WO2004095130A1

WO2004095130A1 - Method of processing silver halide photographic lightsensitive material

Info

Publication number: WO2004095130A1
Application number: PCT/JP2003/005150
Authority: WO
Inventors: Toyoki Nishijima
Original assignee: Konica Minolta Photo Imaging, Inc.
Priority date: 2003-04-23
Filing date: 2003-04-23
Publication date: 2004-11-04

Abstract

A method of processing a silver halide photographic lightsensitive material that realizes high image density and excellent image density stability even when processing is performed with a regenerated processing solution. In particular, a method of processing a silver halide photographic lightsensitive material, the silver halide photographic lightsensitive material comprising a support and, superimposed thereon, at least one lightsensitive layer and at least one non-lightsensitive layer, characterized in that an alkyl alcohol derivative compound is contained in the lightsensitive layer or non-lightsensitive layer and that an overflow solution of color developer occurring at the time of continuous processing after imagewise exposure of the silver halide photographic lightsensitive material is regenerated and used in the processing of the silver halide photographic lightsensitive material.

Description

Processing method of silver halide photographic light-sensitive material

The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly, to a method for processing a silver halide photographic light-sensitive material excellent in stability of image density of a processed image using a reproduction processing solution. Background art

In recent years, the photographic industry has demanded a silver halide photographic light-sensitive material that can be rapidly processed, has high image quality, and can always maintain stable performance.

In the current situation of such a factory, approaches are being made from two aspects of silver halide photographic materials and developing solutions in order to achieve rapid processing to meet the needs. With regard to the developing solution, many attempts have been made to optimize the temperature and pH and to use additives such as a development accelerator. However, these methods often involve performance degradation such as an increase in capri. On the other hand, it is known that the composition of the silver halide emulsion used in the silver halide photographic light-sensitive material has an effect on the development speed. In particular, the silver halide having a high silver chloride content is used. It is known that when an emulsion is used, a remarkably high developing speed is exhibited.

It is also necessary to improve not only the silver halide emulsion but also the color-forming component such as a coupler having a high coupling speed with the oxidized color developing agent. For this reason, power blur, high-boiling organic solvents, and color mixing prevention in silver halide photographic materials It is also necessary to adjust the addition of agents and anti-fading agents.

In addition, in order to speed up the development process, to reduce the cost of the development process and to reduce the amount of waste liquid, a method of reusing the used developer solution once and using it has come to be used. That is, it removes accumulated components that are harmful to photographic performance from used color developing solution, adds missing components due to consumption, and does not remove accumulated components of color developing solution used as a replenisher for color developing. There is known a regeneration treatment method in which a regenerating agent is contained and reused.

However, it has been found that in the above-described regenerating process, particularly in the regenerating solution process in the rapid process, the image density tends to vary.

As a result of various studies on the above-mentioned problems, it was found that by using an alkyl alcohol derivative in a silver halide photographic light-sensitive material, a stable image density could be obtained even when a regenerating processing solution was used. It has been reached.

The method of using an alkyl alcohol-based compound in the silver halide photographic light-sensitive material according to the present invention has already been disclosed (for example, see Patent Document 1). No mention was made of any of the issues by

Accordingly, it is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material which is excellent in image density stability of a processed image using a reproduction processing solution. (Patent Document 1)

Japanese Patent Application Laid-Open No. H11-2888666 (Claims) Disclosure of the Invention The above object of the present invention is achieved by each of the following constitutions.

(1) A method for processing a silver halide photographic material having at least one photosensitive layer and at least one non-photosensitive layer on a support, wherein the photosensitive layer or the non-photosensitive layer comprises an alkyl alcohol derivative. A silver halide photographic light-sensitive material containing a compound is exposed imagewise, and then an overflow of a color developing solution for continuous processing is regenerated. A method for processing a silver halide photographic light-sensitive material, characterized by using a color developing solution thus prepared.

(2) The total calcium content of the silver halide photographic light-sensitive material, 0. 0 1~ 1 O mg Z , characterized in that m is ² (1) processing of silver halide photographic materials according to Method.

(3) The silver halide photographic light-sensitive material according to (1) or (2), wherein the silver halide photographic material contains an anionic surfactant having a benzene ring or a naphthalene ring. Processing method.

(1) The silver halide photograph according to any one of (1) to (3), wherein the silver halide photographic material has a total gelatin content of 6.2 g / ² or less. Processing method of photosensitive material. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention relates to a method for processing a silver halide photographic material having at least one light-sensitive layer and at least one light-insensitive layer on a support, wherein the light-sensitive layer or the non-light-sensitive layer is The silver halide photographic light-sensitive material containing the alkyl alcohol derivative compound is exposed imagewise, and then the overflow solution of the color developing solution at the time of continuous processing is regenerated to process the silver halide photographic light-sensitive material. The reproduced color expression It is characterized by using an image liquid.

First, the alkyl alcohol derivative compound according to the present invention will be described. The alkyl alcohol derivative compound according to the present invention is preferably a compound represented by the following general formula (1).

General formula (1)

R i-O H

In the general formula (1), R i represents a saturated or unsaturated alkyl group or a cycloalkyl group. The alkyl group is preferably an alkyl group having 10 or more carbon atoms. Further, the alkyl group and the cycloalkyl group may be substituted with a substituent. Examples of the substitution group include, for example, an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, a halogen atom, a cyano group, etc., a physics-chemical dictionary (published by Iwanami Shoten, 3rd edition). The substituents described on page 564 are exemplified. The number of carbon atoms contained in R is preferably 10 or more.

The alkyl alcohol derivative compound represented by the general formula (1) may be contained in any of the constituent layers in the silver halide photographic light-sensitive material according to the present invention.

Further, the compound represented by the general formula (1) is preferably used in a mass ratio of 0.01 to 100 times with respect to the dye-forming coupler. From the viewpoint of physical properties, it is preferable to use it in a range of 0.05 to 5 times. Further, the compound represented by the general formula (1) is preferably used by emulsifying and dispersing, and is further preferably used by dispersing in the same dispersion liquid as the pigment forming power blur.

Hereinafter, specific examples of the alkyl alcohol derivative compound represented by the general formula (1) used in the present invention are shown, but the alkyl alcohol derivative compound represented by the general formula (1) used in the present invention is shown below. The alkyl alcohol derivative compound is not limited by these. Exemplified compound 1: CH s (CH: ₇ CH ₂ OH

Exemplified compound 2: CH ₃ (CH: IO CH ₂ OH

Exemplified compound 3: CH s (CH; “CH ₂ OH

Exemplified compound 4 • LL 3 (CH; 0 28

Example Compound _{5: CH 2 = CH (CH} 2) 10 C rJ Exemplified Compound 6

Illustrative compound 7

Illustrative compound 8

Illustrative compound 9

Illustrative compound 10

Illustrative compound 11

Illustrative compound 12

Illustrative compound 13

Illustrative compound 14

The compound represented by the above general formula (1) is preferably liquid at ordinary temperature, and preferably has a boiling point of 150 ° C. or higher.

