JPH05173307A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce deterioration of light resistance and increase of stains even at the time of rapid processing and to improve whiteness by incorporating a specified compound in a photosensitive layer or nonphotosensitive layer and specifying the processing time in a color developing solution. CONSTITUTION:The processing time in the color developing solution is regulated to <=30sec, and the photosensitive layer or nonphotosensitive layer formed on a support contains at least one of the compounds represented by formula I in which each of R1 and R2 is a substituent and at least one of them is nalkoxy or aryloxy; X is halogen; and each of l, m, or n is an integer of 0-4. One of this photosensitive silver halide emulsion layers contains silver halide grains containing silver chloride in an amount of >=90mol% and alkoxylated or aryloxylated 2-(1-hydroxyphenyl and/or 2-(1-hydroxyphenyl-X-halogenated)= benzotriazole.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material which is excellent in rapid processing property, light resistance, color turbidity resistance and sweating resistance.

[0002]

BACKGROUND OF THE INVENTION Recently, in the photographic industry, there has been a demand for a silver halide photographic light-sensitive material capable of rapid processing, high image quality, and always maintaining stable performance.

That is, a silver halide photographic light-sensitive material is usually
Continuous processing is being carried out by the automatic developing machine installed at each processing site, but as part of improving the service for users, it is required that the processing is completed and returned to the user within the day of the development reception date. Recently, it has become even more necessary to return the product within a few hours from the reception desk, and the need for rapid processing is increasing. Furthermore, since shortening the processing time improves the production efficiency and enables cost reduction, rapid processing is required.

In order to meet the current situation and needs of the market as described above, two approaches, that is, a light-sensitive material and a processing solution, are used to achieve rapid processing. Many attempts have been made to optimize the temperature and pH of the processing liquid and to add additives such as a development accelerator. As the development accelerator, British Patent 81
1-phenyl-3-pyrazolidone described in 1,185, U.S. Patent
N-methyl-p-aminophenol described in 2,417,514, N, N, N ', N'-tetramethyl-described in JP-A-50-15554
Examples include p-phenylenediamine. However,
These methods do not provide sufficient swiftness and often cause performance deterioration such as increased fog. On the other hand, although the halogen composition of the silver halide emulsion used in the light-sensitive material affects the developing rate, it has been found that particularly high developing silver halide exhibits a remarkably high developing rate.

However, there has been a problem that when the rapid processing as described above is performed, particularly when a large amount of processing is continued, the maximum concentration is likely to decrease with the lapse of time of the processing. This problem is insufficient although some are improved by the rapid processability imparting technology as described above, and there is a new problem that these rapid processability imparting technologies tend to cause deterioration of color turbidity resistance. Occurs. As a means for improving color turbidity resistance, a method of adding a hydroquinone-based color turbidity inhibitor to a non-photosensitive intermediate layer is known. It is necessary to add a large amount of the turbidity preventive agent. In this case, there arises a problem that the fading of the dye image tends to increase when the processed image is stored in the bright place. Therefore, as a result of various investigations, the present inventors have found that not only improving light fastness but also improving color turbidity resistance and perspiration resistance by performing a rapid treatment with a specific ultraviolet absorber, and arrived at the present invention. ..

[0006]

OBJECTS OF THE INVENTION Therefore, the object of the present invention is to suppress the occurrence of color turbidity during rapid processing, to provide excellent light fastness of a processed image and to suppress an improved increase in perspiration resistance. It is to provide a method of processing materials.

[0007]

The above object of the present invention is a processing method for processing a silver halide photographic light-sensitive material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support with a color developer. Where the photosensitive layer or the non-photosensitive layer contains at least one of the compounds represented by the following general formula (I) and / or general formula (II), and the processing time with a color developer is 30 seconds or less. And a method of processing a silver halide photographic light-sensitive material.

[0008]

[Chemical 4]

[0009]

[Chemical 5]

[0010]

DETAILED DESCRIPTION OF THE INVENTION The general formula (I) according to the present invention.
In the compound represented by, the substituents represented by R ₁ and R ₂ include an alkyl group (eg, methyl group, ethyl group, hexyl group, octyl group), aryl group (eg, phenyl group), alkoxy group (eg, methoxy group). Group, butoxy group,
Hexyloxy group, octoxy group), aryloxy group (for example, phenoxy group) and the like. These groups may be branched or may be substituted with other substituents. However, at least one of R ₁ and R ₂ represents an alkoxy group or an aryloxy group. X represents a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.).
l, m and n represent an integer of 0-4. However, the sum of l and m is 1 or more.

Next, examples of typical compounds represented by the general formula (I) according to the present invention will be given.

[0012]

[Chemical 6]

[0013]

[Chemical 7]

[0014]

[Chemical 8]

[0015]

[Chemical 9]

[0016]

[Chemical 10]

[0017]

[Chemical 11]

[0018]

[Chemical 12]

[0019]

[Chemical 13]

[0020]

[Chemical 14]

[0021]

[Chemical 15]

[0022]

[Chemical 16]

In the compound represented by the general formula (II) according to the present invention, the substituent represented by R ₁ and R ₂ is an alkyl group (eg, methyl group, ethyl group, hexyl group,
Octyl group), aryl group (eg phenyl group), alkoxy group (eg methoxy group, butoxy group, hexyloxy group, octoxy group), aryloxy group (eg phenoxy group) and the like. X and Y represent a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.). n is 1
Is an integer of 4 and l, m and p are integers of 0-4.

