivity on the support. Each photosensitive layer may have any number of layers,
1 to 5 layers are preferable, and 2 layers and 3 layers are particularly preferable. When each photosensitive layer is composed of multiple layers, a high-sensitivity layer,
It is preferably composed of layers having substantially the same color sensitivity, but different photographic sensitivities, such as a medium-speed layer and a low-speed layer. The "substantially the same color sensitivity" as used herein may be the same in terms of blue photosensitivity, green photosensitivity, and red photosensitivity, and the spectral sensitivity characteristics need not be exactly the same. Further, either a so-called forward layer structure or a reverse layer structure may be used.

A layer having substantially no photosensitivity may be provided between the respective photosensitive layers.

The grain size of the silver halide used in the present invention is not particularly limited, but it is preferably 0.1 to 3 μm in view of image characteristics such as graininess and processability due to the difference in developability depending on the grain size of grains. And more preferably 0.2 to 2
μm. Further, the structure of the silver halide grains is preferably core / shell type silver halide grains. The core / shell type is a silver halide grain having different silver halide compositions between the inside and the surface.

Further, monodisperse grains are preferred, and the ratio S / r of the standard deviation (S) of the grain diameters to the average grain diameter (r) of the entire silver halide grains contained in each silver halide emulsion layer.
The coefficient of variation defined by is preferably 0.4 or less, more preferably 0.33 or less, further preferably 0.25 or less, particularly preferably 0.20 or less.

The average grain size (r) is the grain size (in the case of cubic silver halide grains, the length of one side thereof, or in the case of grains other than cubic grains, converted to cubic grains having the same volume). When the number of particles of (length of one side) ri is ni, it is defined by the following formula 1. The standard deviation (S) of the particle size (ri) is expressed by the following equation 2.

[0024]

[Equation 1]

The monodisperse core / shell type silver halide emulsion used in the present invention as described above is disclosed in JP-A-59-17735.
No. 3, No. 60-138538, No. 59-52238, No. 60-143331,
It can be produced by a known method disclosed in Nos. 60-35726 and 60-258536.

Tabular grains can also be used in the present invention.

In the silver halide emulsion according to the present invention, pAg and pH in the liquid phase for producing and growing silver halide grains, temperature and stirring are controlled in a predetermined pattern, sodium chloride, potassium bromide and iodide. Halides such as potassium,
It is produced by an emulsion producing apparatus by the double jet method, which controls the addition of silver nitrate. Further, a substantially non-photosensitive fine grain emulsion having silver halide grains having a diameter of 0.01 to 0.2 μm can be prepared in the same manner and used for the protective layer and the intermediate layer.

The term "substantially non-photosensitive" means a sensitivity of 1/50 or less of the lowest-sensitivity grains present in the photosensitive emulsion layer.

In the present invention, in order to obtain a wide exposure latitude, silver halide emulsions having different grain sizes or different silver halide compositions may be mixed and used in the same constituent layer.

The silver halide grains having different grain sizes to be mixed and used include silver halide grains having a maximum average grain size of 0.2 to 2.0 μm and minimum average grain sizes of 0.05 to 1.0 μm. A combination of silver halide grains having a different diameter is preferable, and one or more kinds of silver halide grains having an average particle diameter in the middle may be combined. The average grain size of the silver halide grains having the maximum average grain size is preferably 1.5 to 40 times the average grain size of the silver halide grains having the minimum average grain size.

The present invention is a general-purpose color negative film,
It can be applied to various color light-sensitive materials represented by color positive films.

In the color light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 24 μm or less, more preferably 20 μm or less, and more preferably 18 μm.
The following are more preferable. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured at 25 ° C. and 55% relative humidity (2 hr), and the film swelling speed T _1/2 can be measured according to a method known in the art.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. or,
The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (film thickness) / film thickness.

The substantially water-insoluble spectral sensitizing dye for use in the present invention has a solubility of 1 × 10 ⁻⁴ to 27 ° C. in an aqueous system in which an organic solvent and / or a surfactant is not present.
4 × 10 ^-2 mol / liter, preferably 2 × 10 ^-4 to 4 × 10
^A spectral sensitizing dye of ^-2 mol / liter was added in an amount exceeding the solubility and mechanically dispersed in solid fine particles of 1 μm or less.

In contrast to the technique disclosed in the above-mentioned JP-A-3-288842, the present invention has been made for uniformly and effectively adsorbing a photographic spectral sensitizing dye on the surface of silver halide grains. The above-mentioned technique for merely adding in a dispersed manner is different from the intended effect.

In the present invention, the above-mentioned conventionally used organic solvent is not substantially contained. Further, as described above, it does not substantially contain the surfactant which has been conventionally used as a dispersant for sensitizing dyes.

In the present invention, the aqueous system substantially free of organic solvent and / or surfactant is water containing impurities at a level not adversely affecting the silver halide photographic emulsion, and more preferably ion exchange. Refers to water.

The solubility in water of the spectral sensitizing dye in the present invention is a 2 × 10 ^-4 ~4 × 10 ^-2 mol / liter, more preferably 1 × 10 ^-3 ~4 × 10 ^-2 mol / It is a liter.

That is, if the solubility is lower than this range, the dispersion particle size becomes very large and non-uniform, so that the dispersion is precipitated after the dispersion is completed or the dispersion is added to the silver halide emulsion. It was found that when this occurs, the process of adsorbing the dye on the silver halide is hindered.

Further, if the solubility is higher than this range, the viscosity of the dispersion increases more than necessary, air bubbles are entrapped, and the dispersion is hindered. At higher solubility, dispersion becomes impossible. However, it has become clear from the research conducted by the present inventors.

The spectral sensitizing dye in the present invention means a compound which causes electron transfer to silver halide when it is photoexcited when it is adsorbed on silver halide and does not include organic dyes.

