WO2004095132A1 - Silver halide photographic lightsensitive material and method of processing the same - Google Patents

Abstract

A silver halide photographic lightsensitive material, in particular, a silver halide photographic lightsensitive material that can reduce the occurrence of image surface defects even when subjected to mass development processing and is excellent in image stability, and a method of processing the same. More particularly, a 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 the lightsensitive layer or non-lightsensitive layer contains a phenol derivative compound and that the silver halide photographic lightsensitive material in its coating layers contains calcium whose total content is in the range of 10 to 0.01 mg/m2.

Description

 Description Silver halide photographic light-sensitive material and processing method

 The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to a silver halide photographic light-sensitive material and a processing method which are less likely to cause image surface defects even when developed in a large amount and have excellent image stability. 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 order to achieve rapid processing in response to the current situation and needs of such markets, approaches are being taken from two aspects: photosensitive materials and processing solutions. There have been many attempts to optimize the temperature and pH of processing solutions and to add additives such as development accelerators. However, these processes often involve performance degradation such as an increase in capri. On the other hand, although the hagage composition of a silver halide emulsion used in a light-sensitive material affects the development speed, it is known that especially when high chloride silver halide is used, the development speed is remarkably high. ing.

In addition to the improvement of silver halide emulsions, it is also necessary to improve color-forming components such as couplers having a high power ringing speed with oxidized color developing agents. For this reason, it is necessary to adjust the addition of couplers, high-boiling organic solvents, color-mixing inhibitors, anti-fading agents, etc. to be contained in the silver halide photographic light-sensitive material. However, such a rush When a large amount of silver halide photographic light-sensitive material applied to high-speed processing is developed, a problem has been found that surface defects occur in the processed image.

 In particular, when a large amount of rapid processing with a development time of 40 seconds or less is continued, or when the overflow solution of the color developing solution is regenerated and used for the processing of the silver halide photographic light-sensitive material, the image surface is reduced. It turns out that there is a problem that defects are raw.

As a result of various studies on these problems, it was found that the above problems could be solved by a silver halide photographic light-sensitive material using a specific compound and having a calcium content of 10 mg Zm ² or less in the coating layer. The present invention has been made. As another effect, it has been found that the effect of improving the image preservability by the phenolic compound is particularly large in the constitution of the present invention.

 Conventionally, the technology of a fuynol-based compound has been disclosed (see, for example, Patent Document 1); however, there is no description of the constitution of the present invention, nor is it a technology aimed at the effects of the present invention. The present invention relates to a silver halide photographic light-sensitive material having a novel constitution, and in particular, to a silver halide photographic light-sensitive material and a processing method which are less likely to cause image surface defects even when developed in a large amount and have excellent image stability. To provide.

(Patent Document 1)

 Japanese Patent Application Laid-Open No. H11-2880866 Disclosure of the Invention

 The above object of the present invention is achieved by each of the following constitutions.

(1) In a silver halide photographic material having at least one photosensitive layer and at least one non-photosensitive layer on a support, the photosensitive layer or the non-photosensitive layer Wherein the layer contains a phenol derivative compound and the total calcium content of the coating layer of the silver halide photographic material is from 10 mgZm ^{2 to} 0.01 mg / m ² . Silver halide photographic material.

 (2) The silver halide photographic material as described in (1), further comprising an anionic surfactant having a benzene ring or a naphthalene ring.

 (3) After overflowing the silver halide photographic light-sensitive material according to (1) or (2) with imagewise exposure, the overflow solution of the color developing solution generated during continuous processing is regenerated, A method for processing a silver halide photographic material, wherein the method is recycled for processing the silver photographic material. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention relates to 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 comprises containing derivative compound, and the total calcium content contained in the coating設層silver halide photographic material is characterized by a ^{10 m gZm 2 ~0.01 m gZm 2} .

 First, the phenol derivative compound will be described. The compound used in the present invention is a compound represented by the following general formula [A-2]. General formula [A-2]

In the general formula [A-2], R _{A21 to} R _A25 each represent a hydrogen atom or a substituent. Any substituent can be used as long as it is a substitutable group. Examples of such a substituent include an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, a halogen atom, a cyano group, a hydroxyl group, and the like. The substituents described on pages 1561-1564 can be mentioned. R _A21 to R _A25 may be the same or different to each other physician, R _A21 to R _A25 may be bonded to form a cyclic compound with each other. R _{A21 to} R _A25 may be linear or branched. At least one of R _A2 ^ is preferably a substituent. R _{A21 to} R _A25 are preferably a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or a halogen atom.