In the silver halide photographic material according to the present invention, the total force Rushiumu content in the coated film, but is preferably in the range of 0. 01~ 10 m gZm ^2, the calcium content here , calcium atom contained in the silver halide photographic material 1 m ^2, calcium ions, a calcium salt, the mass in terms of calcium atoms all compounds containing calcium, the assay I CP (I nductively C onpied Plasma) The value measured using the emission spectrometry.

This analytical method is described in “Chemical Field, Special Issue No. 127” (Nankodo, published in 1980) and VA F assel: Anal. Chem., 46, 1 110 A (1 974)).

Generally, gelatin, which is advantageously used as a binder in silver halide photographic light-sensitive materials, usually contains several thousand ppm of calcium salts derived from raw materials and manufacturing processes in terms of calcium atoms. For example, for direct viewing silver halide photographic light-sensitive material which has been put to practical use, typically 15 m gZm ² or more calcium is included. In the present invention, the total amount of calcium that is contained in all the layers constituting the silver halide photographic light-sensitive material, arbitrary preferable in the range of 0. 01~1 0 m gZm ² is 0.0 to 8 . and more preferably in the range of Om g / m ^2.

In the present invention, in order to reduce the total power content of the silver halide photographic light-sensitive material, a method of using gelatin having a low calcium content as a binder or a support for producing a silver halide photographic light-sensitive material can be used. A coating solution or a composition containing gelatin, such as a silver halide emulsion, a dispersion of a hydrophobic compound such as a coupler, or a gelatin solution, which is contained in the coating solution, is washed with noodle water, dialysis, ultrafiltration, etc. Desalting may be used, but it is preferable to use gelatin having a low calcium content.

In order to reduce the calcium content in gelatin, an ion exchange treatment is generally preferably used. For example, as described in Japanese Patent Application Laid-Open No. 63-296035, the gelatin solution is used in the production or use of gelatin as an ion exchange resin, particularly a cation exchange resin for removing calcium ions. Is preferably used.

Examples of gelatin having a low calcium content include acid-treated gelatin in which calcium is hardly mixed in the production process.

The gelatin used in the present invention is subjected to an ion exchange treatment in view of the effects of the present invention. Lime-treated gelatin is preferred. In addition, an oxidation treatment with hydrogen peroxide or the like can be performed for the purpose of reducing photographic activity.

Gelatin is preferred as a binder contained in each constituent layer of the silver halide photographic light-sensitive material according to the present invention, and in the present invention, the total content of gelatin is preferably 6.2 g / m ² or less, preferably from 4.0 to 6. a ^{2 g / m 2, 5. 0~6} . 0 is more preferably g / m ^2, 5. in particular it 1-5. a 7 g / m ² preferable.

The silver halide photographic light-sensitive material according to the present invention preferably contains an anionic surfactant having a benzene ring or a naphthalene ring. The anionic surfactant has a benzene ring or a naphthalene ring and an anion group. The surfactant is not particularly limited as long as it is a surfactant, but a surfactant having a sulfonic acid group as an anion group is preferable. Further, a surfactant in which a sulfonic acid group is directly substituted on a benzene ring or a naphthalene ring is preferable. Addition of these compounds can contribute to stabilization of coupler dispersion.

Preferred compounds include the following, but the present invention is not limited to these surfactants.

S-1: Sodium dodecylbenzenesulfonate

S—2: sodium octadecyl benzene sulfonate

S-3: isopropyl naphthalene sulfonic acid

The anionic surfactant according to the present invention may be added to any layer in the silver halide photographic light-sensitive material, and the addition amount is appropriately determined by designing various characteristics of the silver halide photographic light-sensitive material. You.

The silver halide used in the silver halide emulsion layer according to the present invention includes chloride Any silver halide such as silver, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide and the like can be mentioned. The silver halide used in the silver halide photographic light-sensitive material according to the present invention is exemplified. The grains preferably have a silver chloride content of 95 mol% or more, a silver bromide content of 5 mol% or less, and a silver iodide content of 0.5 mol% or less. More preferably, it is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%. The silver halide particles may be used alone or as a mixture with other silver halide particles having different compositions. It may be used by mixing with silver halide grains having a silver chloride content of 95 mol% or less.

In a silver halide layer containing silver halide grains having a silver chloride content of 95 mol% or more, a silver chloride content of 95 mol% of all silver halide grains contained in the emulsion layer is contained. % Of the silver halide grains is 60% by mass or more, preferably 80% by mass or more. The composition of the silver halide grains may be uniform from the inside to the outside of the grains, or the inside and outside compositions of the grains may be different. 'When the inside and outside compositions of the particles are different, the composition may change continuously or may be discontinuous.

The silver halide grains according to the present invention may have any shape. One preferable shape is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, Japanese Patent Application Laid-Open No. 55-26589, Japanese Patent Publication No. 55-42737, and The Journal of Photograph The shape of an octahedron, a tetradecahedron, a dodecahedron, etc. can be obtained by a method described in literatures such as K'Science (J.Ph0t0gr.Sci.) 21, 39 (1973). Particles can be made and used. Further, particles having a twin plane may be used. As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

The grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.1 to 1.2 μm, in consideration of other photographic properties such as rapid processing and sensitivity. Is in the range of 0.2 to 1.0 m. The particle size can be measured by various methods generally used in the technical field. As a typical method, there is “Label Size Analysis Method” (ASTM Symposium-on-Light 'Microscopy, 94-; L page 22, 1955) or “Theory of Photographic Process, 3rd Edition”. (Co-authored by Mies and J. Mus, Chapter 2, published by Macmillan, 1966).

This particle size can be measured using the projected area of the particle or its approximate diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

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

Coefficient of variation = S / R (where S is the standard deviation of the particle size distribution and R is the average particle size.) The particle size referred to here is the diameter of a spherical silver halide particle, In the case of particles having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image of the same area. Various methods known in the art can be used as an apparatus and a method for preparing a silver halide emulsion.

The silver halide emulsion according to the present invention can be prepared by any one of an acid method, a neutral method, and an ammonia method. May be obtained. The particles may be grown at a time or may be grown after seed particles have been made. The method of making the seed particles and the method of growing them may be the same or different.

The form of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but a method obtained by the simultaneous mixing method is preferable. Further, as one form of the double jet method, the pAg controlled double jet method described in JP-A-54-4852-1 can be used.

Also disclosed in JP-A-57-92523 and JP-A-57-92524 are devices for supplying aqueous solutions of water-soluble silver salts and water-soluble laurel salts from an addition device arranged in a reaction mother liquor, published in Germany. Apparatus for continuously changing the concentration of a water-soluble silver salt and water-soluble haeganide salt aqueous solution described in Japanese Patent No. 2,921,164, etc., and a reaction described in Japanese Patent Publication No. 56-501776. An apparatus may be used in which the reaction mother liquor is taken out of the vessel and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

Further, 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 at the time of forming silver halide grains or after the completion of grain formation.

