JPH07333785A - Silver halide photographic material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic material which provides enhanced sharpness and is excellent in whiteness and resistance to curling. CONSTITUTION:This silver halide photographic material, which consists of at least one silver halide emulsion layer and at least one non-photosensitive layer on one side of a reflective carrier comprising resin cover layers provided on both sides of base paper, contains between the support and the silver halide emulsion layer at least two hydrophilic colloid layers each containing white pigment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having improved sharpness, excellent whiteness and curl resistance.

[0002]

2. Description of the Related Art In recent years, demands for high-quality image quality have been increasing, and researches for improving the sharpness of color prints have been conducted conventionally. Improvements have been made in dyestuffs to prevent irradiation. For example, JP-A-50-145125, 50-147712, 61-148448, and 6
1-151649, 62-164043, 62-283336, Research Disclosure RD-17643 (22 December 1978), RD
-18716 (November, 1979, p. 647), etc., describes improvement of dyes. Further, for the same purpose, a method of providing an antihalation layer on a silver halide photographic light-sensitive material is known. For example, U.S. Patent Nos. 2,326,057, 2,882,156, and 2,
839,401, 3,706,563, JP-A-55-33172, 62
-32448, etc.

It is also described in JP-A-63-286849 that the optical reflection density when a colorant such as the diffusible dye or the antihalation layer is used is set to a certain level or more. However, when the optical reflection density is increased, the sharpness is improved and the sensitivity is remarkably lowered, and it is difficult to improve the sharpness while maintaining the practically sufficient sensitivity only by such means. Also, it is necessary to use a large amount of dye in order to increase the reflection density, but if a large amount of dye is used, the gradation will be softened, and the dye used after processing will reduce the white background. This is one of the reasons why a high reflection density cannot be practically applied. The method of providing the antihalation layer is not preferable because it causes fog during storage with time and deteriorates the image quality.

The use of the sensitizing dyes described in JP-A Nos. 4-204644 and 4-365034 is said to improve sharpness, but this is not preferable because it causes a decrease in sensitivity.

On the other hand, studies have also been conducted from the viewpoint of the support. A polyolefin coating layer is provided on both sides of a substrate made of paper in order to make it difficult for the processing liquid to penetrate into the support during the developing and fixing process. The polyolefin coating layer of such a support is mixed with an inorganic white pigment such as titanium dioxide for the purpose of improving the hiding power or resolution, but such a pigment has poor dispersibility in the resin, and The volatile component contained in the pigment causes problems such as foaming in the melt extrusion step to cause film cracking of the coating layer. Therefore, the pigment content in the coating layer cannot be increased to a sufficient level to improve the hiding power or resolution. Generally speaking, when titanium dioxide is used, it is difficult to mix it in a large amount of about 20% by weight or more. Therefore, it cannot be said that the photographic printing paper obtained by using such a photographic printing paper support is sufficiently satisfactory in terms of sharpness.

Patents for forming a layer containing an inorganic white pigment on a paper support are disclosed in JP-A-58-60738 and 59-177541.
It is described in Japanese Patent Laid-Open No. 3-136035. Although it was confirmed that the sharpness was improved, yellowing occurred, and it was found that the whiteness was lowered to a level that cannot be ignored as a product. In addition, the curl resistance is inferior at a humidity of 40 to 70% RH, and when the print is placed under these conditions, the flatness cannot be maintained and the product quality is deteriorated.

[0007]

In order to solve the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material having improved sharpness and excellent whiteness and curl resistance. .

[0008]

The above object of the present invention can be achieved by the following constitution.

(1) A silver halide comprising at least one silver halide emulsion layer and at least one non-photosensitive layer on one side of a reflection support having resin coating layers on both sides of a base paper. A silver halide photographic light-sensitive material, comprising a hydrophilic colloid layer containing at least two white pigments between the support and the silver halide emulsion layer.

(2) The silver halide photographic light-sensitive material according to the item (1), wherein the coating amount of the white pigment contained in the layer far from the support is larger than the coating amount of the white pigment contained in the layer close to the support. material.

(3) The silver halide according to the above (1) or (2), wherein the layer far from the support contains anatase type titanium oxide and the layer close to the support contains rutile type titanium oxide. Photographic material.

(4) The silver halide photograph as described in (1), (2) or (3) above, which has a hydrophilic colloid layer containing the white pigment or titanium oxide applied in an amount of 1.5 g / m ² or more. Photosensitive material.

(5) The total coating amount of the water-soluble binder contained in the hydrophilic colloid layer coated between the support and the silver halide emulsion layer closest to the support is 0.2 g.
/ M ² or more and 3.0 g / m ² or less, the silver halide photographic light-sensitive material according to the above (1), (2) or (3).

The present invention will be described in more detail below.

The white pigment used in the hydrophilic colloid layer containing the white pigment according to the present invention is, for example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate,
Barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used, but titanium dioxide is preferable for various reasons. The white pigment can be applied as a hydrophilic colloid layer containing a white pigment by dispersing it in a water-soluble binder of a hydrophilic colloid such as gelatin that allows the treatment liquid to penetrate.

The coating amount of the white pigment is 0.5 g / m ^{2 to} 20 g / m ²
Is preferable, and more preferably 1.5 g / m ^{2 to} 8 g / m
A range of ² is preferred.