 The compound represented by the general formula [A-2] may be contained in any layer of the silver halide photographic light-sensitive material of the present invention, but it is preferable that the compound represented by the formula (A-2) be contained in the same layer as the dye-forming coupler. It is preferable because the effects of the invention can be remarkably obtained.

 The compound represented by the general formula [A-2] is preferably used in a mass ratio of from 0.01 to 100 times the dye-forming coupler, and furthermore, a silver halide photographic material. From the viewpoint of physical properties, it is preferable to use it in the range of 0.05 to 5 times. The compound represented by the general formula [A-2] is preferably used by emulsifying and dispersing, and more preferably used by dispersing in the same dispersion as the dye-forming coupler.

Hereinafter, specific compound examples of the compound represented by the general formula [A-2] used in the present invention are shown, and the compound represented by the general formula [A-2] used in the present invention includes: It is not limited by. A-1 2— 1 A— 2— 2

A-one 2—3 A-2-4

 A— 2— 5

 A-2-7

? H? ₃ H ₇ (i) OH A— 2— 8

 A— 2— 9 A— 2 10

A-2-11 A— 2— 12

COOCH ₃

According to the present invention, the calcium content in the coating layer of the silver halide photographic light-sensitive material is in the range of 10 mg Zm ² 0.01 mg / m ^2. materials 1 m ² of calcium atom contained in the calcium ions, the force Rushiumu salt, a mass in terms of calcium atoms for compounds to base hand containing calcium as the quantification method I CP (I nductively C onpi edPlasma) Emission analysis is used.

 The details of this analytical method are described in “Chemistry, Special Issue No. 127” (Nankodo, published in 1980) and VA Fassel: Anal. Chem., 46, 111A (1974). There is a description.

Gelatin, which is advantageously used as a binder for light-sensitive materials, usually contains several thousand ppm of calcium salts derived from raw materials and manufacturing processes, in terms of calcium atoms. Specifically, photosensitive materials for direct viewing that have been put into practical use usually contain 15 mg / m ² or more of calcium. In the present invention, the calcium content contained in the coating設層of the photosensitive ^{material, 10 mg / m 2 ~0.} O lm gZm is in the range of ^{2, 5 mg / m 2 ~0} . 0 1 mg Z more favorable preferable range of m ^2.

 In order to reduce the calcium content in the light-sensitive material, a method of using gelatin having a low calcium content as a binder, a coating solution applied to a support during the manufacture of the light-sensitive material, or a halogen solution contained in the coating solution are used. A method comprising desalting a dispersion containing a hydrophobic compound such as a silver emulsion or a coupler, or a gelatin-containing composition such as a gelatin solution by noodle washing, dialysis, ultrafiltration, etc. Preferably, it is used.

 In order to reduce the calcium content in gelatin, generally, ion exchange treatment is preferably used. As described in, for example, JP-A-63-296035, the ion exchange treatment is performed by mixing a gelatin solution with an ion-exchange resin when producing or using gelatin, particularly with a positive ion-exchange resin for removing calcium ions. A contacting treatment is preferably used.

In addition, as a gelatin having a low calcium content, calcium Acid-treated gelatin with less contamination of the medium.

 The gelatin used in the present invention is preferably a lime-processed gelatin subjected to a heat exchange treatment in view of the effects of the present invention. In addition, an oxidation treatment with hydrogen peroxide or the like can be performed for the purpose of reducing photographic activity.

Preferably gelatin as a binder one contained in the layer to be coated into a high port Gen halide photographic light-sensitive material of the present invention, the total coating amount of gelatin is the ^{7. 0 gZm 2 ~4. 0 gZm} 2 Is preferred. The total gelatin coating amount, 6. more preferably ^{2 gZm 2 ~ 5. 0 gZm 2} , 5. 7~5. And most preferably l gZm ^2.

 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, and the activator has a benzene ring or a naphthalene ring and a surfactant having an anion group. Any one may be used as long as it has a sulfonic acid group as the anion group.

 Further, a surfactant in which a sulfonic acid group is directly substituted on a benzene ring or a naphthalene ring is preferable.

 Preferred compounds include the following.

