JPH0429238A - Image forming method for silver halide color reversal photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve sharpness and gradation reproducibility by decreasing the iodine content of monodisperse silver halide particles and high-sensitivity layers and lowering the content of a high boiling org. solvent than the content of silver. CONSTITUTION:This photosensitive material is constituted of the plural silver halide emulsion layers which are substantially the same in blue color sensitiveness but are different in sensitivity. The ratio of the iodine in the high-sensitivity silver halide emulsion layers to the total halogen is made smaller by>=0.3mol% than that in the low-sensitivity emulsion layers. At least one of the mondisperse silver halide emulsions are incorporated into at least one of the blue sensitive silver halide emulsion layers and the weight ratio of the high boiling org. solvent in the blue sensitive silver halide emulsion layers to the silver is set<1. In addition, a silver halide solvent is incorporated into a 1st developer. The sharpness and the gradation reproducibility are improved in this way.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for processing a silver halide color reversal photographic light-sensitive material, and more specifically, to a method for processing a silver halide color reversal photographic light-sensitive material having improved sharpness and color development. The present invention relates to an image forming method.

[Background of the invention]

Silver halide color photographic light-sensitive materials are required to have various performances, but recently the demand for high image quality has been increasing.
For example, there is a strong desire to improve sharpness.

As a means for improving sharpness, it is known to suppress the degree of light scattering by reducing the variation in grain size of a silver halide emulsion, for example. It is also known to reduce the amount of couplers and high boiling point organic solvents to suppress light scattering and improve sharpness.

On the other hand, one of the performance requirements for color reversal photosensitive materials is improved gradation reproducibility. In particular, by increasing the maximum density, the gradation of a part of the image is improved,
There is a need to improve the depiction power of a portion of the image when viewed by projecting it with a projector, or to use it as a printed manuscript.

However, in order to increase the maximum density, it is possible to improve the density by increasing the amount of coupler, high boiling point organic solvent, or silver halide contained in the emulsion layer.
This has the drawback of deteriorating sharpness.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide an image forming method using a silver halide color reversal photographic light-sensitive material, which has improved sharpness and gradation reproducibility.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a method for developing a color reversal photographic light-sensitive material having at least two or more blue-sensitive silver halide emulsion layers having different sensitivities. The ratio of iodine to total halogen in the emulsion layer is 0.3 mol% or more smaller than that in the low-speed emulsion layer, and at least one blue-sensitive silver halide emulsion layer contains at least a monodisperse silver halide emulsion. a silver halide color reversal photographic light-sensitive material, the silver halide color reversal photographic light-sensitive material contains one, and the weight ratio of the high boiling point organic solvent to silver in the blue-sensitive silver halide emulsion layer is less than 1, and the first developer contains the silver halide solvent. This was achieved by the image forming method.

The details of the present invention will be explained below.

The present invention is composed of a plurality of silver halide emulsion layers having substantially the same blue sensitivity or different sensitivities. The above-mentioned blue sensitivity is substantially the same.When a general color multilayer photosensitive material has sensitivity to a blue wavelength region among the spectral wavelengths to which it can be exposed, the sensitivity regions are slightly different from each other for a certain wavelength region. The photosensitive layers are considered to be substantially the same even if their spectral sensitivities are slightly different. The same applies to green sensitivity and red sensitivity other than blue sensitivity.

When layers with different sensitivities are composed of two layers, it is preferable that the high-sensitivity silver halide emulsion layer and the low-sensitivity emulsion layer be coated from the far side when viewed from the support, and the composition is composed of three or more layers. In this case, it is also preferable that the silver halide emulsion layers be coated in the order of sensitivity from the farthest side when viewed from the support.

When the color-sensitive layer is composed of two layers, the sensitivity difference between the high-sensitivity silver halide emulsion layer and the low-sensitivity silver halide emulsion layer is determined by a well-known method, taking into account gradation, etc. Although the calculation is good, - for boat fishing, △12ogE (E is the exposure amount) is 0.2~
1.5 is preferable, and 03 to 1.0 is particularly preferable. Δ12ogE is adjusted to an optimum value depending on the grain size of the silver halide emulsion grains, the degree of chemical ripening, and the inhibitor added. Further, the density share of the high-sensitivity silver halide emulsion layer and the low-sensitivity silver halide emulsion layer is preferably in the range of 10 to 90%, and more preferably 25 to 75%, respectively.