The hydrophilic colloid layer containing the white pigment according to the present invention can be provided between the support and the silver halide emulsion layer closest to the support. Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment-containing hydrophilic colloid layer, an undercoat layer on the support, if necessary,
Alternatively, a non-photosensitive hydrophilic colloid layer such as an intermediate layer can be provided at any position. In the present invention, the hydrophilic colloid layer containing titanium dioxide is composed of at least two layers, and the layer farthest from the support contains anatase type titanium dioxide and the layer closest to the support contains rutile type titanium dioxide. desirable. The hydrophilic colloid layer containing titanium dioxide is composed of at least two layers, and the coating amount of the white pigment contained in the layer farthest from the support is the coating amount of the white pigment contained in the layer closest to the support. More is desirable.

[0018] Preferably the gelatin in the water-soluble binder contained a white pigment-containing hydrophilic colloid layer in the present ^{invention, 0.2g / m 2 ~3.0g / m} 2 is preferable in terms of white as the coating amount.

The white pigment layer according to the present invention preferably has a porosity of 5 to 30% by weight based on the hydrophilic colloid layer. The porosity is obtained from the specific gravity, the film thickness and the like.

To the hydrophilic colloid layer containing the white pigment according to the present invention, in addition to the white pigment, a coloring agent such as yellow, gray, blue, and black colloidal silver, an inorganic colored pigment, an organic colored pigment, and a dye is added. You can do it.

A colorant-containing hydrophilic colloid layer can be coated between the hydrophilic colloid layer containing the white pigment according to the present invention and the support. As the colorant, various known filter dyes can be used in addition to yellow, gray, blue, and black colloidal silver. As such a light-absorbing substance, it is possible to use a substance that absorbs only light in the entire visible spectrum region, or a substance that selectively absorbs light in a certain part of the region as necessary. You can choose. The transmittance of the colorant-containing hydrophilic colloid layer is preferably 50% or less, particularly preferably 30% or less.

The halogen composition of the silver halide grains according to the present invention is the same as that of all the silver halides constituting the silver halide grains.
95% or more of silver chloride and silver chlorobromide which is substantially free of silver iodide must be used. The preferred halogen composition of the silver halide grains is silver chloride in an amount of 97 mol% or more, and more preferably 98 to 99.99 mol% of the total silver halide constituting the silver halide.

The inclusion of grains having a localized silver bromide phase in the vicinity of the surface of silver halide grains as described in JP-A-5-45779 further improves the pressure resistance when wet. For the silver bromide content of the localized phase having a high silver bromide content, X-ray diffraction method (for example, described in "Chemical Society of Japan, New Experimental Chemistry Lecture 6, Structural Analysis" Maruzen) is used. Can be analyzed.

Heavy metal ions can be contained in the silver halide emulsion according to the present invention. Heavy metal ions used include iron, iridium, platinum, palladium,
Examples include Group 8-10 metals such as nickel, rhodium, osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and lead, rhenium, molybdenum, tungsten, and chromium ions. . Of these, transition metal ions of iron, iridium, platinum, ruthenium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of salt or complex salt.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. Also,
U.S. Pat.Nos. 4,183,756 and 4,225,666, JP-A-55-26589
Issue, Japanese Patent Publication No. 55-42737 and The Journal of Photographic Science (J.Photogr.Sci.) 21, 39
(1973) etc., the octahedron,
Particles having a tetradecahedral shape, a dodecahedron shape, or the like can be prepared and used. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape or a mixture of grains having various shapes.

The grain size of the silver halide grain according to the present invention is not particularly limited, but considering other photographic performance such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm, more preferably 0.2. The range is to 1.0 μm. The particle diameter can be measured by various methods generally used in the technical field. A typical method is Loveland's “Particle Size Analysis Method” (ASTM Symposium on Light Microscopy, 94-122).
Page, (1955)) or "Theory of Photographic Process, 3rd Edition".
(Mies and James, co-authored, Chapter 2, published by Macmillan, (1966)).

This particle size can be measured using the projected area of the particle or a diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but the one obtained by the simultaneous mixing method. Is preferred. As one form of the simultaneous mixing method, the pAg controlled double jet method described in JP-A-54-48521 may be used. If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added and used during the formation of silver halide grains or after the completion of grain formation.

The amount of silver coated on the silver halide color photographic light-sensitive material used in the present invention is 0.9 g / m because of its suitability for rapid processing.
² or less is desirable, and preferably 0.7 g / m ² or less.

For the silver halide emulsion according to the present invention, a sensitization method using a sulfur compound, a sensitization method using a gold compound, and a sensitization method using both a sulfur compound and a gold compound can be used.

Examples of the sulfur sensitizer applied to the silver halide emulsion according to the present invention include thiosulfate, allylthiocarbamidourea, allylisothiacyanate, cystine, p-toluenethiosulfonic acid, rhodanine and inorganic sulfur. Can be mentioned.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes other than chloroauric acid, gold sulfide and the like and the above-mentioned gold compounds can be preferably used.

In particular, it is desirable to use a gold sensitizer and a sulfur sensitizer together from the viewpoint of pressure resistance during drying.

The silver halide emulsion according to the present invention is intended to prevent fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fog that occurs during development. Antifoggant known in
Stabilizers can be used. Examples of compounds that can be used for such purpose include compounds represented by the general formula (II) described in JP-A 2-146036, page 7, lower column, and specific examples thereof include: 8 of the publication
(IIa-1) to (IIa-8) and (IIb-1) described on page
~ (IIb-7) compounds and 1- (3-methoxyphenyl)
Examples thereof include compounds such as -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose.