For the reduction sensitization of the silver halide emulsion according to the present invention, a known method can be used. For example, a method of adding various reducing agents can be used, a method of ripening under high silver ion concentration conditions, or a method of ripening under high PH conditions can be used. Examples of the reducing agent used for the reduction sensitization of the silver halide emulsion according to the present invention include stannous salts such as stannous chloride, borane compounds such as tri-t-butylamborane, sodium sulfite, and sulfurous acid rim. Examples thereof include reductones such as sulfites and ascorbic acid, and thiourea dioxide. Of these, thiourea dioxide, ascorbic acid and its derivatives, and sulfites can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above is preferable because of excellent reproducibility.

These reducing agents may be dissolved in a solvent such as water or alcohol and added to the silver halide emulsion for ripening, or may be added during the formation of silver halide grains to perform reduction sensitization simultaneously with the formation of the grains. You may.

The amount of adding these reducing agents are p H of the silver halide emulsion, it is necessary to adjust as etc. silver ion concentration, typically, 1 per silver halide emulsion 1 mole X 1 0- ⁷ ~ 1 X 1 CI— ² moles is preferred.

After reduction sensitization, a small amount of oxidizing agent may be used to modify the reduced nucleus or to deactivate the remaining reducing agent. Examples of the compound used for such a purpose include potassium hexacyanoferrate (Π Ι), bromosuccinimide, p-quinone, potassium perchlorate, aqueous hydrogen peroxide, and the like.

The silver halide emulsion according to the present invention is subjected to reduction sensitization and can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer. As a chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a zeolite sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used, but an thiosensitizer is preferable. Zeosulfate, arylthio thiolba Examples include midthiourea, arylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes such as chloroauric acid, gold sulfate, and gold thiosulfate can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. Dose use of the gold compound, the kind of silver halide emulsion, the type of compound used, but connexion not uniform due to such aging conditions, is usually 1 mol of silver halide per 1 X 10- ⁴ mole ~ 1 X 10 — Preferably ⁸ moles. More preferably 1 X 10- ⁵ mol ~ 1 X 10 ^-8 molar.

The silver halide emulsion according to the present invention includes a known silver halide emulsion for the purpose of preventing capri generated during the process of preparing a silver halide photographic material, reducing performance fluctuation during storage, and preventing capri generated during development. Capri inhibitors and stabilizers can be used. Examples of the compound that can be used for such a purpose include a compound represented by the general formula (II) described in the lower section of page 7 of JP-A-2-14636. Are the compounds of (IIa-1) to (Ila-8), (lib-1) to (lib-7) described on page 8 of the publication and 5 _ mercaptotetrazole and the like. These compounds are added in a step such as a step of preparing silver halide emulsion grains, a step of chemical sensitization, a step of preparing a coating solution or the like at the end of a step of chemical sensitization according to the purpose. In the case where the presence of these compounds perform chemical sensitization, preferably used in an amount of 1 X 10- ⁵ mol ~ 5 X 1 0 one ⁴ mol per mol of silver halide. If added at the end of chemical sensitization, 1 X 10_ ⁶ mol-1 X 10 per mol of silver halide Preferably the amount of about _ ² moles, 1 X 1 0- ⁵ mol ~ 5 X 1 0 - ³ mol is more preferable. In the coating solution preparation step, when added to the silver halide emulsion layer, the amount of 1 X 1 CI- ⁶ mol ~ 1 X 1 0 about one ¹ mol per mol of silver halide preferably, 1 X 1 0- ^s mole ~ 1 X 1 0- ² mol is more preferable. Further, when added to a layer other than the C port Gen halide emulsion layer, the amount in the coating film is, the amount of about 1 X 1 0- ⁹ mol ~ 1 X 1 CT ³ mole are preferred.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, the silver halide photographic light-sensitive material may be used in combination with a yellow coupler, a magenta coupler, and a cyan coupler in a wavelength range of 400 to 90 nm. It has a layer containing a silver halide emulsion spectrally sensitized to a specific region. The silver halide emulsion contains one or more sensitizing dyes in combination.

As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any of known compounds can be used. As the blue-sensitive sensitizing dye, Japanese Patent No. 28388722 is described. BS-1-8 described on pages 1-8-10 of the book can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 110 of the same specification are preferably used. As the red light-sensitive dye, RS-11 to 8 described in pages 11 to 11 of the same specification are preferably used. When the silver halide photographic material according to the present invention is exposed by a printer using a semiconductor laser, it is necessary to use a sensitizing dye having sensitivity to infrared light. The dyes of IRS-1 to 11 described on pages 12 to 14 of JP-A-4-285595 are preferably used. It is preferable to use supercolored sensitizers SS-1 to SS-9 described on pages 14 to 15 of the same publication in combination with these dyes. When the silver halide photographic light-sensitive material according to the present invention is exposed using a laser, it is advantageous to use an exposure apparatus using a semiconductor laser in terms of miniaturization of the apparatus. In scanning exposure, the exposure time per pixel corresponds to the exposure time actually received by the silver halide emulsion, but the exposure time per pixel is defined as laser-light scanning exposure. In the spatial change of the light flux intensity, the point where the light intensity becomes 1/2 of the maximum value is defined as the outer edge of the light beam, and the line parallel to the scanning line and passing through the point where the light intensity becomes the maximum is When the distance between two points where the outer edges intersect is defined as the beam diameter (beam diameter) Z (scanning speed), the exposure time per pixel can be considered. As the exposure time per pixel becomes shorter, the relationship between the exposure time and the color density tends to become more complicated. The present invention is particularly effective when an apparatus having a shorter exposure time per pixel is used.

Examples of a laser printer device that can be applied to such a system include, for example, JP-A-55-4071, JP-A-59-11062, JP-A-63-19977, JP-A-2-74942, and JP-A-2-74942. No. 236583, Japanese Patent Publication No. 56-14963, No. 56-40822, European Regional Patent No. 77, 410, Electronic and Telecommunications Department Technical Research Report Vol. 80, No. 244, and Movie and TV Technology Magazine 1984Z6 (382), 34- Some are described on page 36.

In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, as dyes having absorption in the visible region, there can be mentioned, for example, AI-18 to JP2838722; 11 is preferably used. Examples of the infrared absorbing dye include the general formulas (I) and (I) described in the lower left column of page 2 of JP-A-11-280750. W 200

16

The compounds represented by (1) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and are preferable because there is no contamination by residual color. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication.

5 The coupler used in the silver halide photographic light-sensitive material according to the present invention includes a power coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a power coupling reaction with an oxidized form of a color developing agent. Any compound capable of forming a dye can be used, but a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, and a magnetic coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm.

Typical examples are a 10-coupler and a cyan coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

Examples of the yellow coupler that can be preferably used in the silver halide photographic light-sensitive material according to the present invention include couplers represented by the general formula (Y-11) described on page 8 of Japanese Patent No. 2916702. Can be. Specific compounds include those described as YC-1 to YC-9 on pages 9 to 11 of the same specification. Among them, YC-8 and YC-9 described on page 11 of the same specification are preferable because they can reproduce yellow with a preferable color tone. Examples of the magenta coupler include a coupler represented by general formulas (Μ-Μ) and (Μ-Π) described on page 12 of Japanese Patent No. 29166702. Specific compounds are described in pages 13-16 of the same specification.