Even when the color sensitivity is composed of three or more layers, the optimum value can be determined by the same method.

In the present invention, it is particularly preferable that the blue-sensitive layer has two layers.

In the present invention, the difference in iodine content between an emulsion with a low iodine content and an emulsion with a high iodine content may be at least 0.3 mol %, preferably between 0.5 and 3 mol %.

Further, the iodine content of the emulsion of the silver halide emulsion layer having a low iodine content is preferably 0.5 to 5.7 mol%,
1.5 to 4.5% is more preferred. Further, the silver halide emulsion layer having a high iodine content preferably has a content of 0.8 to 6 mol%, more preferably 2 to 5 mol%.

In the present invention, a monodisperse silver halide emulsion is defined as a silver halide emulsion whose weight is within a grain size range of ±20% around an average grain size of 7, or which is 60% or more of the total silver halide grain weight. It is preferably at least 70%, particularly preferably at least 80%.

Here, the average particle size is the frequency n1 of particles having particle size r1.
The product of "i3" x "11" or the maximum grain size ri
Define.

(3 significant digits, round off the smallest digit.) The grain size here means the diameter in the case of spherical silver halide grains, or the projected image in the case of grains with shapes other than spherical. This is the diameter when converted to a circular image with circumferential area.

The particle size can be obtained, for example, by magnifying the particles 10,000 to 50,000 times using an electron microscope, projecting the particles, and actually measuring the particle diameter or area at the time of projection on the print.

(The number of grains to be measured is indiscriminately 1000 or more.) Particularly preferred highly monodispersed emulsions of the present invention are those with a degree of monodispersity defined by 20 or less, more preferably 15 or less. It is.

Here, the average particle size and particle size standard deviation are determined from rl defined above.

A method for obtaining a monodisperse emulsion is to add a water-soluble silver salt and a water-soluble halide solution to a gelatin solution containing seed particles.
It can be obtained by adding pi under the control of a double jet method. Particularly preferred production methods include JP-A-54-48521 and JP-A-58-49938.
No. 60-122935, No. 59-46640, etc. can be referred to.

The average grain size of the silver halide emulsion of the present invention is 0.05 to 10
The range is preferably 90 μm, more preferably 0.1 to 5.0 μm.

In the present invention, monodisperse/10-genide silver grains having a (111) crystal habit are particularly preferred.

The silver halide grains used in the silver halide emulsion of the present invention may have a uniform silver halide composition distribution, or may be core/shell grains in which the halogen composition differs between the inside of the grain and the surface layer. It is preferable that the silver iodide content on the grain surface is low. Preferably they are core/shell particles.

The silver halide emulsion of the present invention may be used by mixing two or more separately formed silver halide emulsions having different grain sizes or compositions after completion of chemical sensitization.

In the present invention, the monodisperse silver halide emulsion is contained in either or both of the blue-sensitive high-speed layer and the low-speed layer. Preferably, the low-speed layer contains a monodisperse silver halide emulsion having a (111) plane, and when it is contained in the low-speed layer, the surface ratio is 50% or more, preferably 75% or more (Ill ) is preferably included.

Further, in the present invention, it is preferable that monodisperse silver halide grains are used in the low-speed layer, in which case the high-sensitivity layer may be monodisperse silver halide grains, or halogen grains with a wide particle size distribution may be used. It may also be silver oxide particles. Preferably, silver halide grains with a wide grain size distribution are used in the high-sensitivity layer.

In the present invention, it is preferable that the total silver amount is 2.1 g/m2 or more in terms of silver. More preferably 15-2.1g
/ m2.

In such a case, the effect of improving sharpness is especially large, which is preferable.

In the present invention, the weight ratio of the high-boiling organic solvent to silver is the ratio of the weight of silver halide contained per unit area in the blue-sensitive layer converted to silver and the weight of the high-boiling organic solvent.

In the present invention, the weight ratio is less than 1 and includes 0. Preferably, the weight ratio is in the range of 0.75 to 0, particularly preferably 5 to 0.05.