Next, examples of typical compounds represented by the general formula (II) according to the present invention will be given.

[0025]

[Chemical 17]

[0026]

[Chemical 18]

The compounds represented by the general formulas (I) and (II) according to the present invention preferably have a spectral absorption maximum wavelength in a solution in ethyl acetate of 340 nm to 370 nm and a molecular absorption at the absorption maximum wavelength. Coefficient is 18000l ・ cm ^-1・ mol ^-1
It is above, and more preferably, the spectral absorption maximum wavelength is 34
The molecular extinction coefficient is 4 nm to 360 nm and the spectral absorption maximum wavelength is 20000 l · cm ⁻¹ · mol ⁻¹ or more.

More preferably, the spectral absorption maximum wavelength is 34
It has a molecular extinction coefficient of 24000 l · cm ⁻¹ · mol ⁻¹ or more at a spectral absorption maximum wavelength of 6 nm to 355 nm. Furthermore 390n
The molecular extinction coefficient in m is preferably 2000 l · cm ⁻¹ · mol ⁻¹ or less, more preferably 1000 l · cm ⁻¹ · mol ⁻¹ or less.

Therefore, preferable spectral absorption characteristics are that the spectral absorption maximum wavelength is 344 nm to 360 nm, and the molecular extinction coefficient at the spectral absorption maximum wavelength is 20000 l · cm ⁻¹ · mol ⁻¹ or more, and
The molecular extinction coefficient at 390 nm is 2000 l · cm ⁻¹ · mol ⁻¹ or less. Most preferably, the spectral absorption maximum wavelength is 346 nm to 355.
nm and the molecular extinction coefficient at the spectral absorption maximum wavelength
The molecular extinction coefficient at 390 nm is 24,000 l · cm ⁻¹ · mol ⁻¹ or more and 2,000 l · cm ⁻¹ · mol ⁻¹ or less.

The compounds represented by the general formulas (I) and (II) can be used in combination with other benzotriazole type ultraviolet absorbers. Further, the compound of the general formula (I) and the general formula (I
The compound of I) can also be used in combination.

The compounds represented by the general formulas (I) and (II) may be added to either the photosensitive layer or the non-photosensitive layer, but are preferably added to at least the non-photosensitive layer. It is preferably added at least to the non-photosensitive layer on the side of the photosensitive layer farthest from the support opposite to the support. The amount added is not limited, but is preferably 0.05 to 15 g / m ² , and more preferably 0.1 to 5 g / m ² .

Silver halide grains having a silver chloride content of 90 mol% or more are used in at least one of the light-sensitive silver halide emulsion layers of the present invention. Preferably, the silver halide grains have a silver chloride content of 90 mol% or more, a silver bromide content of less than 10 mol%, and a silver iodide content of 0.5 mol% or less. More preferably, it is a silver chlorobromide having a silver bromide content of 0.2 to 2 mol%.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention may be used alone or in combination with other silver halide grains having different compositions. Further, it may be used as a mixture with silver halide grains having a silver chloride content of 10 mol% or less.

Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more according to the present invention, chloride occupying all silver halide grains contained in the emulsion layer. The proportion of silver halide grains having a silver content of 90 mol% or more is 60% by weight or more, preferably 80% by weight or more.

The composition of the silver halide grain of the present invention may be uniform from the inside to the outside of the grain,
The composition inside and outside the particle may be different. When the composition inside and outside the particle is different, the composition may continuously change or may be discontinuous.

The grain size of the silver halide grain of the present invention is not particularly limited, but considering other photographic performance such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2 μm. It is a range. The particle size is
It can be measured by various methods generally used in the art. A typical method is Loveland's "particle size analysis method" (ASTM Symposium
On Light Microscopy, 1955, 94-122
Page) or "The Theory of Photographic Process" (Mith and James, 3rd edition, Chapter 2 published by Macmillan, Inc. (1966)).

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

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
Monodisperse silver halide grains having a variation coefficient of 0.22 or less, more preferably 0.15 or less in the grain size distribution of silver halide grains are preferred. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation.

[0039]

[Equation 1]

Here, ri represents the particle size of each particle and ni represents the number thereof. The term "particle size" used herein means the diameter of a spherical silver halide grain, and the diameter of a cube or a non-spherical grain when the projected image is converted into a circular image of the same area. ..

The silver halide grains used in the emulsion of the present invention may be those obtained by any of the acidic method, the neutral method and the ammoniacal method. The particles may be grown at one time,
The seed particles may be grown and then grown. The method of forming seed particles and the method of growing seed particles may be the same or different.