20 11 to MC-11 can be mentioned. Among them, MC-8 to MC-11 described on pages 15 to 16 of the same specification are preferable because they are excellent in reproducing colors from blue to purple and red, and are also excellent in detail description. Shear which can be preferably used for the silver halide photographic light-sensitive material according to the present invention. Examples of the coupler include couplers represented by general formulas (C-I) and (C-II) described on page 17 of Japanese Patent No. 2916702. Specific compounds include those described as CC-1 to CC_9 on pages 18 to 21 of the same specification.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material according to the present invention, the water-insoluble high-boiling organic solvent having a boiling point of 150 ° C or more is usually used. If necessary, dissolve using a low boiling point or water-soluble organic solvent in combination, and emulsify and disperse in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the 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 simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. As a high-boiling organic solvent that can be used for dissolving and dispersing the coupler, a phthalic acid ester such as octyl phthalate and a phosphoric ester such as tricresyl phosphate are preferably used.

Alternatively, instead of using a high-boiling organic solvent, a coupler and a water-insoluble and organic solvent-soluble polymer compound may be dissolved in a low-boiling or water-soluble organic solvent, if necessary, in a hydrophilic binder such as an aqueous gelatin solution. In addition, a method of emulsifying and dispersing by various dispersing means using a surfactant may be used. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (N-t-butylacrylamide).

In order to shift the absorption wavelength of the color-forming dye, the compound (d-11) described in Japanese Patent No. 2916702, page 33, and the compound described in page 35 of the same document (- Compounds such as 1) can be used. In addition, U.S. Pat. The fluorescent dye releasing compound described in No. 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 is preferably 1 × 10 to ^{3 to} 5 mol, more preferably 1 × 10 mol per mol of silver halide. As used 1 0 ² to 1 mols.

In the present invention, it is preferable to add an oil-soluble dye. Oil-soluble dyes

It refers to an organic dye having a solubility in water at 0.01 ° C. of 0.01 or less, and is preferably a compound having a molecular absorption coefficient of 2000 or more at the maximum absorption wavelength at a wavelength of 400 nm or more. Preferred compounds include the compounds shown on page 26 of the specification of Japanese Patent No. 2,799,580. Specific examples of preferable compounds include Compounds 1 to 27 described on page 29 or page 32 of the same specification. Among them, compound 4 and

9 is particularly preferred. The oil-soluble dye is preferably added to the non-photosensitive layer.

It is preferably added in an amount of 0 SS mg / Z m ^2.

In the silver halide photographic light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder as described above. However, if necessary, other gelatin, gelatin derivatives, gelatin and other polymers may be used. Hydrophilic colloids such as proteins other than graft polymers, gelatin, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers and copolymers can also be used.

As the reflective support according to the present invention, any material may be used, such as a white pigment-containing polyethylene-coated paper, a baryta paper, a vinyl chloride sheet, a polypropylene containing a white pigment, a polyethylene terephthalate support, or the like. Can be done.

Among them is a support having a polyolefin down resin layer on both surfaces, and mass of preferably ² 1 7 g Z m 2 or less of the support, more preferably ² 1 5 g / m 2 or less. Further, the polyolefin resin layer preferably contains a white pigment.

As the white pigment used in the reflective support according to the present invention, an inorganic or organic white pigment can be used, and an inorganic white pigment is preferably used. For example, sulfates of alkaline earth metals such as barium sulfate, alkaline earth carbonates such as calcium carbonate, carbonates of earth metal, finely divided gay acid, silicas such as synthetic silicates, calcium silicate, alumina , Alumina hydrate, titanium oxide, 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 mass or more in the water-resistant resin layer, and more preferably 1% by mass or more.

The content is preferably at least 103% by mass, more preferably at least 15% by mass. The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention 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, as the coefficient of variation described in the above publication.

More preferably, it is 1510 or less.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion of the support surface, antistatic property) One or more subbing layers to improve the properties, dimensional stability, rub resistance, hardness, antihalation, friction properties or other properties)

20 may be applied.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As coating methods, paint coating and curtain coating, which can apply two or more layers simultaneously, are available. Especially useful.

In general, silver halide photographic light-sensitive materials are used in the development of a silver halide photographic light-sensitive material from a silver halide photographic light-sensitive material to a developing solution, such as a sensitizing dye or an inhibitor. Is known to elute and accumulate in the developer, thereby suppressing the development reaction.

Therefore, it is necessary to reduce the amount of eluted substances in the developer and to maintain the concentration constant. In a normal developing method, halide ions and organic compounds are eluted from a silver halide photographic material into a developing solution, and further, a developing agent, a preservative and an alkaline agent are consumed and reduced. Therefore, a replenisher is added to the developer in order to keep these concentrations substantially constant and maintain the developing characteristics, and the amount of the replenisher is allowed to flow out of the developer tank system as an overflow solution, and is added to the developer. The accumulated halide ion organic compounds are removed out of the system. In addition, the replenisher was used to replenish the deficient components, such as the consumed developing agent, to maintain the concentration of the developer constant.

In the present invention, the silver halide photographic light-sensitive material is regenerated from an overflow of a color developing solution that is generated when the silver halide photographic light-sensitive material is continuously processed after the imagewise exposure, and is reused in the processing of the silver halide photographic light-sensitive material. It is also referred to as a reproduction processing method). In the present invention, continuous processing is performed by processing a silver halide photographic light-sensitive material having the characteristic of containing an alkyl alcohol derivative compound in the above-mentioned light-sensitive layer or non-light-sensitive layer by the above-mentioned reproduction processing method. Even if it is performed, a stable image density can always be obtained. In addition, by reusing the developing solution, cost reduction and environmental load reduction can be achieved.

As a method for regenerating the color developing solution, any known method may be used. For example, JP-A-3-693936, JP-A-3-194552, JP-A-55-144424 Nos. 53-132343, 57-146249, and 61-95352. Regeneration method using an ion-exchange resin, and components eluted in a developer described in JP-A-3-174154. Regeneration method in which a deficient component is added as a regenerating agent without particular removal of the catalyst, JP-A-51-85722, JP-A-54-37731, JP-A-56-1049, JP-A-56-27142, JP-A-56 Nos. 33644, 56-149036, JP-B-61-10199, and 61-52459 using electrodialysis.

Of these, a regeneration method using an ion exchange resin and a regeneration method using a regenerant are preferable from the viewpoint of maintainability, cost and ease of use.

Known compounds can be used as the aromatic primary amine developing agent used in the color developing solution according to the present invention. Examples of these compounds include the following compounds.