 S-1: Sodium dodecylbenzenesulfonate

 S—2: sodium octadecylbenzenesulfonate

 S-3: isopropyl naphthalene sulfonic acid

 The surfactant may be added to any layer in the silver halide photographic light-sensitive material, and the amount added is appropriately determined according to the design of the light-sensitive material.

The silver halide used in the silver halide emulsion layer according to the present invention includes any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide and the like. Two

9

 The silver halide grains preferably used in the present invention 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%. The following is preferred. More preferably, it is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%. The silver halide grains may be used alone or as a mixture with other silver halide grains having different compositions. Further, 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. % Or more 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 example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) 2 Particles having shapes such as octahedron, tetrahedron, and dodecahedron can be prepared and used by methods described in documents such as 1, 39 (1973). Further, particles having twin planes may be used.

As the silver halide grains according to the present invention, grains having a single shape may be used. Alternatively, particles of various shapes may be mixed.

 The particle size of the silver halide grains according to the present invention is not particularly limited, and is preferably 0.1 to 1.2 μτα, more preferably 0.1 to 1.2 μτα, in consideration of other photographic properties such as power and rapid processing and sensitivity. It is in the range of 0.2 to 1.0 m. The particle size can be measured by various methods generally used in the five technical fields. A typical method is Lapland's "Particle Size Analysis" (ASTM Symposium 'On' Light-Microscopy, pp. 94-122, 1955) or 3rd Edition ”(co-authored by Mies and J. Muss, Chapter 2, published by Macmillan, 1966).

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

 The size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse. Preferably the coefficient of variation is 0.22 or less, more preferably 0.2.

It is a monodisperse silver halide grain of 15 15 or less. 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, For particles other than cubes and spheres, the projected image is converted to a circular image of the same area.

Represents a diameter of 20. 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 may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time Alternatively, the seed particles may be grown after they are 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 haematogenide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. preferable. Further, as one form of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

 Further, a water-soluble silver salt and a water-soluble halide salt are supplied from an addition device disposed in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524. Apparatus for supplying an aqueous solution, apparatus for continuously adding aqueous solutions of a water-soluble silver salt and a water-soluble halide salt described in German Published Patent No. 2,921,164, etc. 6-5 0 1 7 7 6 A device for taking out the reaction mother liquor out of the reactor and concentrating by ultrafiltration method to form grains while keeping the distance between silver halide grains constant, etc. May be used.

 If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a compound such as a tetracyclic compound or a sensitizing dye may be added to the nitrogen-containing compound 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 a high silver ion concentration condition, or a method of ripening under a high pH condition can be used.

The reducing agent used for the reduction sensitization of the silver halide emulsion according to the present invention includes: Examples thereof include stannous salts such as tin, borane such as tri-t-butylamborane, sulfites such as sodium sulfite and sulfurous lime, reductones such as ascorbic acid, and thiourea dioxide. Of these, thiourea dioxide, ascorbic acid and its derivatives, and sulfites can be preferably used. The method using a reducing agent as described above is preferable because of its excellent reproducibility, as compared with the case of performing a reduction sensation by controlling the silver ion concentration and pH during ripening.

 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 depending on the etc. silver ion concentration, in general, the silver halide emulsion per mol 0 ^7-1 0 _ ² mol is preferred.

 After the reduction reaction, a small amount of an oxidizing agent may be used to modify the reduction nucleus or deactivate the remaining reducing agent. Examples of the compound used for such a purpose include hexacyanoferrate (III) oxide, promosuccinimide, p-quinone, perchloric acid phosphate, hydrogen peroxide, and the like.

The silver halide emulsion according to the present invention can be used in combination with a reduction sensitization method, 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, an iris sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, and an io sensitizer is preferable. . Examples of the sensitizer include thiocyanate sulfate, arylthiocarbamidothiourea, arylisothiocyanate, cystine, p-toluenethiosulfo. And rhodanine.

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 to be used include dimethyl monodanin, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually from 1 × 10 to ⁴ mol to IX 10_ per mol of silver halide. Preferably it is ⁸ moles. More preferably 1 X 10- ⁵ mol ~ 1 X 10 one ⁸ mol.