The support used in the present invention is a paper base having a resin layer on both sides thereof, and the resin layer on the side coated with the silver halide emulsion layer contains a white pigment. It is a paper support.

The raw paper used in the paper support of the present invention can be selected from the raw materials generally used for photographic printing paper. Examples thereof include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various raw materials for laminated paper. Generally, natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, etc. can be widely applied. Any type of paper such as neutral paper and acid paper may be used.

The thickness of the paper is preferably 40 μm to 250 μm.

Further, the support may be blended with additives such as sizing agents, fixing agents, tension enhancers, densities, antistatic agents, dyes and antifoggants, which are generally used in papermaking, Further, a surface sizing agent, a surface tension agent, an antistatic agent, or the like may be appropriately applied to the surface.

As a method of applying a resin coating layer on the support used in the present invention, a method of laminating a polyolefin resin or a polyethylene terephthalate resin is known.

The olefin resin mainly used for the laminate can be selected from ethylene, α-olefins and a mixture of at least two kinds thereof. Among them, the widely used polyolefin resin is low density polyethylene, high density polyethylene or a mixture thereof.

Generally, a resin laminate can be formed by melt-extruding a resin composition on a support and coating it. In order to carry out this melt extrusion coating method, usually, a resin composition is melt extrusion coated in a form of a single layer or a plurality of layers from a slit die of an extruder on a running support. Usually, the melt extrusion temperature is preferably 200 to 250 ° C.

The thickness of the resin coating layer is not particularly limited and is usually 15 to 60 μm.

Examples of the white pigment used in the resin coating layer of the support used in the present invention include rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, and the like.
Barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used, but titanium dioxide is particularly preferable.

Titanium dioxide may or may not be surface-treated with aluminum hydroxide, alcohol, a surfactant or the like. These white pigments are normally contained in an amount of 16% by weight or less, preferably 13% by weight or less, more preferably 10% by weight or less, based on the resin of the resin coating layer on the side of the reflective support on which the photographic emulsion is coated. Most preferred is 7% by weight or less.

The silver halide color photographic light-sensitive material according to the present invention comprises a layer containing a silver halide emulsion spectrally sensitized in a specific region in the wavelength range of 400 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. Have. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes. Useful sensitizing dyes include cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

As the coupler used in the silver halide color photographic light-sensitive material according to the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by a coupling reaction with an oxidant of a color developing agent is used. Any compound that can be formed can be used, but as a typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm. , Wavelength range 600-750nm
The one known as a cyan coupler having a maximum spectral absorption wavelength is typical.

As the yellow coupler, various acylacetanilide type couplers can be used.

As the magenta dye-forming coupler, a 5-pyrazolone type coupler, a pyrazolone benzimidazole type coupler, a pyrazoloazole type coupler, an open chain acylacetonitrile type coupler and the like can be used.

As the cyan dye forming coupler, naphthol type couplers, phenol type couplers, imidazole type couplers and the like can be used.

The yellow coupler which can be preferably used in the silver halide color photographic light-sensitive material according to the present invention is described in JP-A-4-114154, page 8, general formula (Y-
The couplers represented by I) can be mentioned. Specific compounds include those described as YC-1 to YC-9 on pages 9 to 11 of the same publication. Among them, YC-8 and YC-9 described on page 11 of the same publication are preferable because they can reproduce yellow of a preferable color tone, but the present invention is not limited thereto.

As the magenta coupler which can be preferably used in the silver halide color photographic light-sensitive material according to the present invention, a magenta coupler described in JP-A-4-114154, page 12, can be used.
Examples thereof include couplers represented by I) and (M-II). Specific compounds are described in MC-1 to
Mention may be made of those described as MC-11. Among them, the couplers represented by formula (M-I) are particularly preferable for enhancing the effect of the present invention, and specific compounds MC-8 to MC-1 described on pages 15 to 16 of the same publication.
You can list the ones listed as 1,
The present invention is not limited to this.

A cyan coupler which can be preferably used in the silver halide color photographic light-sensitive material according to the present invention is represented by the general formula (C-C) described on page 17 of JP-A-4-114154.
Examples thereof include couplers represented by I) and (C-II). Specific compounds are described in CC-1 to 18-18 of the publication.
The compounds described as CC-14 can be mentioned, but the present invention is not limited thereto.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually used in a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high boiling point organic solvent that can be used for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic-solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. Examples of the water-insoluble organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-1 described in JP-A-4-114154, page 33)
Compounds such as the compound (A′-1) described in 1) and page 35 of the same publication can be used. In addition to this, U.S. Pat.
The fluorescent dye-releasing compound described in 4,187 can also be used.

Gelatin is used as a binder in the silver halide color photographic light-sensitive material according to the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, Hydrophilic colloids such as sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymeric substances such as homopolymers or copolymers can also be used in combination with gelatin.

The gelatin used in the silver halide color photographic light-sensitive material of the present invention may be lime-processed gelatin or acid-processed gelatin, and may be beef bone, cowhide, pig skin or the like. Gelatin produced as a raw material may be used, but lime-processed gelatin made from cow bone or pig skin is preferable.

In the present invention, the photosensitive silver halide from the silver halide emulsion layer closest to the support on the side coated with the silver halide emulsion layer to the hydrophilic colloid layer farthest from the support. From the viewpoint of suitability for rapid processing and sensitivity, the total amount of gelatin contained in the emulsion layer and the non-photosensitive hydrophilic colloid layer is preferably 7.5 g or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material of the present invention.