The spectral sensitizing dye of the present invention may be any one having a solubility in water in the range of 2 × 10 ^-4 to 4 × 10 ^-2 mol / liter, preferably a cyanine dye.
More preferably, it is a cyanine dye having a hydrophilic group (eg, —SO ₃ H, —COOH, etc.).

Specific examples and solubilities in water will be given below, but the present invention is not limited thereto.

[0044]

[Chemical 3]

[0045]

[Chemical 4]

[0046]

[Chemical 5]

In the present invention, various dispersers are effectively used for mechanically pulverizing and dispersing the spectral sensitizing dye in an aqueous solvent. Specifically, a high speed stirrer, a ball mill, a sand mill, a colloid mill, an attritor, an ultrasonic disperser or the like is used. A high speed stirrer is preferred in the present invention.

The high-speed stirring type disperser may have a dissolver having a plurality of impellers mounted on the vertical axis or a multi-axis dissolver having a plurality of vertical axes. In addition to the dissolver alone, a high-speed stirring type disperser having anchor blades is more preferable.

As a concrete working example, after water is put in a tank whose temperature can be adjusted, a certain amount of the powder of the spectral sensitizing dye is put therein, and the mixture is agitated by a high-speed agitator for a certain time under temperature control. Then, crush and disperse. The pH and temperature at which the spectral sensitizing dye is mechanically dispersed are not particularly limited, but the desired particle size cannot be reached even after long-term dispersion at low temperature, and reaggregation or decomposition at high temperature occurs. Occurs, and the desired photographic performance cannot be obtained, and when the temperature is raised, the viscosity of the solution system lowers, so that the efficiency of pulverization and dispersion of solids is greatly reduced. Therefore, the dispersion temperature is 15 ~
It is more preferably 50 ° C. Furthermore, the stirring rotation speed during dispersion requires a long time to obtain a desired particle size at low rotation speeds, and at high rotation speeds, bubbles are entrained and the dispersion efficiency is reduced, so dispersion is performed at 1000 to 6000 rpm. More preferably.

The fact that the solid fine particles of the spectral sensitizing dye dispersed by the method of the present invention are 1 μm or less means that the particle size based on the volume average diameter of spheres is 1 μm or less, which is measured by a general method. it can.

The dispersion used in the present invention means a suspension of a spectral sensitizing dye, preferably a spectral sensitizing dye having a weight ratio of 0.2% to 5.0% in the suspension. Used.

The dispersion of the spectral sensitizing dye prepared according to the present invention may be added directly to the silver halide emulsion,
Water may be used as the diluting solution at this time, although it may be appropriately diluted before addition.

In the case of constituting the light-sensitive material of the present invention, the silver halide emulsion is generally used after physical ripening and spectral sensitization. Additives used in such processes are Research Disclosure No.17643, No.1
8716 and No.308119 (respectively RD17643, RD18
716 and RD308119).

The places described below are shown.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A item 23 648 Spectral sensitizer 996 IV-A, B, C, 23-24 648-9 D, H , I, J items Supersensitizer 996 IV-AE, J items 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Chemical sensitization of emulsions used in the present invention The feeling is more specifically a sulfur-containing chemical that can react with silver ions, a sulfur sensitizing method using active gelatin, a selenium sensitizing method using a selenium compound, a reduction sensitizing method using a reducing substance, and gold. The noble metal sensitization method using other noble metal compounds can be used alone or in combination.

In the present invention, for example, a chalcogen sensitizing method can be used as the chemical sensitizer, and among them, a sulfur sensitizer and a selenium sensitizer are preferable.

Examples of the sulfur sensitizer include thiosulfate,
Examples thereof include allyl thiocarbamide, thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, and rhodanine.

Others, US Pat. Nos. 1,574,944 and 2,410,6
89, 2,278,947, 2,728,668, 3,501,313, 3,656,955, West German Application Publication (OLS) 1,422,869, JP-A-56-24937, 55-4501.
The sulfur sensitizers described in No. 6 and the like can also be used.

The amount of the sulfur sensitizer added varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but as a guide, it is about 1 mol per mol of silver halide. It is preferably about 10 ^-7 mol to about 10 ^-1 mol.

As the selenium sensitizer, aliphatic isocyanates such as allyl isoselenocyanate, selenoureas, selenoselenides, selenides such as diethyl selenide, and the like can be used. Specific examples thereof are US It is described in Japanese Patent Nos. 1,574,944, 1,602,592 and 1,623,499. Further, reduction sensitization can be used together.

Examples of the reducing agent include stannous chloride, thiourea dioxide, hydrazine and polyamine. Further, a noble metal compound other than gold, for example, a palladium compound or the like can be used together.

The silver halide grains of the emulsion used in the present invention preferably contain a gold compound.

The gold compound preferably used in the present invention may have a gold oxidation number of +1 valence or +3 valence, and various kinds of gold compounds are used.

As a typical example, chloroaurate is potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, gold. Examples include selenide.

The gold compound may be used to sensitize the silver halide grains, or may be used so as not to substantially contribute to the sensitization.

The amount of the gold compound added varies depending on various conditions, but as a guide, from 10 ^-8 mol per mol of silver halide
It is 10 ^-1 mol, preferably 10 ^-7 mol to 10 ^-2 .

Further, these compounds may be added at any of the steps of silver halide grain formation, physical ripening, chemical ripening and after chemical ripening.

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

The following is the relevant description part.