In the present invention, examples of high boiling point organic solvents include phenol derivatives, phthalic acid alkyl esters, phosphoric esters, citric esters, benzoic esters, alkylamides, fatty acid esters, trimenoic esters, etc. that do not react with the oxidized form of the developing agent. Organic solvents at temperatures above 10°C are used. Specifically, an example is U.S. Patent No. 2,322,0
No. 27, No. 2,533,514, No. 2,835,57
No. 9, No. 3,287,134, No. 2,353,262
No. 2,852,383, No. 3,554.755, No. 3.676137, No. 3,676, 142, No. 3,700,454, No. 3.748141, No. 3,
No. 779,765, No. 3,837,863, British Patent No. 958,441, No. 1,222,753, ○LS2
, 538, 889, JP 47-1031, JP 49-90523, JP 50-23823, JP 51-
No. 26037, No. 51-27921, No. 51-279
No. 22, No. 51-26035, No. 51-26036, No. 50-62632, No. 531520, No. 53-
No. 1521, No. 53-15127, No. 54-1199
No. 21, No. 54-119922, No. 55-25057
Examples include, but are not limited to, those described in Japanese Patent Publication No. 55-36869, No. 56-19049, No. 56-81836, and Japanese Patent Publication No. 4829060.

In the present invention, the high boiling point organic solvent is a dye-format coupler.
It may be added to the emulsion layer after being dispersed with a low boiling point organic solvent, or it may be added to the emulsion layer separately from the coupler by dispersing only a high boiling point organic solvent and a low boiling point organic solvent.

In the emulsion layer of a light-sensitive material, a dye is formed by a coupling reaction with an oxidized form of an aromatic primary amine developer (e.g., p-) unilene diamine derivative, aminophenol derivative, etc.) during color development processing. Dye-forming couplers are used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a clast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Also, these dye-forming couplers are 1
It can be either 4-equivalent, in which 4 molecules of silver ions need to be reduced to form a molecular dye, or 2-equivalent, in which only 2 molecules of silver ions need to be reduced. .

Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Compounds that release photographically useful 7-ragments such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. Instead of the DIR coupler, a DIR compound that undergoes a coupling reaction with an oxidized developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include
Intra-molecular nucleophilic reaction at the base circle separated by the coupling reaction, in which the inhibitor is directly bound to the knobling position, and in which the inhibitor is bound to the coupling position via a divalent group,
Included are those in which the inhibitor is bonded so as to be released by an intramolecular electron transfer reaction or the like (referred to as timing DIR couplers and timing DIR compounds). Further, after release of the inhibitor, a diffusible one and a non-diffusible one can be used alone or in combination depending on the purpose.

A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include, for example, U.S. Pat.
No. 5,057, No. 3,265゜506, No. 3,408
, No. 194, No. 3,551.155, No. 3,582゜322, No. 3,725,072, No. 3,891.4
No. 45, West German Patent No. 1,547,868, West German Patent Application No. 2,219,917, West German Patent Application No. 2,261, 361, No. 2,414,006, U.S. Patent No. 1,425,020, Japanese Patent Publication No. 51 No.-10783, JP-A-47-26133
No. 4873147, No. 50-6341, No. 50
-87650, 50-123342, 50-1
No. 30442, No. 51-21827, No. 51-102
No. 636, No. 52-82424, No. 52-11521
No. 9, No. 58-95346, etc.

As magenta dye-forming couplers, known 5-pyrazolone couplers and pyrazolopenzimitazole couplers are used.
Pyrazolotriazole couplers, open-chain anlycetonitrile couplers, indacylon couplers, and the like can be used. Specific examples of magenta coloring couplers that can be used include:
For example, U.S. Patent Nos. 2,600,788 and 2,983,
No. 608, No. 3,062゜653, No. 3,127,2
No. 69, No. 3,311,476, No. 3,419゜39
No. 1, No. 3,519,429, No. 3,558,319
No. 3, 582.

No. 322, No. 3,615,506, No. 3,834,9
No. 08, 3.89].

445, West German Patent No. 1,810,464, West German Patent Application (OL S) No. 2,408,665, West German Patent Application No. 2,417
, No. 945, No. 2.418.959, No. 2,424,
No. 467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 49-74
No. 027, No. 49-74028, No. 49-12953
No. 8, No. 50-60233, No. 50-159336, No. 51-208.26, No. 51-26541, No. 52-42121, No. 52-58922, No. 53-
Examples include those described in No. 55122 and No. 57-35858.