In the photographic emulsion layer and other hydrophilic colloid layers of the silver halide color photographic light-sensitive material according to the present invention, a hardener which crosslinks binder (or protective colloid) molecules to enhance the film strength is used alone or in combination. By doing so, the dura is cured.

In addition to the above compounds, various photographic additives can be added to the silver halide color photographic light-sensitive material of the present invention.

As such examples, for example, ultraviolet absorbers (eg benzophenone compounds, benzotriazole compounds etc.), development accelerators (eg 1-aryl-3-pyrazolidone compounds etc.), water-soluble anti-irradiation dyes. (For example, azo compound, styryl compound, oxonol compound, etc.), film physical property improving agent (liquid paraffin, polyalkylene glycol, etc.), color turbidity preventing agent (diffusion-resistant hydroquinone compound, etc.), color image stabilizer (for example, Hydroquinone derivatives, gallic acid derivatives, etc.), water-soluble or oil-soluble optical brighteners, and ground color tone adjusting agents.

In addition to these, competitive couplers, fogging agents, development inhibitor releasing couplers (so-called DIRs)
A coupler), a development inhibitor releasing compound and the like can be added.

In the silver halide color photographic light-sensitive material according to the present invention, when the silver halide emulsion layer and the hydrophilic colloid layer used in the present invention are coated on the support used in the present invention, the coating property is improved. A thickening agent may be used for the purpose. As a coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are useful.

To form a photographic image using the silver halide color photographic light-sensitive material of the present invention, the image recorded on the negative is optically formed on the silver halide photographic light-sensitive material to be printed. You can image it and bake it,
After converting the image into digital information, CRT the image.
An image may be formed on a (cathode ray tube), and this image may be formed on a silver halide photographic light-sensitive material to be printed and printed, or scanning is performed by changing the intensity of laser light based on digital information. You may bake it.

The silver halide color photographic light-sensitive material according to the present invention can form an image by performing color development processing known in the art.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds may be mentioned as examples of these compounds.

(CD-1) N, N-diethyl-p-phenylenediamine (CD-2) 2-amino-5-diethylaminotoluene (CD-3) 2-amino-5- (N-ethyl-N-lauryl amino)
Toluene (CD-4) 4-amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline (CD-5) 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl ) Amino) aniline (CD-6) 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl] -aniline (CD-7) N- (2-amino-5-diethylamino Phenylethyl) methanesulfonamide (CD-8) N, N-dimethyl-p-phenylenediamine (CD-9) 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline (CD-10) 4- Amino-3-methyl-N-ethyl-N- (β-ethoxyethyl) aniline (CD-11) 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline The color developing agent is Usually 1 x 10 ^-2 per liter of developer
It is used in the range of from 2 × 10 ^-1 mol, and from the viewpoint of rapid processing, it is preferably used in the range of from 1.5 × 10 ^-2 to 2 × 10 ^-1 mol per liter of the color developing solution. The color developing agent may be used alone or in combination with other known p-phenylenediamine derivatives.

The color developer according to the present invention may contain the following developer components in addition to the above components. As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, silicates, etc. may be used alone or in combination to prevent precipitation. , P
It can be used in combination within a range that maintains the H stabilizing effect. Further, disodium hydrogen phosphate, for the purpose of preparation or for the purpose of increasing ionic strength,
Various salts such as dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate and borate can be used.

If necessary, inorganic and organic antifoggants can be added. For the purpose of suppressing development, halide salt ions are often used,
To finish the development in a very short time, chloride ions are mainly used, and potassium chloride, sodium chloride, etc. are used. The amount of chloride ion is approximately 3.0 × 10 ^-2 mol or more, preferably 4.0 × 10 ^-2 , per liter of color developing solution.
It is about 5.0 × 10 ^-1 mol. Bromide ions can be used within a range that does not impair the effects of the present invention, but have a large effect of suppressing development, and are approximately 1.0 × 10 ⁻³ mol or less, preferably 5.0 × 10 ⁻⁴ mol, per liter of color developing solution. The following is desirable.

Furthermore, if necessary, a development accelerator can be used. As the development accelerator, US Pat.
648,604, 3,671,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. patents 2,533,990
No. 2,531,832, No. 2,950,970, No. 2,577,127 and polyethylene glycol and its derivatives described in JP-B-44-9504, nonionic compounds such as polythioethers,
Organic solvents and organic amines described in JP-B-44-9509, ethanolamine, ethylenediamine, diethanolamine,
Triethanolamine and the like are included. Also, US Patent 2,
Phenethyl alcohol and others described in 304,925, acetylene glycol, methyl ethyl ketone,
Examples thereof include cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like.

Further, in the color developing solution, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other compounds described in JP-B Nos. 47-33378 and 44-9509. Can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent may be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol sulfate, phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N,
N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually 0.01 to 1.0 g per liter of the developing solution.

Each component of the color developing solution can be prepared by sequentially adding and stirring to a fixed amount of water. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Further, more generally, a color developing solution is prepared by adding a plurality of components, each of which can coexist stably, in a concentrated aqueous solution or in a small container prepared in advance in a solid state into water and stirring. You can also

In processing the silver halide color photographic light-sensitive material of the present invention, the color developing solution is used at an arbitrary pH.
Although it can be used in the range, it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0, from the viewpoint of rapid processing.