CD-I: N, N—Jetil-p—Phenylenediamine

CD-2: 2-Amino-5-Jetylamino Toluene

CD_3: 2-amino-1 5-(N-ethyl-N-laurylamino) Toluene CD-4: 4-(N-ethyl-1 N-(; 3 -hydroxyshethyl) amino) anilin

CD-5: 2-Methyl-41- (N-ethyl-N- (1-hydroxyxethyl) amino) anilin

CD-6: 4-amino-3-methyl-N- (β- (methanesulfonamide) ethyl) -aniline

CD—7: N— (2-amino-5-Jetylaminophenylethyl) methane sulfonamide CD-8: N, N-dimethyl p-phenylenediamine

CD-9: 4 Amino 3-Methyl-N-Ethyl-1-N-Methoxyxylaniline

CD-10: 4-Amino-3-methyl-N-ethyl-N-(^-ethoxyethyl) aniline

CD-I1: 4-amino-3-methyl-N-ethyl-N-(; 9-butoxyethyl) aniline

Color developing agent used in the present invention is usually developer 1 liter per 1 X 1 0_ used in ² to 2 X 10- ¹ mols, from the viewpoint of rapid processing color developer 1 liter The amount is preferably used in the range of 1.5 X 10-2 to ² X 10-1 ^per mole. The color developing agent used in the silver halide photographic light-sensitive material processing method of the present invention may be used alone or in combination with other known p-phenylenediamine derivatives. A preferred developer in the method for processing a silver halide photographic light-sensitive material of the present invention is substantially free of benzyl alcohol. Here, “substantially not contained” means that benzyl alcohol is 2 m 1 / L or less, and it is most preferable that the benzyl alcohol is not contained at all in the present invention.

The color developing solution used in the present invention may contain the following developing solution components in addition to the above components. Examples of the alkaline agent include, for example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, sodium phosphate, potassium phosphate, borax, and gait alone or in combination. They can be used in combination as long as no precipitation occurs and the pH stabilizing effect is maintained. Furthermore, for the purpose of dispensing, or for the purpose of increasing ion strength, sodium hydrogen phosphate, sodium hydrogen phosphate, sodium bicarbonate, bicarbonate Various salts such as limestone and borates can be used.

Further, in the color developing solution according to the present invention, JP-A-63-146043, JP-A-63-146042, JP-A-63-146041, JP-A-63-146041, and JP-A-64-16043, JP-A-63-146042, in place of hydroxylamin conventionally used as a preservative. Nos. 63-146040, 63-135938 and 63-118748, and hydroxylamine derivatives and hydroxamic acids and hydrazines described in JP-A-64-62639 and JP-A-1-303438. Hydrazides, phenols, monohydroxyketones, α-aminoketones, sugars, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, Condensed amines are preferably used as the organic preservative.

These compounds can be used in combination with conventionally used hydroxylamin and the above-mentioned organic preservative. However, it is more preferable not to use hydroxyammine from the viewpoint of developing characteristics.

Furthermore, if necessary, a development accelerator can be used. Examples of the development accelerator include various pyridinium compounds represented by U.S. Pat. Nos. 2,648,604 and 3,671,247 and JP-B-44-9503, and other cationic compounds. Cationic dyes such as phenosafranine; neutral salts such as thallium nitrate; U.S. Pat. Nos. 2,533,990; 2,531,832; 2,950,970; Non-ionic compounds such as polyethylene glycol and derivatives thereof and polythiols described in Japanese Patent Publication No. 577,127 and JP-B-44-9504, and organic solvents, organic amines and ethanol described in JP-B-44-9509. Amines, ethylenediamines, jetanolamines, triethanolamines and the like. Also described in US Patent No. 2,304,925. The listed phenethyl alcohol and others include acetylene glycol, methylethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like.

Further, the color developing solution used in the present invention may contain, as necessary, ethylene glycol, methyl cellulose, methanol, acetone, dimethylformamide, β-cyclodextrin, etc. The compounds described in JP-A Nos. 33778 and 449-1595 can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, Ν-methyl-1-ρ-aminophenol sulfate, phenylidone, Ν, N'-getyl-1-ρ-aminophenol hydrochloride, Ν, Ν, Ν ', Ν'-tetramethyl One ρ-phenylenediamine hydrochloride and the like are known, and the amount of addition is usually 0.01 to 1.0 Og per liter of developer. In addition, if necessary, a competitive coupler, a fogging agent, a development inhibitor releasing type power blur (a so-called DIR coupler), a development inhibitor releasing compound, etc. can be added.

Furthermore, various additives such as other anti-stin agents, anti-sludge agents, and layering effect promoters can be used.

Each component of the color developing solution can be prepared by sequentially adding and stirring a certain 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. More generally, a plurality of components, each of which can stably coexist, is added to a concentrated aqueous solution or a solution prepared in advance in a small container in a solid state in water, and stirred for use in the present invention. A color developing solution can also be prepared.

Sulfite concentration of the color developing solution according to the present invention is good preferable less 1 X 1 0- ² mol ZL. Particularly 0 are hints 7 X 1 0 one ³ moles ZL good when the following, preferred when the following 5 X 1 0- ³ mol ZL especially including 0.

In the present invention, the above-mentioned color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, it is preferable that ρ—9.5 to 13.0, and more preferably, ρΗ9.5-13.0. It is used in the range of 8 to 12.0.

The processing temperature of color development used in the present invention is preferably 35 ° C. or more and 70 ° C. or less. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the lower the temperature, the more preferable. The color development time is preferably within 45 seconds in the present invention.

The processing step essentially comprises a color developing step, a bleach-fixing step, and a rinsing step (including a stabilizing treatment in place of rinsing), but steps with additional or equivalent meanings as long as the effects of the present invention are not impaired. Can be replaced by For example, the bleach-fixing step can be separated into a bleaching step and a fixing step, or a bleaching step can be performed before the bleach-fixing step. As a processing step used in the image forming method of the present invention, a bleach-fixing step is preferably provided immediately after the color developing step.

The bleaching agent that can be used in the bleach-fixing solution used in the present invention is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is a compound 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. Most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or amino acids The carboxylic acid may be an alkali metal salt, an ammonium salt or a water-soluble amine salt.

Specific examples of these compounds include compounds [2:] to [20] described in JP-A No. 1-205262, pages 58-59.

These bleaches are used in an amount of 5 to 45 ° g, more preferably 20 to 250g, per liter of the bleach-fix solution. The bleach-fixing solution contains a silver halide fixing agent in addition to the bleaching agent as described above, and if necessary, a solution containing a sulfite as a preservative is applied. Also, a bleach-fixing solution having a composition containing a large amount of a halide such as ammonium bromide in addition to the ethylenediaminetetraacetate (鉄) bleaching agent and the silver halide fixing agent, and an ethylenediaminetetraacetate (III) ) 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 can be used. As the halide, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can be used. .