Phenol or naphthol couplers are generally used as cyan dye type couplers.

Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Pat.
, 476.563-1 3,737゜326, 3
, No. 758,308, No. 3,893.044, JP-A-47-37425, No. 50-10135, No. 50-
No. 25228, No. 50112038, No. 50-117
Couplers described in Japanese Patent Application Laid-open No. 422, No. 50-130441, etc., and JP-A No. 58-98731 are preferred.

Dye-forming couplers that do not need to be adsorbed onto the surface of silver halide crystals Colored couplers DIR couplers DIR
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be dispersed using various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. It can be selected as appropriate depending on the situation. For the oil-in-ice emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied.
Dissolve in a high-boiling point organic solvent of 0°C or higher using a low-boiling point and/or water-soluble organic solvent as necessary, and use a surfactant in a hydrophilic binder such as an aqueous gelatin solution to create a stirrer, homogenizer, and colloid. It may be emulsified and dispersed using a dispersion means such as a mill, a flow jet mixer, or an ultrasonic device, and then added to the desired hydrophilic colloid liquid.

A step of removing the low boiling point solvent may be included simultaneously with the dispersion or dispersion.

As a high boiling point solvent for coupler dispersion, the above-mentioned boiling point 15
An organic solvent having a temperature of 0°C or higher is used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene.

Dye-forming couplers, DIR couplers Colored couplers When DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid and sulfonic acid, they are hydrophilic as an alkaline aqueous solution. It can also be incorporated into sex colloids.

Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used.

The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, by adding metal ions using complex salts, these metal elements can be contained inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, they can be reduced inside the particles and/or on the particle surfaces. Can provide sensitizing nuclei.

The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. That is, sulfur sensitization using a sulfur-containing compound capable of reacting with silver ions or active gelatin, selenium sensitization, reduction sensitization using a reducing substance, gold or other noble metal sensitization may be used alone or Can be used in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dyes can be used alone or in combination of two or more. The sensitizing dyes may be used alone or in combination. Along with the sensitizing dye, the emulsion contains a supersensitizer, which is a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye. It's okay.

Anti-capri agents, stabilizers and the like can be added to the silver halide emulsion of the present invention. Gelatin is advantageously used as a binder for the emulsion. The emulsion layer and other hydrophilic colloid layers can be hardened and can contain plasticizers and dispersions (latexes) of water-insoluble or water-soluble synthetic polymers.

Couplers are used in the emulsion layer of color light-sensitive materials.

Furthermore, by coupling with a competing coupler having a color correction effect and an oxidized form of a developing agent, a development accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifogging agent, Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layers may contain dyes that are leached from the light-sensitive material or bleached during the development process.

A matting agent, a lubricant, an image stabilizer, a formalin scavenger-1 ultraviolet absorber, a fluorescent brightener, a surfactant, a development accelerator, or a development retardant can be added to the photosensitive material.

Supports include paper laminated with polyethylene, polyethylene terephthalate film, baryta paper,
Cellulose triacetate etc. can be used.

In order to obtain a dye image using the light-sensitive material of the present invention, a commonly known color reversal process can be performed after exposure. That is, after the silver halide exposed in the first development is subjected to monochrome development processing, the unexposed silver halide is fogged in a light fog or a fogging bath, and then a dye image is obtained by color development. .

The processing of the color reversal light-sensitive material that is an embodiment of the present invention usually involves the following steps: black and white development (first development) - stop, one water wash, one reversal, one water wash, one color development, one stop, one water wash, one adjustment bath, one water wash, one bleach, and one constant water wash. The steps of wearing, washing, stabilizing, and drying are used. This step may further include a prebath, a predural bath, a neutralization bath, and the like. Further, water washing after stopping, reversing, color development, conditioning bath or bleaching may be omitted.

Reversal may be performed in a fog bath or by re-exposure. It is also possible to omit a fogging agent by adding it to the color developing bath.

Furthermore, the conditioning bath can also be omitted.

Further, the bleaching-washing and fixing may be performed using only a bleach-fixing bath.