The processing temperature for color development according to the present invention is 15 ° C.
As described above, the temperature is preferably 45 ° C or lower, and particularly preferably 20 ° C or higher and 45 ° C or lower.

The color development time is conventionally about 3 minutes and 30 seconds, but in the present invention, it is within 1 minute. Further, it is preferable to perform the treatment within 50 seconds.

When the silver halide photographic light-sensitive material according to the present invention is subjected to a running process while continuously replenishing the color developing solution, the overflow of the color developing solution is reduced,
In order to reduce environmental damage due to waste liquid, the replenishing amount of the color developing solution is preferably 20 to 150 ml per 1 m ² of the light-sensitive material. Further more preferably the waste by substantially overflow replenishment amount that does not occur, 20 per light-sensitive material 1 m ² as the specific replenishing amount
More preferably, it is 60 ml. Under such conditions, the performance of the silver halide photographic light-sensitive material is likely to change, and the silver halide photographic light-sensitive material according to the present invention can be particularly advantageously used under such conditions.

The silver halide photographic light-sensitive material of the present invention is bleached and fixed after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a washing process is performed. Further, as a substitute for the water washing treatment, a stabilizing treatment may be performed. As a development processing apparatus used for the development processing of the silver halide photographic light-sensitive material of the present invention, even if it is a roller transport type that conveys the light-sensitive material sandwiched between rollers arranged in a processing tank,
The endless belt method may be used in which the photosensitive material is fixed to the belt and conveyed, but a method of forming a processing tank in a slit shape and supplying the processing liquid to the processing tank and conveying the photosensitive material is also used. A spray method for atomizing, a web method by contact with a carrier impregnated with a treatment liquid, a method with a viscous treatment liquid, and the like can also be used.

[0083]

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

Example 1 A paper support was prepared by laminating high density polyethylene on both sides of a paper pulp weighing 180 g / m ² . However, a reflective support was prepared by laminating molten polyethylene containing 13% by weight of surface-treated anatase type titanium oxide dispersed on the side on which the emulsion layer was coated. Each layer having the following constitution was coated on this reflective support to prepare a silver halide photographic light-sensitive material. The coating liquid was prepared as follows.

First Layer Coating Liquid Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34 g, dye image stabilizer 3.34 g, stain inhibitor ( HQ-1) 0.33 g, compound A 5.0 g, and high boiling point organic solvent (DBP) 5.0 g were dissolved by adding 60 cc of ethyl acetate, and this solution was added with 10% of 20% surfactant (SU-1) 10%. 220cc gelatin solution
A yellow coupler dispersion was prepared by emulsifying and dispersing with an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a coating solution for the first layer.

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 1 and 2.

Further, as a hardening agent (H-1), (H-2)
Was added. As a coating aid, a surfactant (SU-
2) and (SU-3) were added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount was 0.04 g / m ² .

[0088]

[Table 1]

[0089]

[Table 2]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate / sodium salt SU-3: Di (2,2,3,3,4) sulfosuccinate , 4,5,5-Octafluoropentyl) / sodium salt DBP: dibutylphthalate DNP: dinonylphthalate DOP: dioctylphthalate DIDP: di-i-decylphthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine
Sodium Compound A: pt-octylphenol

[0091]

[Chemical 1]

[0092]

[Chemical 2]

[0093]

[Chemical 3]

[0094]

[Chemical 4]

[0095]

[Chemical 5]

[0096]

[Chemical 6]

(Preparation of blue-sensitive silver halide emulsion) The following (A) was added to 1 liter of a 2% gelatin aqueous solution kept at 40 ° C.
30) while controlling the liquids) and (B liquid) to pAg = 7.3 and pH = 3.0
Simultaneously added over a period of time, and further add the following (C liquid) and (D liquid)
Simultaneous addition was carried out over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water added (Solution B) Silver nitrate 10 g Water added 200 cc (Solution C) K ₂ IrCl ₆ 2 × 10 ^-8 mol / mol Ag Sodium chloride 102.7g K ₄ Fe (CN) ₆ 1 × 10 ^-5 mol / mol Ag potassium bromide 1.0g Water added 600cc (D liquid) Silver nitrate 300g Water added 600cc After the addition of Kao Atlas Demol N After desalting with 5% aqueous solution and 20% magnesium sulfate aqueous solution, mixed with gelatin aqueous solution, average particle size 0.85μm, variation coefficient of particle size distribution 0.07, silver chloride content 99.5 mol% monodisperse A cubic emulsion EMP-1 was obtained.

The following compounds were used for EMP-1.
Optimal chemical sensitization was performed at 60 ° C. to obtain a blue-sensitive silver halide emulsion for comparison (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-3 8 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX (preparation of green-sensitive silver halide emulsion) (solution A) and solution B
A monodisperse cubic emulsion E having an average grain size of 0.43 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (C liquid) are changed.
MP-2 was obtained.

The following compounds were used for EMP-2.
Optimal chemical sensitization was carried out at 55 ° C. to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (preparation of red-sensitive silver halide emulsion) (solution A) and solution (B)
A monodisperse cubic emulsion E having an average grain size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1 except that the addition time of (C solution) and the addition time of (C solution) are changed.
MP-3 was obtained.

The following compounds were used for EMP-3.
Optimal chemical sensitization was carried out at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX Supersensitizer RS-2 3 × 10 ⁻³ mol / mol AgX The sample thus obtained is referred to as Sample 101 (for comparison).

STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0106]

[Chemical 7]

The sample thus prepared was subjected to optical wedge exposure by a conventional method and then processed according to the following development processing steps.

Treatment process Treatment Temperature Time Replenishment amount Color development 38.0 ± 0.3 ℃ 45 seconds 80cc Bleach fixing 35.0 ± 0.5 ℃ 45 seconds 120cc Stabilization 30-34 ℃ 60 seconds 150cc Dry 60-80 ℃ 30 seconds Development processing The composition of the liquid is shown below.

Color developing solution tank solution and replenishing solution tank solution replenishing solution pure water 800cc 800cc triethylenediamine 2g 3g diethylene glycol 10g 10g potassium bromide 0.01g-potassium chloride 3.5g-potassium sulfite 0.25g 0.5g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0g 10.0g N, N-diethylhydroxylamine 6.8g 6.0g triethanolamine 10.0g 10.0g diethylenetriaminepentaacetic acid sodium salt 2.0g 2.0g fluorescence increase Whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to make the total volume 1 liter.
Adjust to 10 and replenisher to pH = 10.60.

Bleach-fixing solution Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc 2-Amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 cc Add water to make the total volume 1 liter, and adjust to pH = 6.5 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenishing solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1.0 g Ammonia water (ammonium hydroxide 25 % Aqueous solution) 2.5 g Nitrilotriacetic acid / trisodium salt 1.5 g Add water to bring the total volume to 1 liter, and adjust to pH = 7.5 with sulfuric acid or aqueous ammonia.

The sample thus obtained was designated as Sample 1. In addition, Sample 5 was prepared in the same manner as Sample 1. However, as shown in Tables 3 and 4, S-1 layer, S-2 layer and S-3 layer were applied between the support and the first layer from the side closer to the support.

<Sharpness> Each sample was exposed to a resolution test chart with red light and subjected to the above-mentioned treatment, and then the obtained cyan image was recorded on a microdensitometer PDM-5 (Konica).
(Manufactured by Co., Ltd.), the concentration was measured, and the value represented by the following formula was used as the sharpness evaluation value.

Sharpness (R) = (Dmax-Dmin of dense line print image of 3 lines / mm) / (Dmax-Dmin in large area) where Dmax: maximum density, Dmin: minimum density The larger the value, the better the sharpness.

<Whiteness> Using a Hunter whiteness meter (D type, manufactured by Toyo Seiki Seisaku-sho, Ltd.) according to the method of JIS P 8123, the whiteness was measured at a wavelength of 475 nm. If the whiteness value is 90 or more and the opacity value is 95 or more, there is no practical problem.

<Evaluation of Curl> The sample after the above development treatment was
After cutting into 10 cm × 10 cm, it was allowed to stand for 24 hours under the condition of 23 ° C. and 60% RH, and the curl degree was determined by the reciprocal of the radius of curvature.

If curl = 1 / radius of curvature (m) 6 is exceeded, the handling will be extremely poor and the level will not be practical.

[0118]

[Table 3]

[0119]

[Table 4]

Compound A: Di-n-octyl phthalate 16m
10.6 g of gelatin and 1.2 g of a surfactant (dodecylbenzenesulfonic acid) were dissolved in a mixed solution of 1 and 32 ml of ethyl acetate, and the mixture was emulsified and dispersed by a homogenizer.

Compound B: n-hexadecane is converted to the above compound A
Emulsified and dispersed in the same manner as in Table 3 and Table 4 show that samples having at least two hydrophilic colloid layers containing a white pigment between the support and the photosensitive silver halide emulsion layer according to the present invention are sharp. It can be seen that it has excellent whiteness and curl resistance.

Further, a sample in which the amount of white pigment applied to the white pigment-containing layer far from the support is larger than the amount of white pigment applied to the white pigment-containing layer close to the support, or the white pigment-containing layer far from the support contains anatase titanium dioxide. It is understood that the sharpness is improved and the whiteness and curl resistance are excellent even in the sample containing rutile-type titanium dioxide in the white pigment-containing layer near the support containing the above. Further, it is understood that the sharpness and the curl resistance are further improved in all the samples in which the coating amount of the white pigment is 1.5 g / m ² or more.

Example 2 A sample was prepared in the same manner as in Example 1. Note that S-1, S-2
The amounts of gelatin applied to the S and S-3 layers are shown in Tables 5 and 6.

[0124]

[Table 5]

[0125]

[Table 6]

Compound A: Di-n-octyl phthalate 16m
10.6 g of gelatin and 1.2 g of a surfactant (dodecylbenzenesulfonic acid) were dissolved in a mixed solution of 1 and 32 ml of ethyl acetate, and the mixture was emulsified and dispersed by a homogenizer.

Compound B: n-hexadecane is converted to the above compound A
Emulsified and dispersed in the same manner as in Table 5 and Table 6 show that the amount of gelatin coated is 0.2 g / m ²
It can be seen that the whiteness is further improved in the samples of 3.0 g / m ² or less.

Example 3 Each layer of the following constitution was coated on a 110 μm-thick support obtained by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide on the first layer side of the other side. Then, a multilayer color photographic light-sensitive material was produced.

(Preparation of Emulsion EM-1) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5). ) Is added at the same time by the control double jet method to obtain a particle size of 0.30
A μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so as to obtain a cubic particle shape. An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 40: 60) were simultaneously added to the obtained core emulsion by the control double jet method to obtain average grains. Diameter 0.42 μm
The shell was formed until At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-1. The breadth of distribution of this emulsion EM-1 was 8%.