The soluble silver salt and the soluble halogen salt may be reacted by any of a forward mixing method, a back mixing method, a double mixing method, or a combination thereof, but the double mixing method is preferable. Further, the pAg-controlled double jet method described in JP-A-54-48521 can be used as one form of the simultaneous mixing method. Further, if necessary, a silver halide solvent such as thioether may be used.

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
55-26589, Japanese Patent Publication No. 55-42737, The Journal of Photographic Science (J.Phot
gr.Sci), 21 , 39 (1973) and the like, particles having a shape such as an octahedron, a tetrahedron and a dodecahedron 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 may be a mixture of grains having various shapes.

The silver halide grains used in the emulsion of the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt during the grain forming process and / or the growing process. , An iron salt or a complex salt may be used to add a metal ion to the inside of the particle and / or the surface of the particle so that the metal ion can be incorporated therein. Nucleus can be imparted.

In the emulsion containing the silver halide grains of the present invention (hereinafter referred to as the emulsion of the present invention), unnecessary soluble salts may be removed after the growth of the silver halide grains is completed.
Alternatively, it may be contained as it is. The removal of the salts can be carried out according to the method described in Research Disclosure 17643.

The silver halide grain used in the emulsion of the present invention may be a grain in which a latent image is mainly formed on the surface, or may be a grain mainly formed inside the grain. Grains whose latent image is mainly formed on the surface are preferable.

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

In the present invention, a chalcogen sensitizer can be used as the chemical sensitizer. The chalcogen sensitizer is a general term for a sulfur sensitizer, a selenium sensitizer, and a tellurium sensitizer. For photographic use, the sulfur sensitizer and the selenium sensitizer are preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate,
Rhodanine can be mentioned. Others, U.S. Patent 1,574,944
No. 2, No. 2,410,689, No. 2,278,947, No. 2,728,668,
No. 3,501,313, No. 3,656,955, West German application published (OLS)
The sulfur sensitizers described in 1,422,869, JP-A-56-24937 and JP-A-55-45016 can also be used. The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as pH, temperature and size of silver halide grains, but as a guide, it is 10 ^-7 to 10 ^-1 mol per mol of silver halide. A molar amount is preferable.

A selenium sensitizer can be used in place of the sulfur sensitization. As the selenium sensitizer, aliphatic isoselenocyanates such as allyl isoselencyanate, selenoureas, selenoketones, selenoamides, Selenocarboxylates and esters, selenophosphates, diethyl selenide, selenides such as diethyl diselenide can be used, and specific examples thereof are described in U.S. Patents 1,574,944, 1,602,592, and 1,623,499. Have been described.

Further, reduction sensitization can be used together. The reducing agent is not particularly limited, but examples thereof include stannous chloride, thiourea dioxide, hydrazine and polyamine.

It is also possible to use a noble metal compound other than gold, such as a palladium compound, in combination.

The silver halide grains according to the present invention preferably contain a gold compound. As the gold compound preferably used in the present invention, the oxidation number of gold may be +1 or +3, and various gold compounds are used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric azide, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, gold selenide and the like. Be done.

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

The amount of the gold compound added varies depending on various conditions, but as a guide, from 10 ^-8 mol per mol of silver halide
It is 10 ^-1 mol, preferably 10 ^-7 mol to 10 ^-2 mol. Further, these compounds may be added at any of the steps of grain formation of silver halide, physical ripening, and completion of chemical ripening.

The emulsion of the present invention can be spectrally sensitized in a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more.

In the silver halide photographic light-sensitive material of the present invention, dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used, but in particular, as a dye having absorption in the visible region,
AI described in Japanese Patent Application No. 2-51124, pages 117-118
The dyes 1 to 11 are preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 are used. It has preferable spectral characteristics, has no influence on the photographic characteristics of the silver halide photographic emulsion, and is free from contamination due to residual color.
Specific examples of preferable compounds include the exemplified compounds (1) to (4) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication.
5) can be mentioned.

The coupler used in the silver halide photographic light-sensitive material according to the present invention forms a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Although any compound that can be used can be used, as a particularly 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, A typical one is known as a cyan coupler having a spectral absorption maximum wavelength in the wavelength region of 600 to 750 nm.

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is a coupler represented by the general formula (YI) described on page 8 of Japanese Patent Application No. 2-234208. Can be mentioned.
Specific compounds are described in YC-1 to YC-9 on pages 9 to 11 of the same specification.
Can be mentioned. Among them, YC-8 and YC-9 described on page 11 of the same specification are preferable because they can reproduce yellow of a preferable color tone.

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, there are described general formulas (M-I) and (M-II) described on page 12 of Japanese Patent Application No. 2-234208. ) And a coupler represented by Specific compounds include those described as MC-1 to MC-11 on pages 13 to 16 of the same specification. Among them, MC-8 to MC-11 described on pages 15 to 16 of the same specification are excellent in color reproduction from blue to purple and red,
It is also preferable because it has excellent detail depiction.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
Japanese Patent Application No. 2-234208, the general formula (C-
Examples thereof include couplers represented by I) and (C-II). Specific compounds are described in CC-1 on pages 18 to 21 of the specification.
To those described as CC-9 can be mentioned.