[Items] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, 25-26 XIII-C Light absorber 1003 VIII 25-26 Light-scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricating oil 1006 XII 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matting agent 1007 XVI Developer 1011 XX-B (Contained in photosensitive material) Also, deterioration of photographic performance due to formaldehyde gas In order to prevent it, it is preferable to add to the light-sensitive material a compound capable of being immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure (RD) No. No. 17643, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,051, 4,022,620, and 4,326,024.
No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-107
39, UK Patents 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,023, 4,511,649
And those described in European Patent No. 279,473A are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,636 are preferred.
No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230.
(June 1984), JP-A-60-43659, 61-72238,
No. 60-35730, No. 55-118034, No. 60-185951, No. 4,500,630, No. 4,540,654, No. 4,556,630,
Those described in International Publication WO88 / 04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers. US Pat. No. 4,052,
No. 212, No. 4,146,396, No. 4,228,233, No. 4,29
No. 6,200, No. 2,369,929, No. 2,801,171, No. 2,7
72,162, 2,895,826, 3,772,002, 3,
No. 758,308, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No.
249,453A, US Pat. Nos. 3,446,622, and 4,333,999.
No. 4,775,616, No. 4,451,559, No. 4,427,76
No. 7, No. 4,690,889, No. 4,254,212, No. 4,296,1
Those described in 99, JP-A-61-242658 and the like are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are Research Disclosure No. 1
7643, Item VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258,
Those described in British Patent 1,146,368 are preferred. or,
U.S. Pat.No. 4,774,181 A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling described in U.S. Pat. It is preferable to use a coupler having as a leaving group.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent No. 2,125,5.
70, European Patent 96,570, West German Patent (Publication) 3,234,
Those described in No. 533 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820, 4,080,211 and US Pat.
4,367,282, 4,409,320, 4,576,910, and British Patent 2,102,173.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention.
The DIR coupler that releases the development inhibitor is RD17 described above.
643, Patents described in Section VII-F, JP-A-57-151944
Nos. 57-154234, 60-184248, 63-37346, and US Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As couplers which release an engraving agent or a development accelerator imagewise upon development, there are described in British Patent No. 2,097,140.
No. 2,131,188, JP-A-59-157638, and 59-17084.
Those described in No. 0 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427, US Pat. Nos. 4,283,427 and 4,33.
No. 8,393, No. 4,310,618, multi-equivalent couplers, JP-A-60
-185950, JP-A-62-24252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound, or D
IR redox-releasing redox compounds, EP 173,
No. 302A, a coupler which releases a dye that recovers color after withdrawal, R.I. D. No. 11449, No. 24241, and bleaching accelerator releasing couplers described in JP-A No. 61-201247, U.S. Pat.
Ligand releasing couplers described in JP-A-63-75747
Leuco dye releasing couplers described in U.S. Pat.
Examples thereof include couplers releasing a fluorescent dye described in 4,774,181.

Further, various couplers can be used in the present invention, specific examples of which are described in the following RD. The relevant parts are shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VII C to G item Magenta coupler 1001 VII-D item VII C to G item Cyan coupler 1001 VII-D item VII C to G item Colored coupler 1002 VII-G section VII G section DIR coupler 1001 VII-F section VII F section BAR coupler 1002 VII-F section Other useful residues Release coupler 1001 VII-F section Additives used in the present invention are RD308119XIV. It can be added by the dispersion method described.

In the present invention, the aforementioned RD17643, 28th
The supports described on page RD 18716 647-8 and RD 308119 XIX can be used.

The light-sensitive material of the present invention includes the above-mentioned RD308119.
An auxiliary layer such as a filter layer or an intermediate layer described in the section VII-K can be provided.

The outermost surface of the photographic constituent layer of the light-sensitive material of the present invention
The pH is 5.0 to 7.0, preferably 5.5 to 6.5.
It can be measured by the method described in 245153.

Suitable supports which can be used in the present invention are, for example, RD. No. 17643, page 28 and No. 18716, page 647, right column to page 648, left column.

As a specific support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate film or the like can be used. The thickness of the support is usually 50 to 200 μm.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable that it is housed in a cartridge. The most common cartridges are
It is a 135 format Patrone. Other cartridges proposed in the following patents can also be used (Shokai 58-6
7329, JP-A-58-181035, JP-A-58-182634, Shoukai-sho 58
-195236, U.S. Pat.No. 4,221,479, Japanese Patent Application No. 63-57785
No. 63-183344, 63-325638, Japanese Patent Application No. 1-21862
No. 1, No. 1-25362, No. 1-30246, No. 1-20222, No. 1-218
63, 1-37181, 1-333108, 1-85198, 1-1
72595, 1-172594, 1-172593, U.S. Pat.
46,418, 4,848,693, 4,832,275).

Further, the present invention can be applied to Japanese Patent Application No. 4-16934, entitled "Small Photographic Roll Film Patrone and Film Camera".

In order to obtain a dye image using the light-sensitive material of the present invention, a commonly known color development process can be carried out after exposure.

The light-sensitive material of the present invention is RD17643, 28-2.
Development processing can be carried out by a usual method described in page 9, RD18716, pages 647 and RD308119, XII.

In the present invention, the specific photographic sensitivity is 25 or more.
It is less than 320, but preferably 50 or more and 200 or less.

The specific photographic sensitivity of the light-sensitive material in the present invention is determined according to the following test method according to ISO sensitivity (according to JIS K 7614-1981).

(1) Test conditions The test is conducted in a room at a temperature of 20 ± 5 ° C. and a relative humidity of 60 ± 10%.
The photosensitive material to be tested is left in this state for 1 hour or more before use.

(2) Exposure The relative spectral energy distribution of the reference light on the exposure surface is as shown below.

Wavelength nm Relative Spectral Energy ( ¹ ) 360 2 370 8 380 14 390 23 400 45 410 57 420 63 430 62 440 81 450 93 460 97 470 98 480 101 490 97 500 100 540 102 550 103 560 100 570 97 580 98 590 90 600 93 610 94 620 92 630 88 640 89 650 86 660 86 670 89 680 85 690 75 700 77 Note ( ¹ ) The value determined by standardizing the value of 560 nm to 100.