As the silver halide fixing agent contained in the bleach-fixing solution, a compound which reacts with silver halide to form a water-soluble complex salt as used in ordinary fixing processing, for example, thiosulfuric acid lime, Representative examples thereof include thiosulfates such as sodium sulfate and ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate and thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount of at least 5 g per liter of the bleach-fixing solution and in a dissolvable range, but generally used in an amount of 70 to 250 g. The bleach-fixing solution contains boric acid, borax, sodium hydroxide, sodium hydroxide, sodium carbonate. Various pH buffers such as aluminum, potassium carbonate, sodium bicarbonate, sodium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide can be used alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants can be contained. Also, preservatives such as bisulfite adducts of hydroxylamine, hydrazine, and aldehyde compounds; organic chelating agents such as aminopolycarboxylic acid; and stabilizers such as nitroalcohol and nitrate; methanol, dimethyl sulfonamide; An organic solvent such as dimethyl sulfoxide can be appropriately contained. The bleach-fixing solution used in the present invention includes JP-B-46-280, JP-B-45-8506, JP-B-46-556, Belgian Patent No. 770910, JP-B-45-8836, and JP-B-53-9854. Various bleaching accelerators described in JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of the bleach-fix solution is used at pH 4.0 or higher, but is generally used in the range of pH 4.0 to 9.5, preferably pH 4.5 to 8.5. Most preferably, it is used in the range of pH 5.0 to 8.5. Use at a temperature of 80 ° C or less, preferably 55 ° C or less, while suppressing evaporation. The processing time for bleach-fixing is preferably from 3 to 45 seconds. In the developing process used in the present invention, a water washing process is performed subsequent to the color developing and bleach-fixing steps. The pH of the washing water applicable to the present invention is in the range of 5.5 to 10.0. The treatment temperature of the water washing treatment is preferably from 15 to 60 ° C, more preferably from 20 to 45 ° C. Further, the time of the water washing treatment is preferably 5 to 90 seconds. In the case of performing the water washing treatment in a plurality of tanks, it is preferable that the treatment is performed in a shorter time in the front tank and the treatment time is longer in the rear tank. In particular, it is preferable to perform the treatment sequentially with a treatment time 20 to 50% longer than that of the preceding tank. As the development processing apparatus used in the processing method of the silver halide photographic light-sensitive material of the present invention, any known apparatus may be used. Specifically, even in the case of a roller transport type in which silver halide photographic photosensitive material is conveyed between rollers arranged in a processing tank, the silver halide photographic photosensitive material is fixed to a belt. An endless belt system for transport may be used, but a processing tank is formed in a slit shape, and a processing liquid is supplied to this processing tank, and a method for transporting the silver halide photographic light-sensitive material or a processing liquid is sprayed. A spray method for forming a liquid, a wet method by contact with a carrier impregnated with a treatment liquid, and a method using a viscous treatment liquid can also be used. In the present invention, a large amount of photosensitive material is processed and run in these color development to drying steps, and elution of components from the photosensitive material into the processing solution, contamination between processing tanks, and evaporation of the processing solution are saturated. The effect is particularly effective when the treatment is performed after stabilization.

In the present invention, the time from exposure to development may be any, but it is preferable that the time be short in order to shorten the overall processing time.

Next, the present invention will be described specifically with reference to examples, but embodiments of the present invention are not limited thereto.

<< Silver halide color photographic light-sensitive material: Preparation of sample 101 >>

(Preparation of silver halide emulsion)

Each silver halide emulsion was prepared by the following method.

(Preparation of red-sensitive silver halide emulsion)

4 In 1 liter of 2% aqueous gelatin solution kept in CTC, add the following (Solution A) and (Solution B) over 30 minutes while controlling pAg to 7.3 ヽ pH to 3.0. At the same time, adjust the following (Solution C) and (Solution D) to a pAg of 8.0 and a pH of 5.5. Were added simultaneously over 180 minutes. At this time, the control of pAg was performed by the method described in JP-A-59-45437, and the control of pH was performed using sulfuric acid or an aqueous solution of sodium hydroxide.

(A liquid)

Sodium chloride 3.4 2 g Potassium bromide 0.0 3 g Add water to 200 ml (solution B)

Silver nitrate 10 g Add water and add 200 ml

(C solution)

Sodium chloride _{1 0 2. 7 g K 2 I} r C 1 6 X 1 0 _ 8 mol / mol _{A g K 4 F e (CN} ) 2 X 1 0- 5 mol / mol A g bromide force Centrum 1.0 g Add water to 600 ml

(D solution)

After adding 300 g of silver nitrate water and adding 600 ml of the above solutions, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate. After that, it is mixed with an aqueous gelatin solution to form a monodispersed cubic emulsion having an average particle size of 0.40 µm, a coefficient of variation in particle size distribution of 0.07, and a silver chloride content of 99.5 mol%. Silver emulsion EMP-1 Obtained.

Next, the average particle diameter was changed in the same manner as in the above silver halide emulsion EMP-1, except that the addition times of the above (Solution A) and (Solution B) and the addition times of (Solution C) and (Solution D) were changed. A silver halide emulsion EMP-1B as a monodisperse cubic emulsion having a particle size distribution of 0.38 m, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol% was obtained.

The silver halide emulsion EMP-1 was optimally chemically sensitized at 60 ° C using the following compounds. Similarly, after optimally sensitizing the silver halide emulsion EMP-1B in the same manner, the silver halide emulsion EMP-1 and the silver halide emulsion EMP-1B were added in a silver content ratio of 1: 1. : 1 to obtain a red-sensitive silver halide emulsion (101 R).

Chio sodium sulfate 1 X 1 0 - ⁴ mol / / Monore A g X chloroauric acid 2 X 1 0 - ⁴ mol / ^kappa mol A g X Stabilizer: STAB- 1 3 X 1 0 - 4 mol / / mol A g X Stabilizer: STAB- 23 X 10 — ⁴ mol / z mono-Ag X Stabilizer: STAB- 33 X 10 — ⁴ mol // mol Ag X 增 Dye: RS-11 X 10 — ⁴ mol // mol AgX sensitizing dye: RS-21 × 10 — ⁴ mol // mol AgX

S T A B— 1 (3-acetamide dopenyl) -1-5-mercaptotetrazole

S TAB—2: 1 _phenyl-5-mercaptotetrazole

S TAB—3: 1— (4-ethoxyphenyl) -1-5-mercaptotetrazole

In the red-sensitive emulsion, SS-1 was added at 2.0 X per mole of silver halide. One to ^{three was} added.

(Preparation of green photosensitive silver halide emulsion)

In the preparation of the silver halide emulsion EMP-1, the average particle size was reduced in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. A silver halide emulsion EMP_2 was obtained as a monodisperse cubic emulsion having a length of 40 m, a coefficient of variation of 0.08, and a silver chloride content of 99.5%. Next, in the preparation of the silver halide emulsion EMP-1, the average was calculated in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. A silver halide emulsion EMP-2B was obtained as a monodisperse cubic emulsion having a particle size of 0.50 m, a variation coefficient of 0.08, and a silver chloride content of 99.5%.

The silver halide emulsion EMP_2 prepared above was optimally subjected to chemical sensitization at 55 ° C using the following compounds. Similarly, after the silver halide emulsion EMP-2B was optimally chemically sensitized, the sensitized silver halide emulsion EMP-2 and the silver halide emulsion EMP-2B were mixed with silver. The mixture was mixed at a ratio of 1: 1 to obtain a green photosensitive silver halide emulsion (101 G).