When the oil-in-water emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material according to 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 to dissolve and disperse 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. A method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder can also be used. 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 color forming dye, the compound (d-11) described on page 33 of Japanese Patent Application No. 2-234208 and the compound (A'-1) described on page 35 of the specification. And other compounds can be used. Besides, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but it is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 mol per mol of silver halide. It is used in the range of × 10 ^-2 to 1 mol.

For the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin, etc. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can be used.

As the reflective support according to the present invention, any material may be used, such as white pigment-containing polyethylene-coated paper, baryta paper, vinyl chloride sheet, white pigment-containing polypropylene, polyethylene terephthalate support and the like. Can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used in the reflective support of the present invention, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, clay and the like. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water resistant resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more as the content in the water resistant resin layer, and further, It is preferable that the content is 13% by weight or more, and 15
More preferably, it is at least wt%. The degree of dispersion of the white pigment in the water resistant resin layer of the paper support according to the present invention is
It can be measured by the method described in JP-A 2-28640.
When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and even more preferably 0.10 or less as the coefficient of variation described in the above publication.

In the silver halide photographic light-sensitive material according to the present invention, the support surface is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or undercoat layer (adhesiveness of the support surface, Applied through one or more undercoat layers for improving antistatic property, dimensional stability, abrasion resistance, hardness, antihalation property, friction property and / or other property) Good.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

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-laurylamino) toluene CD-4) 4- (N-Ethyl-N- (β-hydroxyethyl) amino) 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-diethylaminophenylethyl) 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- (β-butoxyethyl) aniline When used in the image forming method according to the present invention, development for a particularly short time From a processing perspective A compound represented by the following general formula (III) is more preferably used.

[0074]

[Chemical 19]

In the formula, R is a linear or branched alkylene group having 3 carbon atoms, m and n are each an integer of 1 to 4, and HA represents an inorganic or organic acid, for example, hydrochloric acid, sulfuric acid. , Nitric acid, p-toluenesulfonic acid and the like.

These color developing agents are available from Journal of American Chemical Society, Vol. 73, 3100.
It can be easily synthesized by the method described in (1951). General formula (II
Specific examples of the compound represented by I) are shown below.

[0077]

[Chemical 20]

[0078]

[Chemical 21]

The color-developing agent according to the present invention is usually used in the range of 1 × 10 ^-2 to 2 × 10 ^-1 mol per liter of developing solution, and from the viewpoint of rapid processing, per 1 liter of color developing solution.
It is preferably used in the range of 1.5 × 10 ^{-2 to} 2 × 10 ^-1 mol.

The color developing agent used in the image forming method according to the present invention may be used alone or in combination with other known p-phenylenediamine derivatives. In the image forming method according to the present invention, the compound used in combination with the compound represented by the general formula (III) includes (CD-5) and (CD-
6) and (CD-9) are preferred.

These p-phenylenediamine derivatives are
It is generally used in the form of a salt such as sulfate, hydrochloride, sulfite, nitrate, p-toluenesulfonate.

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 together 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, borate and the like can be used.

If necessary, inorganic and organic antifoggants can be added. For the purpose of suppressing development, halide salt ions are often used,
In the image forming method according to the present invention, since it is necessary to finish 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 to} 5.0 × 1 per liter of color developing solution.
It is 0 ^-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 the amount is about 1 liter of color developing solution.
The amount is preferably 1.0 × 10 ⁻³ mol or less, and more preferably 5.0 × 10 ⁻⁴ or less.

Furthermore, if necessary, a development accelerator can also 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
Nos. 2,531,832, 2,950,970, 2,577,127 and polyethylene glycol and its derivatives described in JP-B-44-9504, nonionic compounds such as polythioethers, organic solvents described in JP-B-44-9509 and Organic amine, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like are included. Also,
Phenethyl alcohol described in U.S. Pat.No. 2,304,925 and others, acetylene glycol, methyl ethyl ketone, cyclohexanone, pyridine, ammonia,
Examples thereof include hydrazine, thioethers and amines.

Further, in the color developing solution according to the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication Nos. 47-33378 and 44-9509.
The compounds described in each publication 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 1
It is used at 0.01 to 1.0 g per liter. In addition to these, competing couplers, fogging agents, development inhibitor-releasing couplers (so-called DIR couplers), development inhibitor-releasing compounds and the like can be added as required.

Furthermore, various additives such as other stain preventing agents, sludge preventing agents, and multi-layer effect accelerators can be used.

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 a low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Further, more generally, a concentrated aqueous solution of a plurality of components each of which can coexist stably, or a pre-prepared in a small container in a solid state in water is added to the color developing solution according to the present invention by stirring. Can also be prepared.

In the present invention, the above color developing solution can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH value is from 9.5 to 1.
It is preferably 3.0, more preferably pH 9.8 to 12.0
Used in the range of.

The processing temperature for color development according to the present invention is 35 ° C.
It is preferably 70 ° C or lower. The higher the temperature, the shorter the treatment time is, which is preferable. However, it is preferable that the temperature is not so high in view of the stability of the treatment liquid, and the treatment temperature is preferably 37 ° C. or higher and 60 ° C. or lower.