The illuminance change on the exposed surface is performed by using an optical wedge, and in any part of the optical wedge used, the variation of the spectral transmission density is within 10% in the wavelength region of 360 to 700 nm and within 10% in the region of 400 nm or more. Use within 5%.

The exposure time is 1/100 second.

(3) Development Processing From exposure to development processing, the photosensitive material to be tested is kept at a temperature of 20 ± 5 ° C. and a relative humidity of 60 ± 10%.

The development process is completed within 30 minutes or more and 6 hours after exposure.

Development Processing British Journal of Photog
C-41 treatment by Eastman Kodak Co. described in raphy Annual 1988, P.196-198 is performed.

(4) Concentration measurement Concentration is represented by log ₁₀ (Φ ₀ / Φ). Φ ₀ is an illumination light flux for density measurement, and Φ is a transmitted light flux of the measured portion. The geometric condition for density measurement is that the illumination light flux is a parallel light flux in the normal direction, and the standard is to use the total light flux that is transmitted as a transmitted light flux and diffused in a half space, and standard when other measurement methods are used. Correct with density strips. In addition, the emulsion film surface shall face the light-receiving device side during measurement. Density is measured with Status M densities of blue, green, and red, and its spectral characteristics are the values shown in Table 1 and Table 2 as the overall characteristics of the light source, optical system, optical filter, and light receiving device used for the thermometer. To

[0103]

[Table 1]

[0104]

[Table 2]

(5) Determination of specific photographic sensitivity Using the results of processing and density measurement under the conditions (1) to (4), the specific photographic sensitivity is determined by the following procedure.

Exposure doses corresponding to 0.15 higher densities with respect to the respective minimum densities of blue, green and red are expressed in lux · second and are respectively H _B , G _O and H _R.

The larger value (lower sensitivity) of H _B and H _R is defined as H _s .

The specific photographic sensitivity S is calculated according to the following formula.

[0109]

[Equation 2]

To obtain a dye image using the light-sensitive material of the present invention, color photographic processing is carried out after exposure. Color processing is
A color development processing step, a bleaching processing step, a fixing processing step, a water washing processing step and a stabilization processing step are carried out if necessary. Instead of the processing step using the bleaching solution and the processing step using the fixing solution, one bath is used. The bleach-fixing solution can be used for the bleach-fixing treatment step, or the mono-bath processing step can be carried out using the one-bath development bleach-fixing treatment solution for color development, bleaching and fixing in one bath. .

These treatment steps may be combined to perform a pre-hardening treatment step, a neutralizing step thereof, a stop fixing treatment step, a post-hardening treatment step and the like. In these treatments, instead of the color development treatment step, a color developing agent or its precursor may be contained in the material and the development treatment may be carried out by an activator treatment step, or the activator treatment may be applied to the monobath treatment. You can Typical processing is shown below among these processings. (These steps include any one of a washing step, a washing step and a stabilizing step as the final step.) ・ Color development processing step-bleaching step-fixing step-prehardening step-color development Processing step-Stop fixing processing step-Water washing processing step-Bleaching processing step-Fixing processing step-Water washing processing step-Post-hardening processing step-Color development processing step-Water washing processing step-Supplementary color development processing step-Stop processing step-Bleach Processing step-Fixing processing step-Activator processing step-Bleaching fixing processing step-Activator processing step-Bleaching processing step-Fixing processing step-Mono bath processing step The processing temperature is usually selected in the range of 10 ° C to 65 ° C. 65 ° C
The temperature may exceed. It is preferably treated at 25 ° C to 45 ° C.

The color developing solution comprises an alkaline aqueous solution containing the color developing agent of the present invention.

The color developing agent of the present invention has the general formula (1) above.
Indicated by.

Of these substituents, preferable R ¹ and R ² are hydrogen atom, halogen atom, alkyl group, alkoxy group, alkoxycarbonylamino group, ureido group, sulfonamide group, alkylthio group, carbamoyl group, carboxamide group, An alkylamino group, a heterocyclic group and the like, more preferably an alkyl group, among them, methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methanesulfonamidoethyl, 3 -Methanesulfonamidopropyl,
2-methanesulfonylethyl, 2-methoxyethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobutyl, 4 Each group of -carbamoylbutyl, 2-carbamoyl-1-methylethyl and 4-nitrobutyl is preferable, and a methyl group and an ethyl group are particularly preferable.

Preferred substituents for R ³ are methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methoxyethyl, 2-methanesulfonamidoethyl, 2-acetamidoethyl. , 2-carbamoylethyl, 3-carbamoylpropyl, 3-carbamoylpropyl, 3-carbamoylaminopropyl and 3-hydroxy-1-methylpropyl groups, with methyl, ethyl and propyl groups being most preferred.

The substituent of R ⁴ is preferably an alkylene group having a main chain of 2 or more carbon atoms, more preferably ethylene, 2-methylethylene, trimetine, tetramethylene, 2-methyltrimethine, 1-methyl. An ethylene group, particularly an alkylene group having a main chain of 2 carbon atoms is preferable, and an ethylene group is particularly preferable.

R ² and R ³ , and R ² and R ⁴ may together form a condensed ring. R ³ and R ⁴ may together form a heterocycle. The number of rings formed may be one, or may be two or more. The number of members in each ring is not limited, but among them, a 5-membered ring, a 6-membered ring and a 7-membered ring are preferable.

The substituent of R ⁵ is preferably a substituted or unsubstituted alkyl group, and particularly preferable specific examples thereof include a methyl group, an ethyl group, an i-propyl group, a t-butyl group, a chloromethyl group, A methoxymethyl group, an acetamidomethyl group, a 2,2,2-trichloroethyl group, and a 2-methoxyethyl group.

Next, specific examples of the color developing agent of the general formula (1) of the present invention are shown, but the present invention is not limited to these.