Chio sodium sulfate 1 X 1 0 one ⁴ mol / mol A g X chloroauric acid 2 X 1 0- ⁴ mol / mol A g X Stabilizer: STAB- 1 2. 5 X 1 0 _4 mole Z moles A g X stabilizer: STAB- 2 3. 1 X 1 0 one ⁴ Mo g X stabilizer: STAB- 3 3. 1 X 1 0- 4 g sensitizing dye: GS- 1 ⁴ X 1 0- 4 mol / mol A g X (Preparation of blue-sensitive silver halide emulsion)

Addition of (Solution A) and (Solution B) in the preparation of the silver halide emulsion EMP-1 Monodisperse cubes having an average particle size of 0.71 m, a coefficient of variation of 0.08, and a silver chloride content of 99.5% were prepared in the same manner except that the time and the addition time of (solution C) and (solution D) were changed. An emulsion, a silver halide emulsion EMP-3, was obtained. Also, in the preparation of the silver halide emulsion EMP-1, the average grain size was changed in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. A silver halide emulsion EMP-3B was obtained as a monodisperse cubic emulsion having a diameter of 0.64 m, a variation coefficient of 0.08, and a silver chloride content of 99.5%.

The above silver halide emulsion EMP-3 was subjected to optimal chemical sensitivity at 60 ° C using the following compounds. Similarly, after optimally chemical sensitizing silver halide emulsion EMP-3B, the sensitized silver halide emulsion EMP-3 and silver halide emulsion EMP-3B were added to the silver amount. The mixture was mixed at a ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (101B).

Chio sodium sulfate 1 X 1 0- ⁴ mol / 3 Le A g X chloroauric acid 2 X 1 0- ⁴ mol 3 Le A g X Stabilizer: STAB _ 1 2 X 1 0_ 4 mol / 3 Le A g X stable agent: STAB _ 2 2 4 X 1 0 one ⁴ mol / Le A g X stabilizer: STAB _ 3 2 1 X 1 0- 4 mol / Tri-A g X增感dye: BS- 1 4 X 1 0 ^_4 Mol / L Ag X 增 Dye: BS— 21 X 10 ^_4 mol / L Ag X

_{_{_{(CH 2) 3 S0 3 H}}} · N (C 2 H 5) 3

₅ ) ₃

<< Production of silver halide photographic light-sensitive material >>

[Preparation of Sample 101]

A reflective support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side to which the photosensitive layer was applied, molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by mass was laminated. The mass of the obtained support was 220 g / m ² . After subjecting this reflective support to corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following structure was further provided thereon, to prepare Sample 101 as a silver halide color photographic light-sensitive material. The coating solution was prepared as described below.

(Preparation of first layer coating solution)

Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST_2) 3.34 g, (ST-5) 3.34 g, stin inhibitor 0.34 g of (HQ-1), 5.0 g of image stabilizer A, 3.33 g of high boiling organic solvent (DBP) and 1.67 g of high boiling organic solvent (DNP) The solution was added and dissolved, and this solution was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This yellow coupler dispersion was mixed with the blue-sensitive silver halide emulsion (101B) prepared above to prepare a first layer coating solution.

(Preparation of coating solution for layer 2 to layer Ί)

The coating solutions for the second to seventh layers were also prepared using the following additives in the same manner as in the preparation method of the first layer coating solution.

(Each layer configuration) <Seventh layer: protective layer> 2

g ^/ m gelatin 0.70

D I D P 0.00 05 Silicon dioxide 0.03

Gelatin 0.3 0 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Sting inhibitor (HQ-5) 0 . 0 4

PVP (Polyvinyl pigment) 0.03 Anti-irradiation dye (AI-1) 0.01 Fifth layer: Red photosensitive layer>

Gelatin 1.20 Red photosensitive silver halide emulsion (101R) 0.21 Cyan coupler (C-1) 0.25 Cyan coupler (C-12) 0.08 Dye image stabilization (ST-1) 0.10 Sting inhibitor (HQ-1) 0.004

D B P 0.10

D 0 P 0.20 Fourth layer: UV absorbing layer>

Gelatin 0.90 UV absorber (uV-1) 0.28 UV absorber (UV-2) 0.09 UV absorber (UV-3) 0.38 Sting inhibitor (HQ-3) 0.110 Anti-dye (AI-1) 0.02 Third layer: Green photosensitive layer>

Gelatin 1.20 Green photosensitive silver halide emulsion (10 1 G) 0.14 Magenta coupler (M-1) 0.20 Dye image stabilizer (ST-3) 0.20 Dye image stabilization Agent ( _ST- 1 4) 0.1 7

D I D P 0.1 3

D B P 0.13 Anti-irradiation dye (AI1-2) 0.01 Second layer: Intermediate layer>

Gelatin 1.10 Stin inhibitor (HQ-2) 0.03 Stin inhibitor (HQ-3) 0.03 Stin inhibitor (HQ-4) 0.05 Stin inhibitor (HQ-5) 0 . twenty three

DIDP 0.06 Fluorescent whitening agent (W-1) 0.10 Anti-irradiation dye (AI-3) 0.01 First layer: blue-sensitive layer>

Gelatin 1.10 Blue-sensitive silver halide emulsion (10 1 B) 0.26 Yellow coupler (Y-1) 0.70 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer (ST-2) 0.10 Sting inhibitor (HQ-1) 0.01 Dye image stabilizer (ST-5) 0.10 Image stabilizer A 0.15 DNP 0.05

D B P 0.10 Support: Reflective support Polyethylene laminated paper (containing a trace amount of colorant) The amount of each of the silver halide emulsions described above was expressed in terms of silver. In addition, (H-l) and (H-2) are added to each of the above coating solutions as a hardening agent, and the following surfactant (SC-1) is added as a coating aid, and The tension was adjusted.

S U—1: sodium i-propylnaphthalenesulfonate

S C-1: Sodium decyl sulfonate

DBP: dibutyl phthalate

DNP: dinonyl phthalate

D 0 P: Dioctyl phthalate

D I D P: di-i-decylphthalate

H-1: Tetrakis (vinylsulfonylmethyl) methane

H—2: 2,4-dichloro-6-hydroxy-s-triazine ′ sodium HQ-1: 2,5-zy

HQ—2: 2,5-di-sec-dodecylhydroquinone

HQ-3: 2,5-di-sec-tetradecyl hydroquinone

HQ—4: 2—sec—dodecyl mono 5—sec—tetradecinole / pydroquinone

HQ-5: 2,5-di [(1,1-dimethyl-41-hexyloxycarbonyl) butyl] hydroquinone

Image stabilizer A: P-t-octylphenol

Y-1

S— 丄 S oz

— 丄 s

9T

(i) «H ^{£ t} 0O- {\)> — NS ^z O ε— 丄 s

Z— 丄 S οτ

Ray s

6S STS00 / C00Zdf / X3d 0 £ IS60 contract OAV oz

Z-N

One IV

ε-Λη

Of STS00 / C00Zdf / X3d 0 £ IS60 contract OAV AI-3

W-1

The total calcium content of Sample 101 prepared above was 210 mg / m ^{2 as} measured by ICP emission spectrometry. In addition, the total amount of gelatin is, Ru 6. 5 gZm ² der o

[Preparation of Samples 102 to L07]

In the preparation of Sample 101, an alkyl alcohol derivative compound (A-1: oleic alcohol) was added in an amount of 0.5 times the amount of M-11 when the magenta coupler (M-1) in the third layer was dispersed. Calcium content in all layers (change of gelatin type: use of lime-processed lime-exchanged bone gelatin), total amount of gelatin used in all layers (gelatin content of green photosensitive layer as third layer) Samples 102 to 107 were prepared in the same manner except that the type of surfactant added to all layers (the amount of addition was the same as SC-1 of Sample 101) was changed as shown in the table below. Produced. In the table below, compound A: alkyl alcohol derivative compound, SA agent: surfactant, Ca: calcium, Ge1: gelatin. (3rd layer) (all layers)

No.Compound A S A agent C a content Total G e 1

mg / mg / m

10 1 None s c 1 6.