The color development time is conventionally about 3 minutes and 30 seconds, but in the present invention, it is within 25 seconds. Furthermore, it is preferable to carry out in the range of 20 seconds to 3 seconds.

The processing steps substantially consist of a color developing step, a bleach-fixing step, and a water washing step (including a stabilizing treatment as an alternative to water washing). However, steps may be added or equivalent meaning is provided within a range not impairing the effects of the present invention. Can be replaced with a process having. For example, the bleach-fixing step can be separated into a bleaching step and a fixing step, or the bleaching step can be performed before the bleach-fixing step. As the processing step used in the image forming method of the present invention, it is preferable to provide a bleach-fixing step immediately after the color developing step.

The bleaching agent that can be used in the bleach-fixing solution used in the image forming method of the present invention is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is one in which an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid or citric acid is coordinated with a metal ion such as iron, cobalt or copper. The most preferred organic acid used to form such a metal complex salt of an organic acid includes
Mention may be made of polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific examples of these compounds are described in JP-A-1-
No. 205262, compound [2] described in pages 58 to 59
[20] can be mentioned.

These bleaching agents are used in an amount of 5 to 450 g, preferably 20 to 250 g, per liter of the bleach-fixing solution. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition containing a large amount of a halide such as ammonium bromide in addition to the ethylenediaminetetraacetic acid iron (III) acid bleaching agent and the silver halide fixing agent, and further ethylenediaminetetraacetic acid iron (III) acid It is possible to use a special bleach-fixing solution having a composition comprising a combination of a bleaching agent and a large amount of a halide such as ammonium bromide. Examples of the halide include hydrochloric acid, hydrobromic acid, in addition to ammonium bromide,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can also be used.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide as used in ordinary fixing processing to form a water-soluble complex salt, such as potassium thiosulfate or sodium thiosulfate. Typical examples thereof include thiosulfates such as ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount of 5 g or more per liter of the bleach-fixing solution in a range where they can be dissolved, but generally 70 to 250 g. The bleach-fix solution contains various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide. They may be contained alone or in combination of two or more. Furthermore,
Various optical brighteners, antifoaming agents or surfactants may be contained. Further, hydroxylamine, hydrazine, preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, methanol,
An organic solvent such as dimethyl sulfonamide or dimethyl sulfoxide may be appropriately contained. The bleach-fixing solution according to the present invention includes JP-A-46-280 and JP-B-45-8506.
No. 46-556, Belgian Patent 770910, Japanese Patent Publication No. 45-883
Various bleaching accelerators described in No. 6, No. 53-9854, JP-A Nos. 54-71634 and 49-42349 can be added.

The pH of the bleach-fixing solution is used at 4.0 or higher, but it is generally used in the range of pH 4.0 to 9.5, preferably
Used at pH 4.5-8.5. Most preferably, pH 5.0-8.5
Used in the range of. The treatment temperature is 80 ° C. or lower, preferably 55 ° C. or lower to prevent evaporation and use. The processing time for bleach-fixing is preferably 3 to 45 seconds, more preferably 5 to 30 seconds.

In the developing process according to the present invention, the above-mentioned color developing and bleach-fixing steps are followed by washing with water.
Hereinafter, preferred embodiments of the water washing treatment will be described.

As the compound preferably used in the washing solution, a chelating agent having a chelate stabilizing constant for iron ions of 8 or more is preferable. Here, the chelate stabilization constant is defined by LG Sillen and AEMartell, “Stability Consta.
nts of Metal ion Comple-xes ", The Chemical So
ciety, London (1964), S.Chaberek, AEMartell
Written, "Organic Sequestering Agents", Wiley (1959)
It means a commonly known constant such as.

Examples of the chelating agent having a chelate stability constant of 8 or more for iron ions, which is preferably used in the washing solution, include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Be done. The iron ion means ferric ion. As a specific compound of the chelating agent having a chelate stability constant of 8 or more with ferric ion, there is disclosed in JP-A 1-2051.
The compounds described in No. 62, page 63, line 15 to page 64, line 17 can be mentioned.

The amount of the above chelating agent used is preferably 0.01 to 50 g, and more preferably 0.05 to 20 g, per liter of the washing solution. Further, as a compound added to the washing solution, an ammonium compound is mentioned as a particularly preferable compound. These are supplied by ammonium salts of various inorganic compounds. Specifically, JP-A 1-205162, page 65, page 5
The compounds described in lines 11 to 66, line 11. The amount of ammonium compound added is 1.
0 × 10 ^-5 mol or more is preferable, more preferably 0.001 to 5.
It is in the range of 0 mol, and more preferably in the range of 0.002 to 1.0 mol.

Further, it is desirable that the washing solution contains sulfite in a range where bacteria are not generated. The sulfite salt contained in the washing solution may be any one such as an organic substance or an inorganic substance as long as it releases a sulfite ion, but is preferably an inorganic salt, and as a preferable specific compound,
Sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite, cartaraldehyde bis sodium bisulfite, succinic acid Aldehyde bis sodium bisulfite etc. are mentioned.