[0120]

[Chemical 6]

[0121]

[Chemical 7]

[0122]

[Chemical 8]

[0123]

[Chemical 9]

[0124]

[Chemical 10]

[0125]

[Chemical 11]

[0126]

[Chemical 12]

[0127]

[Chemical 13]

[0128]

[Chemical 14]

[0129]

[Chemical 15]

[0130]

[Chemical 16]

[0131]

[Chemical 17]

[0132]

[Chemical 18]

[0133]

[Chemical 19]

The color developing agent of the present invention is used in a concentration of preferably 0.1 to 30 g, and more preferably 1 to 10 g per liter of color developing solution.

The color developing agents may be used alone or in combination of two or more kinds. Furthermore, the color developing agent may be incorporated in a color photographic material. In this case, the silver halide color photographic light-sensitive material can be treated with an alkaline solution (activator solution) instead of the color developing solution.

The color developing solution can be prepared by using an alkaline agent usually used in developing solutions such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. Further, various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or a development modifier such as citrazinic acid, and a preservative such as hydroxylamine or sulfite are contained. You may. Further, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide, dimethylsulfoxide and the like can be appropriately contained.

The pH of the color developing solution is usually 7 or more, preferably about 9-13.

In the color developer used in the present invention, if necessary, an antioxidant such as diethylhydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol,
Hydroxamic acid, pentose or hexose, pyrogallol-1,3-dimethyl ether and the like may be contained.

Various chelating agents can be used in combination in the color developer as a sequestering agent. For example, as the chelating agent, ethylenediaminetetraacetic acid, aminopolycarboxylic acid such as diethylenetriaminepentaacetic acid, 1-
Organic phosphonic acids such as hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1, Examples thereof include phosphonocarboxylic acid such as 2,4-tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compound.

The bleaching process may be carried out simultaneously with the fixing process as described above, or may be carried out individually.
As the bleaching agent, a metal complex salt of an organic acid is used, and for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid, citric acid, or the like in which a metal ion such as iron, cobalt or copper is coordinated is used. Among the above-mentioned organic acids, the most preferable organic acid is polycarboxylic acid or aminopolycarboxylic acid. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′,
N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylene Diamine tetraacetic acid etc. can be mentioned.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

These bleaching agents are preferably 5-450 g /
Used in L.

As the bleaching solution, in addition to the bleaching agent as described above, a solution having a composition containing sulfite as a preservative can be used if necessary. The bleaching solution may be a solution containing an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and having a composition in which a large amount of a halide such as ammonium bromide is added. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

As the bleaching solution, JP-A-46-280 and JP-B-45-8 can be used.
No. 506, No. 46-556, Belgian Patent No. 770,910, Japanese Patent Publication
45-8836, 53-9854, JP-A-54-7163 and 49-42
Various bleaching accelerators described in, for example, No. 349 can be added.

The pH of the bleaching solution is 2.0 or more, but it is generally 4.0 to 7.0, preferably 4.0 to 6.5, and most preferably 4.0 to 6.0.

The main bleaching agent preferably used in the bleaching solution or the bleach-fixing solution according to the present invention is a ferric complex salt of an organic acid represented by the following general formula [C].

[0147]

[Chemical 20]

[In the formula, A _{1 to} A ₄ may be the same or different and each represents —CH ₂ OH, —COOM or —PO ₃ M ₁ M ₂ . M,
M ₁ and M ₂ each represent a hydrogen atom, an alkali metal or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. The compound represented by formula [C] will be described in detail below.

In the formula, A _{1 to} A ₄ are Japanese Patent Application No. 1-260628 12
Since it has the same meaning as A _{1 to} A ₄ described from line 15 to page 15 to line 3 from page 15, detailed description will be omitted.

Preferred specific examples of the compound represented by the above general formula [C] are shown below.

[0151]

[Chemical 21]

[0152]

[Chemical formula 22]

As the ferric iron complex salts of these compounds (C-1) to (C-12), sodium salt, potassium salt or ammonium salt of these ferric iron complex salts can be optionally used.

Of the above-mentioned compound examples, those particularly preferably used in the present invention include (C-1), (C-3),
(C-4), (C-5) and (C-9), and particularly preferred is (C-1).

In the present invention, the bleaching solution or the bleach-fixing solution may contain, as the bleaching main agent, an iron complex salt of the compound represented by the general formula [C] and a ferric iron complex salt of the following compound.

[A′-1] Ethylenediaminetetraacetic acid [A′-2] trans-1,2-cyclohexanediaminetetraacetic acid [A′-3] Dihydroxyethylglycinic acid [A′-4] Ethylenediaminetetrakismethylenephosphonic acid [A′-4] A'-5] Nitrilotrismethylenephosphonic acid [A'-6] diethylenetriaminepentakismethylenephosphonic acid [A'-7] diethylenetriaminepentaacetic acid [A'-8] ethylenediaminedioltohydroxyphenylacetic acid [A'-9] hydroxy Ethyl ethylenediamine triacetic acid [A'-10] ethylenediamine dipropionic acid [A'-11] ethylenediamine diacetic acid [A'-12] hydroxyethyliminodiacetic acid [A'-13] nitrilotriacetic acid [A'-14] nitrilo-3 Propionic acid [A'-15] triethylene Tetraminehexaacetic acid [A'-16] ethylenediaminetetrapropionic acid [A'-17] β-alaninediacetic acid The amount of the ferric organic acid complex salt added is in the range of 0.01 to 2.0 mol per liter of the bleaching solution or the bleach-fixing solution. It is preferably contained, and more preferably in the range of 0.05 to 1.5 mol / l.

The bleaching solution, the bleach-fixing solution and the fixing solution include imidazole and its derivatives described in JP-A 64-295258 or compounds represented by the general formulas [I] to [IX] described in the specification. And, by containing at least one of these exemplified compounds, it is possible to exert an effect on promptness.