A known developing agent can be used for the first developer used in the present invention. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. l-7enyl-3-pyrazolidone), aminophenols (e.g. N-methyl p-aminophenol) are used.
, l-phenyl-3-pyrazolines, ascorbic acid and 1.2, 3. as described in U.S. Pat. No. 4,067.872.
A 4-tetrahydroquinoline ring, an intrene ring, or a condensed heterocyclic compound can be used alone or in combination.

The black and white developer used in the present invention may also include preservatives (e.g. sulfites, bisulfites, etc.), buffers (e.g. carbonates, boric acid, borates, alkanolamines), alkaline agents (e.g. oxides, carbonates), solubilizing agents (e.g. polyethylene glycols, esters thereof)
, pH adjusters (for example, organic acids such as acetic acid), sensitizers (for example, quaternary ammonium salts), development accelerators, surfactants, toning agents, antifoaming agents, hardeners, viscosity imparting agents, etc. It is possible to contain the following.

It is necessary to include a compound which acts as a silver halide solvent in the first developing solution used in the present invention, and the above-mentioned sulfite added as a preservative usually plays this role. The sulfite and other usable silver halide solvents include KSCN.

Na5CN, LS03, Na25o3, K2S2O5
, Na, 5.0. , K, S, 03, and Na2S2O3.

If the amount of these silver halide solvents used is too small, the progress of development will be slowed down, and if it is too large, the silver halide emulsion will fog, so there is a preferable amount to use, but determining the amount is difficult. This can be easily done by a person skilled in the art.

For example, when using 5CN-, o, o per developer IQ
os~0.02 mol, especially 0.02 mol. It is preferable that the amount of O is 1 to 0.015 mol, and when S○3'- is used, it is 0.01 to 0.015 mol.
It is preferably 0.05 to 1 mol, especially 0.1 to 0.5 mol.

Furthermore, antifoggants (for example, halides such as potassium bromide and sodium bromide, benzimidazoles, benzotriazoles, benzothiazonyls, tetrazoles, thiazoles, etc.), chelating agents (for example, ethylenediaminetetraacetic acid, These alkali metal salts, polyphosphates, nitriloacetates) can be contained.

The pH value of the developer thus adjusted is selected to be sufficient to provide the desired density and contrast, and is preferably in the range of about 8.5 to about 11.5. The present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Comparative sample I of a multilayer color light-sensitive material was prepared by sequentially coating each layer having the following composition on a subbed cellulose triacetate film support from the support side. The coating amount of each component is shown in g/m2. However, for silver halide, the coating amount is expressed in terms of silver.