At least 1.0 × 10 ^-5 mol of the above-mentioned sulfite is preferably added to 1 liter of the washing solution, and 5 × 1 is added.
More preferably, it is 0 ^{−5 to} 1.0 × 10 ⁻¹ mol. It may be added directly to the washing solution, but it is preferably added to the washing replenisher.

The water-washing solution used in the present invention preferably contains a mildew-proofing agent, which can prevent sulfidation and improve image storability. Examples of the mildew-proofing agent that can be used in the washing liquid according to the present invention include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guadinine compounds, morpholine compounds, and quaternary phosphonium compounds. ,
They are ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, pyronone compounds and amino compounds. Specific compounds are described in JP-A 1-205162.
The compounds described on page 68, line 10 to page 72, line 16 are mentioned. Among these compounds, particularly preferably used compounds are thiazole compounds, sulfamide compounds and pyronone compounds.

The amount of the antifungal agent added to the washing liquid is preferably 0.001 to 30 g, and more preferably 0.003 to 5 g, per liter of the washing liquid.

The washing liquid according to the present invention preferably contains a metal compound in combination with a chelating agent. Such metal compounds include Ba, Ca, Ce, Co, In, La, Mn, Ni, B
Examples thereof include compounds of i, Pb, Sn, Zn, Ti, Zr, Mg, Al and Sr. These metal compounds are halide salts,
It can be supplied as an inorganic or organic salt such as a sulfate, a carbonate, a phosphate or an acetate, a hydroxide or a water-soluble chelate compound. The amount of these compounds added is preferably 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻¹ mol, and 4.0 × 1
More preferably, it is 0 ^{−4 to} 2.0 × 10 ⁻² mol.

In addition to the above, a compound having an aldehyde group may be used as the one contained in the washing solution according to the present invention. As specific compounds, Exemplified Compound 1 to Exemplified Compound 32 described on pages 73 to 75 of JP-A 1-205162 can be mentioned. The compound having an aldehyde group is preferably used in the range of 0.1 to 50 g, and particularly preferably in the range of 0.5 to 10 g, per liter of the washing solution.

Ion exchange water treated with an ion exchange resin may be used as the washing water according to the present invention. The pH of the wash water applicable to the present invention is in the range of 5.5 to 10.0. As the pH adjuster applicable to the present invention, any of generally known alkali agents and acid agents can be used.

The treatment temperature of the water washing treatment is preferably 15 ° C to 60 ° C, more preferably 20 ° C to 45 ° C. Further, the time of the water washing treatment is preferably 5 to 60 seconds, more preferably 5 to 50 seconds. When the water washing treatment is performed in a plurality of tanks, it is preferable that the earlier tank is treated in a shorter time and the latter tank is treated in a longer time. Particularly, it is preferable to sequentially perform the treatment with a treatment time of 20% to 50% longer than that in the previous tank.

When the multi-tank counter flow current system is used as the method of supplying the washing liquid in the washing treatment step according to the present invention, it is preferable that the washing liquid is supplied to the post-bath and allowed to overflow into the pre-bath. Of course, it can also be processed in a single tank. As a method for adding the above compound, various methods such as adding as a concentrated solution to the washing tank or adding the above compound and other additives to the washing solution supplied to the washing tank and using this as a washing replenisher Is used.

The amount of washing water in the washing step according to the present invention is preferably 0.1 to 50 times, and particularly 0.5 to 50 times the carried-in amount of the pre-bath (normal bleach-fixing solution or fixing solution) per unit area of the light-sensitive material.
30 times is preferable.

The washing tank in the washing treatment according to the present invention is 1
˜5 tanks are preferable, and 1 to 3 tanks are more preferable.

As a developing processing apparatus for the silver halide photographic light-sensitive material used in the image forming method of the present invention, any known apparatus may be used. Specifically, it may be a roller transport type in which the photosensitive material is conveyed by sandwiching it between rollers arranged in a processing tank, or an endless belt method in which the photosensitive material is fixed and conveyed in a belt, The processing tank is formed in a slit shape, the processing solution is supplied to the processing tank and the photosensitive material is conveyed, the spray method for spraying the processing solution, and the web method by contact with the carrier impregnated with the processing solution A method using a viscous treatment liquid can also be used.

In the image forming method of the present invention, the time from exposure to development may be any time, but a shorter time is preferable in order to shorten the overall processing time. The silver halide photographic light-sensitive material according to the present invention is
Even when the time from exposure to development is 30 seconds or less, the change in image density is small and a high-quality image can be stably obtained, so that it can be advantageously used.

[0115]

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

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of paper pulp having a basis weight of 180 g / m ² . However, on the side on which the emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed therein was laminated to prepare a reflective support. Each layer having the constitution shown below was coated on this reflective support to prepare a multilayer silver halide photographic light-sensitive material, Sample 101. The coating liquid was prepared as follows.

Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67 g, additive (HQ-1) 0.67 g and high 60 ml of ethyl acetate was added to 6.67 g of the boiling point organic solvent (DNP) to dissolve it, and this solution was 9.5 ml of 15% surfactant (SU-1).
A yellow coupler dispersion liquid was prepared by emulsifying and dispersing it in 220 ml of a 10% gelatin aqueous solution containing a using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardening agent, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. As the coating aid, surfactants (SU-2), (S
U-3) was added to adjust the surface tension.

The layer structure is as shown in the table below.

[0119]

[Table 1]

[0120]

[Table 2]

[0121]

[Chemical formula 22]

[0122]

[Chemical formula 23]

[0123]

[Chemical formula 24]

[0124]

[Chemical 25]

[0125]

[Chemical formula 26]

(Preparation of Blue-Sensitive Silver Halide Emulsion) The following (solution A) was added to 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C.
And (Solution B) were simultaneously added over 30 minutes while controlling pAg = 6.5 and pH = 3.0, and the following (Solution C) and (Solution D) were added.
Simultaneous addition was performed over 180 minutes while controlling pAg = 7.3 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 0.07 g Water added 200 ml (Solution B) Silver nitrate 10 g Water added 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 2.10 g Water added 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain average grains. A monodisperse cubic emulsion EMP-1 having a diameter of 0.85 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.0 mol% was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B1).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 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 method of green-sensitive silver halide emulsion) Addition time of (A liquid) and (B liquid) and (C liquid) and (D liquid)
In the same manner as EMP-1 except that the addition time of
A monodisperse cubic emulsion EMP-2 having an average grain size of 0.43 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.0 mol% was obtained. EMP-2 with the following compounds at 55 ℃ 120
Chemical ripening to obtain a green-sensitive silver halide emulsion (Em-G
1) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Method for Preparing Sensitive Silver Halide Emulsion) Addition Time of (A Solution) and (B Solution) and (C Solution) and (D Solution)
In the same manner as EMP-1 except that the addition time of
A monodisperse cubic emulsion EMP-3 having an average grain size of 0.50 μm, a coefficient of variation (S / R) = 0.08 and a silver chloride content of 99.0 mol% was obtained. EMP-3 with the following compounds at 60 ℃ 90
Red sensitized silver halide emulsion (Em-R
1) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX

[0132]

[Chemical 27]

[0133]

[Chemical 28]

1000% 2% gelatin aqueous solution kept at 40 ° C
The following (Solution E) and (Solution F) are added in ml to pAg = 6.5, pH = 3.0
Controlled to 30 minutes at the same time, the following (G
Solution 1) and (solution H) are controlled to pAg = 7.3 and pH = 5.5 1
Simultaneously added over 80 minutes. At this time, pAg control is described in JP-A-59-
According to the method described in No. 45437, the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide. Then (I
Solution) and (J Solution) were added simultaneously over 2 minutes. Thus, a monodisperse cubic emulsion EMP-4 having an average grain size of 0.43 μm, a coefficient of variation (S / R) = 0.08 and a silver chloride content of 99.0 mol% was obtained. Analysis using X-ray revealed that the maximum value of the silver bromide content in the portion containing a high concentration of silver bromide was 61 mol%.

(Solution E) Sodium chloride 3.44 g Water was added to 200 ml (Solution F) Silver nitrate 9.9 g Water was added to 200 ml (Solution G) Sodium chloride 103.2 g (Solution K) 50 ml Water was added to 600 ml (Solution H) Silver nitrate 297 g Water added 600 ml (solution I) Potassium bromide 2.17 g Water added 15 ml (solution J) Silver nitrate 3.1 g Water added 15 ml (solution K) 1-phenyl-5-mercaptotetrazole Methanol solution (1% ) In preparing the green-sensitive emulsion (Em-G1), the emulsion (EM
A green-sensitive emulsion (Em-G2) was prepared in the same manner except that the emulsion (EMP-4) was used instead of P-2).

In the preparation of Sample 101, the fourth layer and the sixth layer
Each sample was prepared in the same manner except that the ultraviolet absorber in the layer was changed as shown in Table 3.

Each sample was wedge-exposed to green light with an exposure time of 0.5 seconds by an ordinary method, and then developed in the following development processing step.

(Processing step) Processing step Processing temperature Time Replenishment amount * Color development 38.0 ± 0.3 ℃ 20 seconds 80 ml Bleach fixing 35.0 ± 0.5 ℃ 20 seconds 120 ml Water wash 30-34 ℃ 60 seconds 150 ml Dry 60-80 ℃ 30 seconds * Replenishment amount is the amount per m ^{2 of} processed light-sensitive material.

The composition of the developing solution is shown below.

Color developer tank liquid Pure water 800 ml Tritylenediamine 2 g Diethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 3.5 g Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4- Aminoaniline sulfate 6.0 g N, N-diethylhydroxylamine 6.8 g Triethanolamine 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 2.0 g Potassium carbonate 30 g Water In addition, adjust the total volume to 1 liter and adjust to pH = 10.10.