In addition to the above accelerators, the exemplified compounds described on pages 51 to 115 of JP-A-62-123459 and pages 22 to 25 of JP-A-63-17445. The exemplified compounds described in JP-A-53-95630 and JP-A-53-28426 can be similarly used.

In addition to the above, the bleaching solution or the bleach-fixing solution may contain halides such as ammonium bromide, potassium bromide and sodium bromide, various fluorescent whitening agents, defoaming agents or surfactants. it can. The bleaching treatment time using the bleaching solution of the present invention is preferably within 1 minute, particularly preferably 15 seconds to 45 seconds.

As the fixing solution, those having a generally used composition can be used. As the fixing agent, a compound which reacts with silver halide to form a water-soluble complex salt as used in a usual fixing process, for example, thiosulfate such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, potassium thiocyanate. , Sodium thiocyanate,
Typical examples thereof include thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount in the range of 5 g / L or more so that they can be dissolved, but generally 70 to 250 g / L is used. The fixing agent may be partly contained in the bleaching solution,
On the contrary, a part of the bleaching agent may be contained in the fixing solution.

The bleaching solution and the fixing solution include boric acid, borax,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Various pH of potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
It may contain a buffering agent, an antifoaming agent, or a surfactant. Further, hydroxylamine, hydrazine, preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, hardening agents such as water-soluble aluminum salts, An organic solvent such as methanol, dimethylformamide, and dimethylsulfoxide may be appropriately contained.

The fixer is used at a pH of 3.0 or higher, but is generally used at 4.5-10, preferably 5-9.5, and most preferably 6-9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of the organic acids described in the above bleaching step, and preferably the compound and the concentration in the processing solution are the same as in the above bleaching step.

As the bleach-fixing solution, a solution containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition in which a small amount of a halide such as ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and the above silver halide fixing agent such as ammonium bromide is added, or conversely, a halide such as ammonium bromide. It is also possible to use a special bleach-fixing solution having a composition in which a large amount of is added. Examples of the halides include ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide,
Ammonium iodide or the like can also be used.

Examples of the silver halide fixing agent that can be contained in the bleach-fixing solution include the fixing agents described in the above fixing processing step. The concentration of the fixing agent and the pH buffer and other additives which can be contained in the bleach-fixing solution are the same as those in the fixing processing step.

The pH of the bleach-fixing solution is used at 4.0 or more, but it is generally used at 5.0 to 9.5, preferably 6.0 to 8.5.
And most preferably 6.5 to 8.5.

[0167]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all of the following examples, the addition amount of each component of the silver halide color light-sensitive material is shown by the coating amount expressed in g / m ² . However, for silver halide, the coating amount in terms of silver is shown, and for the sensitizing dye, the coating amount per mol of silver halide in the same layer is shown in mol unit.

Example 1 On a subbed cellulose triacetate film support,
Sample A, which is a multilayer color light-sensitive material composed of each layer having the composition shown below, was prepared.