1st layer (antihalation layer) Black colloidal silver 0.24 Ultraviolet absorber U -10,14 Ultraviolet absorber U -20,072 Ultraviolet absorber U -30,072 Ultraviolet absorber U -40,072 High boiling point solvent 0 -1 0.31 High boiling point solvent 0-2 0.098 Poly-N-hinylpyrrolidone 0.15 Seratin
2.02 2nd layer (intermediate layer) High boiling point solvent ○-30,011 Gelatin 1.17 3rd layer (
Low-sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes S-1 and S-2 (silver iodide 3.0 mol%, 0.57 μm) 0.05
6 Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes S-1 and S-2 (silver iodide 3.0 mol%, 0.27 μm) 0.50
4 Coupler C-10,37 High boiling point solvent 0-2 0.093 PolyN
Vinylpyrrolidone 0.074 gelatin
1.35 Fourth layer (high sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes S-1 and S-2 (silver iodide 3.0 mol%, 0.57 μm)0 .71 Coupler C-10,85 High boiling point solvent 0-2 0.21 PolyN vinylpyrrolidone 0.093 Gelatin
1.56 5th layer (intermediate layer) Color mixing prevention agent p, s -10,20 High boiling point solvent 0-3 0.25 Matting agent M A -10,0091 Gelatin l・35 6th layer (
Low-sensitivity green-sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dyes S-3 and S-4 (silver iodide 3.0 mol%, 0.60 μm) 0.05
6 Silver iodobromide emulsion spectrally sensitized with green sensitizing dyes S-3 and S-4 (silver iodide 3.0 mol%, 0.27 μm) 0.51 Coupler M -10, 31 Coupler M -20 ,076 High boiling point solvent 0-3 0.059 PolyN
Vinylpyrrolidone 0.074 gelatin
1.29 7th layer (high sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dyes S-3 and S-4 (silver iodide 3.0 mol%, 0.60 μm)0 .83 Silver iodobromide emulsion spectrally sensitized with green sensitizing dyes S-3 and S-4 (silver iodide 3.0 mol%, 0.27 pm)0.
092 Coupler M -10,80 Coupler M -20,19 Color mixing inhibitor A S -10,055 High boiling point solvent o -30,16 PolyN vinylpyrrolidone 0.12 Gelatin 1.91 8th layer (intermediate layer) Gelatin 0 ,90 9th layer (
yellow filter layer) Yellow colloidal silver 0.11 Color mixing inhibitor A S-10,068 High boiling point solvent o -30,085 Matting agent MA -10,012 Gelatin 0.68 10th layer (low sensitivity blue sensitive layer) Blue enhancement Silver iodobromide emulsion spectrally sensitized with sensitive dyes S-5 and S-6 (silver iodide 3.0 mol%, 0.42 μm) 0.60 Coupler Y -10,86 Image stabilizer G-10, 012 High boiling point solvent 0-3 0.86 PolyN
-Vinylpyrrolidone 0.078 compound F
-10,020 Compound F -20,040 Gelatin 1.50 11th layer (high sensitivity blue sensitive layer) Silver iodobromide emulsion (silver iodide) spectrally sensitized with blue sensitizing dyes S-5 and S-6 3.0 mol%, 0.85 μm) 0.79 Coupler Y -11,24 Image stabilizer G-IO,017 High boiling point solvent Q -31,24 Poly-N-vinylpyrrolidone 0.10 Compound F-1 Compound F-2 Gelatin 12th layer (protective layer-1) Non-photosensitive fine grain silver iodobromide 0.08 μm) Ultraviolet absorber U Ultraviolet absorber U- Ultraviolet absorber U- Ultraviolet absorber U Ultraviolet absorber U Ultraviolet absorber U High boiling point solvent 0-1 High boiling point solvent 0-2 Compound F-1 Compound F-2 Gelatin 13th layer (protective layer-2) Slip agent WAX-1 (Silver iodide 1.0 0.039 0.077 1 .73 mole%.

0.075 0.048 0.024 0.024 0.024 0.064 0.13 0.13 0.13 0.075 0.15 1.2 0.041 M) Agent M A -20,0090 Matsu Agent MA-30,051 Surfactant S U-10,0036 Seratin
0.55 (Note: used in each layer,
The average molecular weight of poly-N-vinylpyrrolidone is 3.
50,000) In addition to the above composition, this sample also contained gelatin hardeners H-1, H-2, H-3, water-soluble dyes Al-1, Al-2, Al-3, Antifungal agent DI-1, stabilizer 5T-1, and anti-rust agent AP-4 were added as necessary.

The silver halide emulsion used in each photosensitive layer was JP-A-59-1
It was prepared with reference to the method of Example 1 of No. 78447.

All were monodispersed emulsions with a distribution width of 20% or less.

After desalting and washing with water, each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid, and ammonium thiocyanate. , 7-tetrazaindene, l-phenyl-5-mercaptotetrazole were added.

S ■ ShiQ A Idal silica particles (average particle size 3.5 μm) A Polymethyl methacrylate particles (average particle size 3.017 m) A ((:: : m : n = 30:30:40
)■ caHs(t) caHs(t) C4H9(t) CaHs(t) H3 CQ.

ctHs(t)
H2(CF2CF2)3H[(CH2 CH5O2CH2)3CCH2SO2(CH2)2]
2N(CH2)2SO3K(CH2 CH3O2CH2)20 ■ ■ ■ ■ ■ T l F The silver halide emulsions in the 10th and 11th layers of sample 1 were replaced with those having the composition shown in Table 1, and a high boiling point organic solvent was used. Samples 2 to 11 were prepared in the same manner except that the weight ratio of silver to silver was changed to that shown in Table 1.

Each sample obtained was exposed to white light through a sensimetry wedge. In addition, in order to evaluate sharpness, each sample was exposed to a square wave chart. Further play/
To evaluate the layer resistance, the following (
1) A scratch test and (2) a bending test were conducted.