Color developing solution replenisher Pure water 800 ml Triethylenediamine 3 g Diethylene glycol 10 g Potassium sulfite 0.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 10.0 g N, N- Diethylhydroxylamine 6.0 g Triethanolamine 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 2.5 g Potassium carbonate 30 g Add water to bring the total volume to 1 liter, pH = Adjust to 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 ml 5-amino-1,3,4-thiadiazole-2-thiol 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust to pH = 6.5 with potassium carbonate or glacial acetic acid.

Washing solution Tank solution and replenishing solution Orthophenylphenol 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 Fluorescent brightening agent (Tinopal SFP) 2.0 g 1-hydroxyethylidene-1,1 Jihosuhon acid 1.8 g BiCl ₃ (45% aqueous _{solution) 0.65g MgSO 4 · 7 H 2} O 0.2g PVP ( polyvinylpyrrolidone) 1.0 g of ammonia water (ammonium hydroxide 25% aqueous solution) 2.5 g Nitriloacetic acid trisodium salt 1.5 g Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

Light resistance test of the obtained magenta colored sample,
Color turbidity resistance and perspiration resistance were measured as follows.

[Light resistance test] The PDA-65 densitometer (manufactured by Konica Corporation) was used to measure the green light reflection density before and after fading when each sample was exposed to sunlight for 30 days using an underglass outdoor exposure table. Was measured using. The degree of fading due to light (fading rate) was determined as follows.

Discoloration rate = 100 × (D−D ₀ / D ₀ ) D ₀ = Density before photobleaching (1.0) D = Density after photobleaching [Color turbidity resistance] Each sample was exposed to red light and the temperature of the developing solution was adjusted. Three
The temperature was raised by doubling the processing time to obtain a cyan color image. The green light reflection density at the red light reflection density 1.5 part of the color-developed sample was measured using a PDA-65 densitometer (manufactured by Konica Corporation), and used as a measure of color turbidity resistance.

[Perspiration resistance] Each sample was stored at 85 ° C./60% for 3 weeks, and the perspiration state of the surface was observed.

The results are shown in Table 3 below.

[0149]

[Table 3]

A silver halide photographic light-sensitive material according to the present invention,
In Samples 2 to 13, not only the light resistance is improved, but also the color turbidity resistance and the publication resistance are improved as compared with Comparative Sample 1. On the other hand, in Comparative Sample 14 in which the conventionally known color turbidity preventing agent (HQ-1) was increased, the color turbidity resistance was improved,
Deterioration of light resistance and sweat resistance was observed. In this way, the effect of improving the light resistance, color turbidity, and publication resistance in the rapid processing is an effect that was not expected in the prior art.

Example 2 In the preparation of the color developing solution of Example 1, the color developing agent was N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate (exemplification). Compound (CD-6)) to equimolar amounts of Exemplified Compounds (I-2), (CD-5), (CD-9), and (III
-2) and (CD-6) were replaced by an equal amount of the mixture, and a color developer was prepared in the same manner, and evaluated in the same manner as in Example 1.

Color developing agents (III-2), (CD-
It was found that both 5) and (CD-9) were more excellent in development activity than the exemplified compound (CD-6) used in Example 1 and the effects of the present invention could be obtained. Among them, the color developing agent (III-2) has a large effect, and (CD
It was confirmed that the mixture with -6) also showed excellent effects.

[0153]

Industrial Applicability According to the present invention, a method for processing a silver halide photographic light-sensitive material in which the occurrence of color turbidity during rapid processing is suppressed, the light stability of a dye image is excellent, and perspiration resistance is improved can be obtained.

Claims (5)

[Claims] 1. A process for treating a silver halide photographic light-sensitive material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support with a color developer. Alternatively, a non-photosensitive layer contains at least one of the compounds represented by the following general formula (I), and the processing time with a color developing solution is 30 seconds or less. Processing method. [Chemical 1] In the formula, R ₁ and R ₂ represent a substituent. However, at least one of R ₁ and R ₂ represents an alkoxy group or an aryloxy group. X represents a halogen atom. l, m and n are 0-4
Indicates an integer. However, the sum of l and m is 1 or more. 2. A process for treating a silver halide photographic light-sensitive material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support with a color developer, wherein the light-sensitive layer is a photosensitive layer. Or a silver halide photographic light-sensitive material characterized in that the non-light-sensitive layer contains at least one compound represented by the following general formula (II) and the processing time in a color developer is 30 seconds or less. Processing method. [Chemical 2] In the formula, R ₁ and R ₂ represent a substituent. X and Y represent a halogen atom. n shows the integer of 1-4, l, m, and p show the integer of 0-4. 3. The processing method according to claim 1, wherein the total amount of gelatin in the silver halide photographic light-sensitive material is 7.6 g / m ² or less. 4. A color developing solution containing a color developing agent in an amount of 5 g / l or more.
The processing method described. 5. The processing method according to claim 1, wherein the color developing agent in the color developing solution is a compound represented by the following general formula (III). [Chemical 3] In the formula, R is a linear or branched alkylene group having 3 carbon atoms, m and n are each an integer of 1 to 4, and HA represents an inorganic or organic acid.