102 A—1 s c-1 1 6.

103 A-1 S C-1 1 6.

• 104 A—1 S C—1 6.

105 A-1 s-1 3 (*) 6.

106 A—1 s-1 3 (*) 6.

107 A-1 1s-1 3 (*) 5.

*: Isopropyl naphthalene sulfo Each of the samples obtained as described above was exposed to white light via an optical wedge with an exposure time of 0.5 seconds through an optical wedge according to a conventional method, and then subjected to development processing in the following development processing steps. . Treatment process Treatment temperature Time Replenishment amount

Color development 35.0 ± 0.3 ° C 45 seconds 80 ml / m ² Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds 2 15 ml Zm ²

Stabilized 30 to 34 ° C 60 sec 248m l / m ² Drying 60-80 ° C 30 sec The composition of the developing solution is shown below.

[Color developer tank solution and replenisher] Tank solution Replenisher Pure water 800 ml 1800 ml Triethylene diamine 2 g 3 g Dethylene glycol 10 g 10 g Bromide rim 0.0 1 g-Chloride rim 3.5 g-Potassium sulfite 0.25 g 0.5 g

N-ethyl-N-(/ 3-methanesulfonamidoethyl) 13-methyl-4 monoaminoaniline sulfate 6.0 g 10.0 g

N, N-Getylhydroxylamine 6.8 g 6.0 g Triethanolamine 10.0 g 10.0 g Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 2.0 g Optical brightener ( 4, 4 'diaminostilbene disulfonic acid derivative)

2.0 g 2.5 g Carbonated lime 30 g 30 g Water was added to make the whole volume 1 liter. The tank liquid was adjusted to pH = 10.10, and the replenishment was adjusted to pH = 10.60.

(Bleach-fixer tank solution and replenisher)

Gelatinent ferric ammonium pentaacetate ammonium dihydrate 65 g diethylene triammonium pentaacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 ml

2-amino-1 5-mercapto-1,3,4-thiazima, 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml water was added to make up the whole volume to 1 liter, and the pH was adjusted to 5.0 with carbonated lime or glacial acetic acid.

(Stabilizing solution tank solution and replenisher solution)

0—Feninole 1 1 0 g

5-Chloro-2-methyl-4-1-isothiazolin-3-one 0 2 g 2-Methyl-4-isothiazolin-1 3-one 0 2 g Dethylene glycol 10 g Optical brightener (Tinopearl SFP) 2 • 0 g 1 -Hydroxyshethylidene 1, diphosphonic acid 1 • 8 g bismuth chloride (45% aqueous solution) 65 g magnesium sulfate 7 hydrate 0 • 2 g

PVP (Polyvinyl alcohol) 1 • 0 g Ammonia (25% aqueous ammonium hydroxide) 2 • 5 g Triacetate triacetate / sodium trisodium salt 15 g Add water to make 1 liter The pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia.

At this time, the amount of the overflow solution from the color developing solution was 75 ml for the processing of 1 m ² of the light-sensitive material.

Next, as described in JP-A-7-234487, the replenisher of the color developing solution was regenerated as shown below, and the regenerated replenisher was subjected to a running treatment with a replenishment amount of 0 ml Zm ^2. I went.

(Method of regenerating color developer) The overflow solution of the color developing solution was stocked (stock solution), and the amount of stock solution at the time when 16 L of replenisher was replenished was 9.8 L. Next, add the chemicals listed below to 9.8 L of the stock solution, add water to make 16 L, and reuse it as a regeneration replenisher.

(Formulation of replenisher)

Stock liquid 9.8 L

N-ethyl-N-(-methanesulfonamidoethyl) 3-methyl-4 aminoaniline sulfate 57 g

N, N-Getylhydroxylamine 56 g Triethanolamine 93 g Diethylenetriaminepentaacetic acid sodium salt 12 g Optical brightener (4, '-diaminostilbenesulfonic acid derivative) 16 g Carbon dioxide 186 g Water was added to bring the total amount to 16 liters, and the pH was adjusted to 10 and 60 with KOH.

This regeneration treatment was repeated 20 times for each of the samples 101 to 107. That is, the number of rounds is 40. The regeneration rate was set at 100%.

《Evaluation》

Evaluation, after each 500 m ² treatment the sample, the green light maximum reflection density of the neutral image (Dm a _X) an optical densitometer (X- R ite Corporation X- R ite 3 1 O TR) using Measured. Next, the difference ADmax (maximum value-minimum value) between the green light maximum reflection densities in the sample 500 m ² was measured and calculated, and this was used as a measure of the density variation. The results obtained are shown in the table below. Sample number Concentration variation Maximum concentration Remark Δ Dma XD max

101 0. 025 2.18 Comparative example

102 0.01 2.25 The present invention

103 0. O i l 2.35 The present invention

104 0. O i l 2.33 The present invention

105 0.008 2.40 The present invention

106 0.006 2.42 The present invention

107 0.005 2.44 The present invention From the above table, it can be seen that the silver halide photographic light-sensitive material using the alkyl alcohol derivative compound according to the present invention has a small density variation even when a regenerating processing solution is used, and provides a good image. was gotten. This is an effect not expected in the prior art. Also, the maximum color density itself was higher than the comparative sample. Industrial potential

As described above, according to the present invention, a method for processing a silver halide photographic light-sensitive material which can provide a high image density and has excellent image density stability even when processed using a regenerating processing solution. Can be provided.

Claims

The scope of the claims

1. A method for processing a silver halide photographic material having at least one photosensitive layer and at least one non-photosensitive layer on a support, wherein the photosensitive layer or the non-photosensitive layer comprises an alkyl alcohol After imagewise exposing the silver halide photographic light-sensitive material containing the derivative compound, the overflow solution of the color developing solution at the time of continuous processing is regenerated, and the silver halide photographic light-sensitive material is processed in the following manner. A method for processing a silver halide photographic material, characterized by using a regenerated color developer.

2. The silver halide total calcium content of the photographic light-sensitive material, 0. 01-1 O m C port Gen Kagin'utsushi true photographic material according to claim 1, characterized in that gZm is ² Processing method.

3. The haguchi according to claim 1, wherein the silver halide photographic light-sensitive material contains an anionic surfactant having a benzene ring or a naphthalene ring. A processing method for a silver photographic photosensitive material.

4. The total gelatin content of the silver halide photographic light-sensitive material, 6. according to 2 g, any one of the Claims paragraphs 1 through the third term, which is a ² hereinafter m A method for processing a silver halide photographic material.