(1) Scratch test Fix the sample on a steel plate with the photosensitive layer side up, use a diamond needle with a tip diameter of 0.01 mm, and place the diamond needle on the sample without applying a load of 1°. 1. Oc
It was pressed and moved at a speed of m/sec.

(2) Bending test The radius of curvature of the sample is 3 mm along the direction of change in exposure amount.

Fold with the photosensitive layer inside at a bending angle of 20°,
It was left still for a second.

The sample thus obtained was subjected to the following development treatment.

Processing process Processing time Processing temperature First development
6 minutes 38°C water washing
21ltt inversion 2
// // Color development 6/
lll adjustment 2 tt
tt bleach 5
// // established
4tt
llWash 4tt
tt stable
1 tt Ordinary humidity drying The composition of the processing solution used in the above processing step is as follows.First developer Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone
Monosulfonate 30g Sodium carbonate (monohydrate)
30g 1-phenyl-4-methyl-4-hydroxymethyl-3
Pyrazolidone 2g Potassium bromide 2.5g Potassium thionanate 1.2g Potassium iodide (0,
1% solution) Add 2 ml of water (pH 9,60)
1000m4 inversion Liquid nitrilotrimethylenephosphonic acid g g 0.1g g 5mQ 000mC Hexasodium salt Stannous chloride (dihydrate) p-Aminephenol Sodium hydroxide Add glacial acetic acid water and color developer Tetrapolyphosphoric acid). Lium 3g Sodium sulfite 7g Sodium phosphate (dihydrate) 36° Potassium bromide 1g Potassium iodide (0.1% solution) 90mC Sodium hydroxide 3g Notoranic acid
1.5g N-ethyl-N-β-
[meth]/sulfonamidoethyl 3-methyl-4-aminoaniline sulfate 5.75) (pH 11g 2.2-ethylenedithiogetanol 1g water added (pH 11.70) 10100O
! Adjustment: Add liquid sodium sulfite, ethylenediaminetetraacetic acid, nathioglycerin, glacial acetic acid water (pH 6,15). Bleach: Add liquid ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid, fi-iron (dihydrate), and ammonium bromide water (pH 5,65). ) Fixing solution Add ammonium thiosulfate sodium sulfite Sodium bisulfite water (pH 6,60) Fixing solution Formalin (37% by weight) Amylium 2g (dihydrate) g 0.4m12 mQ 1000mff Thorium (dihydrate) g ( I [[) Ammonium 20g 00g 000mQ 0g g g 1000m12 mff Konidax (manufactured by Konica Corporation) 5m12 Add water 1000m12 For the developed sample, check the density meter 310 manufactured by χ-RITE
The density was measured using a status filter with a mold, and the maximum density measured by blue light was determined and shown in Table 2.

In addition, using a microdentometer PDM-5 (manufactured by Konica) for the square wave chart, the frequency 1 was measured using green light.
The MTF value at 0 lines/mm was measured according to a conventional method, and the relative MTF value with sample 1 as 100% is shown in Table 2. The larger the MTF value, the better the mixture at a ratio of 2:1.

The silver halide grains in the 10th layer of Samples 5 to 11 were placed on top.

As is clear from the results in Table 2, the iodine content of the monodisperse silver halide grains and high-sensitivity layer of the present invention is reduced, And by using less organic solvent than silver,
Shows high maximum sensitivity while maintaining high sharpness.

In addition, each sample was cut into 135-size pieces, loaded into a camera, photographed, and then subjected to the above-mentioned development process, and visually judged the color reproducibility of each sample and the gradation reproducibility of a portion of the shadow.
Again, samples 6 to 11 of the present invention showed superior results compared to the comparative samples.

Claims (1)

[Claims] In a method for developing a color reversal photographic light-sensitive material having at least two or more blue-sensitive silver halide emulsion layers having different sensitivities, iodine in a high-sensitivity silver halide emulsion layer among the emulsion layers is provided. the ratio of halogen to total halogen is 0.3% or more smaller than that in the low-speed emulsion layer, and at least one blue-sensitive silver halide emulsion layer contains at least one monodisperse silver halide emulsion, and A silver halide color reversal photographic light-sensitive material, characterized in that the weight ratio of the high boiling point organic solvent to silver in the blue-sensitive silver halide emulsion layer is less than 1, and the first developer contains a silver halide solvent. Image forming method.