Sample A First layer: Antihalation layer Black colloidal silver 0.15 Ultraviolet absorber (UV-1) 0.30 High boiling point solvent (Oil-1) 0.16 Gelatin 1.64 Second layer: Intermediate layer Gelatin 0.80 Third layer: Low sensitivity Red-sensitive layer Silver iodobromide emulsion (1) 0.44 Silver iodobromide emulsion (3) 0.11 Sensitizing dye (SD-1) 2.6 × 10 ^-5 Sensitizing dye (SD-2) 2.6 × 10 ^-5 Sensitizing Dye (SD-3) 3.1 × 10 ^-4 Sensitizing dye (SD-4) 2.3 × 10 ^-5 Sensitizing dye (SD-5) 2.8 × 10 ^-4 Cyan coupler (C-1) 0.35 Colored cyan coupler (CC -1) 0.065 Compound (GA-1) 2.0 x 10 ^-3 High boiling point solvent (Oil-1) 0.33 Gelatin 0.73 Fourth layer: Medium-sensitive red photosensitive layer Silver iodobromide emulsion (3) 0.39 Sensitizing dye (SD -1) 1.3 × 10 ^-4 sensitizing dye (SD-2) 1.3 × 10 -4 sensitizing dye (SD-3) 2.5 × 10 -4 sensitizing dye (SD-4) 1.8 × 10 -5 cyan coupler C-1) 0.24 Colored cyan coupler (CC-1) 0.040 DIR compound (D-1) 0.025 Compound (GA-1) 1.0 × 10 -3 High boiling solvent (Oil-1) 0.30 Gelatin 0.59 Fifth Layer: High Sensitivity Red-sensitive layer Silver iodobromide emulsion (4) 0.91 Sensitizing dye (SD-1) 8.5 × 10 ⁻⁵ Sensitizing dye (SD-2) 9.1 × 10 ⁻⁵ Sensitizing dye (SD-3) 1.7 × 10 ^-4 Sensitizing dye (SD-4) 2.3 × 10 ^-5 Sensitizing dye (SD-6) 1.1 × 10 ^-5 Cyan coupler (C-2) 0.10 Colored cyan coupler (CC-1) 0.014 DIR compound (D- 1) 7.5 × 10 ^-3 compound (GA-1) 1.4 × 10 ^-3 high boiling point solvent (Oil-1) 0.12 gelatin 0.53 6th layer: intermediate layer gelatin 1.14 7th layer: low sensitivity green photosensitive layer iodobromide Silver emulsion (2) 0.32 Silver iodobromide emulsion (3) 0.74 Sensitizing dye (SD-7) 5.5 × 10 ⁻⁴ Sensitizing dye (SD-1) 5.2 × 10 ⁻⁵ Sensitizing dye (SD-12) 4.8 × 10 ^-5 Magenta Coupler (M-1) 0.15 Magenta Coupler (M-2) 0.37 Colored Magenta Coupler (CM-1) 0.20 DIR Compound (D-2)) 0.020 Compound (GA-1) 4.0 × 10 ^-3 High boiling point solvent (Oil-2) 0.65 Gelatin 1.65 Eighth layer: High-sensitivity green photosensitive layer Silver iodobromide emulsion (5) 0.79 Sensitizing dye (SD-8) 1.4 × 10 ⁻⁴ Sensitizing dye (SD-9) 1.5 × 10 ⁻⁴ Sensitizing dye (SD-10) 1.4 × 10 ⁻⁴ Sensitizing dye (SD-12) 7.1 × 10 ⁻⁵ Magenta coupler (M-2) 0.065 Magenta coupler (M-3) 0.025 Colored magenta coupler (CM) -2) 0.025 DIR compound (D-3) 7.0 x 10 ^-4 compound (GA-1) 1.8 x 10 ^-3 high boiling solvent (Oil-2) 0.15 gelatin 0.46 9th layer: yellow filter layer yellow colloidal silver 0.10 compound (SC-1) 0.14 Compound (FS-1) 0.20 High boiling point solvent (Oil-2) 0.18 Gelatin 1.20 Layer 10: Low-sensitivity blue photosensitive layer Silver iodobromide emulsion (2) 0.27 Silver iodobromide emulsion (3) 0.32 Sensitizing dye (SD-11) 5.4 × 10 ^-4 Sensitizing dye (SD- 12) 2.0 × 10 ^-4 Sensitizing dye (SD-6) 6.5 × 10 ^-5 Yellow coupler (Y-1) 0.62 Yellow coupler (Y-2) 0.31 Compound (GA-1) 4.5 × 10 ^-3 High boiling point solvent (Oil-2) 0.20 Gelatin 1.27 Layer 11: High-sensitivity blue photosensitive layer Silver iodobromide emulsion (5) 0.66 Sensitizing dye (SD-11) 2.8 × 10 ^-4 Sensitizing dye (SD-12) 1.1 × 10 ⁻⁴ Sensitizing dye (SD-6) 1.1 × 10 ⁻⁵ Yellow coupler (Y-1) 0.10 Compound (GA-1) 2.0 × 10 ⁻³ High boiling point solvent (Oil-2) 0.04 Gelatin 0.57 12th layer: First protective layer Silver iodobromide emulsion (average grain size 0.04 μm, silver iodide content 4.0 mol%) 0.30 UV absorber (UV-1) 0.030 UV absorber (UV-2) 0.015 UV absorber (UV -3 0.015 UV absorber (UV-4) 0.015 UV absorber (UV-5) 0.10 Compound (FS-1) 0.25 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Gelatin 1.04 13th layer: Second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, a coating aid Su-1 , Dispersion aid S
u-2, viscosity modifier, hardener H-1, H-2, stabilizer S
T-1, antifoggant AF-1, dye AI-1, AI-
2, two kinds of AF-2 having a molecular weight of 10,000 and 20,000, and a preservative D
I-1 was added.

The emulsions used for the above samples are as follows. The average particle diameter is shown as the particle diameter converted into the diameter of a sphere having the same volume. Further, each emulsion was optimally subjected to gold and sulfur sensitization.

Emulsion name Average grain size AgI Average grain size Crystal habit Diameter / thickness ratio Content (mol%) (μm) Emulsion (1) 2.0 0.27 Normal crystal tetrahedron 1 Emulsion (2) 2.0 0.30 Normal crystal tetrahedral 1 emulsion (3) 8.0 0.38 Twin octahedron 1.5 Emulsion (4) 8.0 0.55 Twin octahedron 1.5 Emulsion (5) 8.0 0.65 Twin octahedron 1.5

[0173]

[Chemical formula 23]

[0174]

[Chemical formula 24]

[0175]

[Chemical 25]

[0176]

[Chemical formula 26]

[0177]

[Chemical 27]

[0178]

[Chemical 28]

[0179]

[Chemical 29]

[0180]

[Chemical 30]

[0181]

[Chemical 31]

Further, Samples A to F were prepared by changing the addition method of the sensitizing dye added at the time of spectral sensitization and the amount of silver coated on each of the red, green and blue photosensitive layers as shown in Table 3. The pH of the outermost surface of the photographic constituent layers of all the samples was adjusted to be 5.9.

[0183]

[Table 3]

Each of the prepared samples A to F was subjected to wedge exposure using white light, and a developing treatment was carried out using the color developing solutions a and b and the bleaching solution m in the following processing step 1. The specific sensitivities of the prepared sample Nos. 1 to 12 are all 80 to 12.
It was in the range of 0. Then, the MTF values of magenta images of these samples were measured to evaluate the sharpness.
The results are shown below in Table 4. Jame for MTF value
s "The Theory of the Photographic Process" 4th
See page 604.

Processing step 1 Processing step Temperature processing time Color development 38 ± 0.3 ° C. 3 minutes 15 seconds Bleach 38 ± 2.0 ° C. 3 minutes 15 seconds Fixing 38 ± 2.0 ° C. 1 minute 30 seconds Stability 38 ± 5.0 ° C. 1 minute Dry 60 ± 5.0 ℃ 1 minute Processing step B Processing step Temperature processing time Color development 38 ± 0.3 ℃ 3 minutes 15 seconds Bleach 38 ± 2.0 ℃ 45 seconds Settling 38 ± 2.0 ℃ 1 minute 30 seconds Stability 38 ± 5.0 ℃ 1 minute Dry 60 ± 5.0 ℃ 1 minute (Color developer a) Water 800ml Sodium bromide 1.3g Potassium iodide 1.2mg Potassium sulfite 3.0g Potassium carbonate 30.0g Hydroxylamine sulfate 2.5g Ethylenediaminetetraacetic acid 2.0g Color development Main drug (4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate) 2.0 × 10 ^-2 mol Add water to make 1 liter, and add potassium hydroxide or 20%.
Adjust to pH 10.05 with sulfuric acid.