(Preparation of Emulsion EM-2) While controlling the aqueous solution containing ossein gelatin at 40 ° C., an aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5). ) Is added at the same time by the control double jet method to obtain a particle size of 0.18
A μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so as to obtain a cubic particle shape. An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 40: 60) were simultaneously added to the obtained core emulsion by the control double jet method to obtain average grains. Diameter 0.25 μm
The shell was formed until At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-2. The breadth of distribution of this emulsion EM-2 was 8%.

(Preparation of Blue Sensitive Emulsion EM-B) EM-1
After sensitizing the dye by adding the sensitizing dye D-1, to 600 mg of T-1 was added per mol of silver to prepare a blue-sensitive emulsion EM-B.

(Preparation of Green Sensitive Emulsion EM-G) A green sensitive emulsion EM-G was prepared in the same manner as the blue sensitive emulsion except that the sensitizing dye D-2 was added to EM-2 for color sensitization.

(Preparation of red-sensitive emulsion EM-R) Red-sensitive emulsion EM-R was prepared in the same manner as blue-sensitive emulsion except that sensitizing dyes D-3 and D-4 were added to EM-2 for color sensitization. It was made.

(Preparation of pan-sensitive emulsion EM-P) Same as the blue-sensitive emulsion except that sensitizing dyes D-1, D-2, D-3 and D-4 were added to EM-1 for color sensitization. Pan-sensitive emulsion EM-
P was prepared.

T-1: 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene

[0138]

[Chemical 8]

Using the above EM-B, EM-G, and EM-R, the color photographic light-sensitive material 1-1 layer to 9th layer having the following constitution were coated in the following constitution. SA as a coating aid
-1 and SA-2, and H-1 as a hardening agent,
Sample 1-1 was prepared using H-2. SA-1: sulfosuccinic acid di (2-ethylhexyl) ester / sodium SA-2: sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) ester / sodium H- 1: 2,4-Dichloro-6-hydroxy-s-triazine / sodium H-2: Tetrakis (vinylsulfonylmethyl) methane layer composition coating amount (g / m ² ) 9th layer gelatin 0.78 (UV absorbing layer) UV absorber (UV-1) 0.065 UV absorber (UV-2) 0.120 UV absorber (UV-3) 0.160 Solvent (SO-2) 0.1 Silica matting agent 0.03 S-7 0.02 or A-1 0.03 or FI- 52 0.025 or any one of S-7, A-1, and FI-52 above was added Eighth layer Gelatin 1.43 (blue sensitive layer) Blue sensitive emulsion EM-B (coated silver amount) 0.4 General sensitive emulsion EM-P (Amount of coated silver) 0.1 Yellow coupler (YC-1) 0.82 Anti-stain agent (AS-2) 0.025 Solvent (SO-1) 0.82 Inhibitor (ST-1, ST-2, T-1) Seventh layer Gelatin 0.54 (Intermediate layer) Color mixture inhibitor (AS-1, 3, 4, 5, 6 equivalents) 0.055 Solvent (SO-2) 0.072 6th layer Gelatin 0.42 (Yellow yellow colloidal silver 0.1 colloidal silver layer) Anti-color mixing agent (AS-1,3,4,5,6 equivalent) 0.04 Solvent (SO-2) 0.049 Polyvinyl Pyrrolidone (PVP) 0.047 Anti-irradiation dye (AI-3) 0.03 Fifth layer Gelatin 0.54 (Intermediate layer) Anti-color mixing agent (AS-1,3,4,5,6 equivalent) 0.055 Solvent (SO-2) 0.072 4th layer Gelatin 1.43 (Green-sensitive layer) Green-sensitive emulsion EM-G (coated silver amount) 0.40 Pan-sensitive emulsion EM-P (coated silver amount) 0.10 Magenta coupler (MC-1) 0.25 Yellow coupler (YC-2) 0.06 Anti-stain agent (AS-2) 0.019 Solvent (SO-1) 0.31 Inhibitor (ST-1, ST-2, T-1) Third layer Gelatin 0.75 (Intermediate layer) Color mixture inhibitor (AS-1, 3, 4, 5, 6 equivalents) 0.055 Solvent (SO-2) 0.072 Anti-irradiation dye (AI-1) 0.01 Anti-irradiation dye (AI-2) 0.01 Second layer Gelatin 1.38 (red-sensitive layer) Red-sensitive emulsion EM-R (coating silver amount) 0.30 General-sensitive emulsion EM-P ( Coated silver amount) 0.06 Cyan coupler (CC-2) 0.44 Solvent (SO-1) 0.31 Anti-staining agent (AS-2) 0.015 Inhibitor (ST-1, ST-2, T-1) First layer gelatin 1.0 ( White pigment layer) Anatase type titanium dioxide 3.0 10th layer Gelatin 6.0 (backside layer) Silica matting agent 0.65 The amount of silver coated is calculated in terms of silver.

SO-1: trioctyl phosphate SO-2: dioctyl phthalate As-1: 2,4-di-t-octylhydroquinone As-2: 2,4-di-t-butylhydroquinone ST-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole ST-2: N-benzyladenine

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[Chemical 9]

[0142]

[Chemical 10]

[0143]

[Chemical 11]

[0144]

[Chemical 12]

(Exposure condition-1) Each of the light-sensitive materials was passed through a red filter (Ratten No. 26) and an ND filter to adjust the ND filter density when exposing white light,
With the minimum exposure amount that minimizes the red light density after development processing
Expose for 0.5 seconds.