(Color developer b) Water 800 ml Sodium bromide 1.3 g Potassium iodide 1.2 mg Potassium sulfite 3.0 g Potassium carbonate 30.0 g Hydroxylamine sulfate 2.5 g Ethylenediaminetetraacetic acid 2.0 g Color developing agent (Compound 70 of the present invention) 2.0 × 10 ^-2 mol Add water to make 1 liter and add potassium hydroxide or 20%
Adjust to pH 10.05 with sulfuric acid.

(Bleaching solution m) Water 700 ml Ethylenediaminetetraacetic acid ferric ammonium salt 0.3 mol Ethylenediaminetetraacetic acid 2.0 g Sodium nitrate 40.0 g Ammonium bromide 150 g Glacial acetic acid 40.0 g Water was added to make 1 liter, and ammonia water or glacial acetic acid was added. Adjust to pH 6.0 using.

(Bleaching solution n) Water 700 ml 1,3-Propylenediaminetetraacetic acid Ammonium ferric salt 0.3 mol Sodium nitrate 40.0 g Ammonium bromide 150 g Glacial acetic acid 40.0 g Water was added to make 1 liter, and ammonia water or glacial acetic acid was added. Adjust to pH 4.4 using.

(Fixer) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2.0 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

(Stabilizing liquid) 900 ml of water

[0191]

[Chemical 32]

Surfactant 1.0 g Formalin 1.0 g Water was added to make 1 liter, and then ammonia water or 20 g was added.
Adjust to pH 8.0 with% sulfuric acid.

[0193]

[Table 4]

From the results shown in Table 4, it can be seen that the sharpness is improved in the present invention. Similar results were obtained for cyan images.

Example 2 The RMS values of the samples Nos. 1 to 12 prepared in Example 1 were measured.

The RMS value was obtained by measuring the minimum concentration of the sample using a Ratten filter manufactured by Eastman Kodak Company under green light with an aperture scanning area of 1800 μm ² (slit width 10 μm, slit length 180 μm.
Scanning was carried out with a microdensitometer (m), and the density measurement sampling number was shown as 1000 times the standard deviation of the fluctuation of the density value.

The RMS value is shown as a relative value when the RMS value of sample No. 1 is 100. The smaller the RMS value, the better the graininess. The results are shown in Table 5 below.

[0198]

[Table 5]

From the results in Table 5, it can be seen that the method of the present invention hardly deteriorates the graininess of the green photosensitive layer even with a low silver content. Similar effects were observed for the blue and red photosensitive layers.

Example 3 The samples A to F prepared in Example 1 were subjected to wedge exposure using white light, and the color developing solutions a and b of Example 1 and the bleaching solution n were processed by the process step 2. The magenta densities in the unexposed areas of Samples Nos. 13 to 24 produced by the development processing were measured to evaluate the bleaching fog. The results are shown in Table 6.

[0201]

[Table 6]

From the results shown in Table 6, it can be seen that bleaching fog is also reduced in the present invention.

Example 4 In the same manner as in Example 1, except that the color developing agent of the color developing solution b in Example 1 was replaced with the exemplified compounds (31), (33) and (42) of the present invention, the sharpness evaluation was performed. When the graininess was evaluated in the same manner as in Example 2 and the bleaching fog was evaluated in the same manner as in Example 3, the effect of the present invention was recognized.

[0204]

The present invention provides one side on a transparent support,
A silver halide color light-sensitive material having a photographic constituent layer composed of at least one red light-sensitive layer, green light-sensitive layer, blue light-sensitive layer and non-light-sensitive layer is developed with a color developing solution containing a color developing agent. And a specific photographic sensitivity of the silver halide color light-sensitive material is 25 or more and less than 320, and the coating amount of silver in terms of metallic silver in the photographic constituent layer is 3.0 g / m ² 5.0g or more
/ M ² or less and the color developing agent is represented by the general formula (1)
By providing an image forming method for a silver halide color photographic light-sensitive material, the method for forming a color image for a silver halide color photographic light-sensitive material having improved sharpness without deteriorating photographic performance is provided. it can.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical indication G03C 7/42

Claims (3)

[Claims] 1. A silver halide color photograph having on one side on a transparent support a photographic constituent layer each comprising at least one red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-photosensitive layer. In the color image forming method of developing a light-sensitive material with a color developing solution containing a color developing agent to obtain a color image, the specific photographic sensitivity of the silver halide color photographic light-sensitive material is 25 or more and less than 320, and a photographic composition The silver coating amount converted to metallic silver in the layer is 3.0 g / m ² or more and 5.0 g /
An image forming method for a silver halide color photographic light-sensitive material, wherein the color developing agent is m ² or less and the color developing agent is represented by the following general formula (1). [Chemical 1] [In the formula, R ¹ and R ² may be the same or different and each represents an arbitrary substituent. R ³ represents an alkyl group, and R ⁴ represents an alkylene group. R ⁵ represents an alkyl group, an aryl group, or a heterocyclic group linked by carbon atoms. ] 2. At least one of the silver halide emulsions in the light-sensitive layer is spectrally sensitized by adding a substantially water-insoluble photographic spectral sensitizing dye in a solid state without using an organic solvent. The method of forming an image of a silver halide color photographic light-sensitive material according to claim 1. 3. The halogenation according to claim 1, wherein in the image forming method for a silver halide color photographic light-sensitive material, a bleaching step is carried out after the color development processing step, and the bleaching time is within 1 minute. Image forming method for silver color photographic light-sensitive material.