(Exposure condition-2) Each light-sensitive material was passed through a green filter (Ratten No. 58) and an ND filter to adjust the ND filter density when white light was exposed,
With the minimum exposure amount that minimizes the green light density after development processing
Expose for 0.5 seconds.

(Exposure condition-3) Each light-sensitive material is passed through a blue filter (Ratten No. 47B) and an ND filter to adjust the ND filter density when exposing white light, so that the green light density after development is minimized. Exposure for 0.5 seconds with the minimum exposure amount.

A daylight fluorescent lamp was used as the light source. The exposed sample was processed under the following processing condition-1 to obtain an image.

Processing Step-1 Temperature Time Immersion (Developer) 37 ° C 12 seconds Fog exposure-12 seconds (1 lux) Development 37 ° C 95 seconds Bleach-fixing 35 ° C 45 seconds Stabilization 25-30 ° C 90 seconds Dry 60- 85 ° C 40 seconds Processing solution composition (color developer) Benzyl alcohol 15.0ml Cerium sulfate 0.015g Ethylene glycol 8.0ml Potassium sulfite 2.5g Potassium bromide 0.6g Sodium chloride 0.2g Potassium carbonate 25.0g T-1 0.1g Hydroxylamine Sulfate 5.0 g Sodium diethylenetriaminepentaacetate 2.0 g 4-Amino-N-ethyl-N- (β-methanesulfonamidoethyl) 4.5 g Metatoluidine 3/2 Sulfate monohydrate Optical brightener (4,4'- Diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 15.0 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.15.

(Bleach-fixing solution) diethylenetriaminepentaacetic acid ferric ammonium 90.0 g diethylenetriaminepentaacetic acid 3.0 g ammonium thiosulfate (70% aqueous solution) 180 ml ammonium sulfite (40% aqueous solution) 27.5 ml 3-mercapto-1,2,4-triazole Adjust the pH to 7.1 with 0.15 g potassium carbonate or glacial acetic acid and add water to bring the total volume to 1 liter.

(Stabilizing liquid) o-Phenylphenol 0.3 g Potassium sulfite (50% aqueous solution) 12 ml Ethylene glycol 10 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.5 g Bismuth chloride 0.2 g Zinc sulfate heptahydrate 0.7 g Water Ammonium oxide (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Fluorescent brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0 g Add water to bring the total volume to 1 liter and add ammonium hydroxide or Adjust the pH to 7.5 with sulfuric acid. The stabilization process is 2
A counter-current system with a tank configuration was adopted.

The prescription of the replenisher for running is shown below.

(Color development replenisher) Benzyl alcohol 18.5 ml Cerium sulfate 0.015 g Ethylene glycol 10.0 ml Potassium sulfite 2.5 g Potassium bromide 0.3 g Sodium chloride 0.2 g Potassium carbonate 25.0 g T-1 0.1 g Hydroxylamine sulfate 5.0 g Sodium diethylenetriamine pentaacetate 2.0g 4-Amino-N-ethyl-N- (β-methanesulfonamidoethyl) 5.4g Metatoluidine 3/2 sulfate monohydrate Fluorescent brightener (4,4'-diaminostilbenedisulfone Acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 18.0 ml Add water to bring the total volume to 1 liter, and adjust to pH 10.35.

(Bleach-fixing solution replenishing solution) Same as the bleach-fixing solution.

(Stabilizer Replenisher) Same as the above stabilizer.

The replenishing amount of the developer replenishing solution, the bleach-fixing solution and the stabilizing solution was 320 ml per 1 square meter of the photosensitive material.

Another part of the sample was exposed under the same conditions as in the case of the new solution treatment and processed in the same manner as in the processing step-1, but the developing solution in the processing step-1 was replenished with the replenished replenisher. Was processed by running the above sample 1 until the total amount thereof was 3 times the capacity of the developing tank, and the resulting developing solution, bleach-fixing solution and stabilizing solution were used for processing. (Running liquid treatment) The same treatment as in Example 1 was performed, and it was confirmed that the material had excellent sharpness, whiteness and curl resistance.

[0158]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having improved sharpness and excellent whiteness and curl resistance.

Claims (5)

[Claims] 1. A silver halide photograph comprising at least one silver halide emulsion layer and at least one non-photosensitive layer on one side of a reflection support having a resin coating layer on both sides of a base paper. A silver halide photographic light-sensitive material characterized by comprising at least two hydrophilic colloid layers containing a white pigment between the support and the silver halide emulsion layer. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the coating amount of the white pigment contained in the layer far from the support is larger than the coating amount of the white pigment contained in the layer close to the support. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the layer farther from the support contains anatase type titanium oxide, and the layer closer to the support contains rutile type titanium oxide. 4. The coating amount of the white pigment or titanium oxide is
4. The silver halide photographic light-sensitive material according to claim 1, which has a hydrophilic colloid layer containing 1.5 g / m ² or more. 5. The total coating amount of the water-soluble binder contained in the hydrophilic colloid layer coated between the support and the silver halide emulsion layer closest to the support is 0.2 g / m ^2. 4. The silver halide photographic light-sensitive material according to claim 1, comprising 3 to 3.0 g / m ² .