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 (Π) described in the lower column on page 7 of JP-A-2-14636, and specific compounds thereof include Are the compounds of (Ila-1) to (IIa-8), (lib-1) to (IIb-7) described on page 8 of the publication, and 1- (3-methoxyphenyl). 15-mercaptotetrazole and the like. These compounds are added according to the purpose in the steps of preparing silver halide emulsion grains, chemical sensitization step, completion of chemical sensitization step, coating liquid preparation step and the like. When performing these presence in the chemical增感compounds preferably used in an amount of 1 X 10_ about ⁵ mol ~ 5 X 10- ⁴ mole per mole of silver halide. When added during chemical增感completed, the amount of 1 X 10- ⁶ mole ~ 1 X 10 approximately one ² mol per mol of silver halide is preferred, 1 X 10- ⁵ mol ~ 5 X 1 CT ³ moles More preferred. In the coating solution preparation step, when added to the silver halide emulsion layer, the amount of 1 X 1 0- ⁶ mol ~ 1 X 1 0 about one ¹ mol per mol of silver halide preferably, 1 X 1 0 mol ~ 1 X 1 0- ² moles is more preferable. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 to ⁹ mol to 1 × 10 to ³ mol.

 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 is combined with a yellow coupler, a magenta coupler, and a cyan coupler to obtain a spectral light in a specific region of a wavelength range of 400 to 900 nm. It has a layer containing the silver halide emulsion that was felt. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

 As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any of the known compounds can be used. As the blue-sensitive dye, Japanese Patent Application No. 2-51112 BS-1 to 8 described on pages 108 to 109 of the specification can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to 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 exposing the silver halide photographic light-sensitive material according to the present invention to 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 in Japanese Patent Application No. 3-73619, pages 12 to 14 are preferably used. It is preferable to use the supersensitizers SS-1 to SS-9 described on pages 14 to 15 of the same specification in combination with these dyes.

When exposing the silver halide photographic light-sensitive material according to the present invention using a laser The use of an exposure apparatus using a semiconductor laser is advantageous in terms of downsizing of the apparatus. In scanning exposure, the exposure time per pixel corresponds to the exposure time actually received by the silver halide emulsion.However, in the case of scanning exposure with one laser beam, the exposure time per pixel is 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 the beam diameter (beam diameter) / (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.

 One example of a laser printer device that can be applied to such a system is described in, for example, Japanese Patent Application Laid-Open Nos. 55-4071, 59-11062, and 63-19.

No. 7947, JP-A-2-74942, JP-A-2-236583, JP-B-56-14963, JP-A-56-40822, European wide-area patent 77,410, Electronics and Telecommunications Department Joint Technical Report 80, 244, And Movie and TV Technology Magazine 1984/6 (3

82), pages 34 to 36, and the like.

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, dyes having absorption in the visible region are described in Japanese Patent Application No. 2-511124, pages 117 to 118. The dyes of AI-11 to 11 are preferably used. Examples of the infrared absorbing dye include the general formulas (I), (I1), and (III) described in the lower left column on page 2 of JP-A-11-280750. The compound represented by the formula has preferred spectral characteristics, and silver halide photographic milk It is preferable because it does not affect the photographic properties of the agent and does not stain due to 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.

 As the coupler used in the silver halide photographic light-sensitive material according to the present invention, a coupling reaction having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by force coupling reaction with an oxidized form of a color developing agent. Any compound capable of forming a substance can be used, but it can be used as a yellow power brush having a spectral absorption maximum wavelength in the wavelength range of 350 to 500 nm, and in a wavelength range of 500 to 600 nm. A typical example is a magenta mirror having a spectral absorption maximum wavelength, and a cyan coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 75 ° 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 a compound represented by the general formula (Y-1) described on page 8 of Japanese Patent Application No. 2-324208. Mention may be made of the couplers represented. 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 of a preferable color tone. Examples of the magenta coupler include couplers represented by general formulas (M-I) and (M-II) described on page 12 of Japanese Patent Application No. 2-324208. 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 reproducing colors ranging from blue to purple and red, and are also excellent in detail descriptive power. Better.

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 Application No. 2-324208. Specific compounds include those described as CC-11 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, a water-insoluble high-boiling organic solvent having a boiling point of 150 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 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 simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. As the high boiling organic solvent that can be used for dissolving and dispersing the coupler, phthalic acid esters such as octyl phthalate and phosphoric acid esters such as tricresyl phosphite 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. As the water-insoluble and organic solvent-soluble polymer used at this time, poly (N-t-butylacrylamide) and the like can be mentioned.

In order to shift the absorption wavelength of the color-forming dye, the compound (d-11) described in Japanese Patent Application No. 2-232430, page 33, the compound (d-11) described in page 35 of the same specification, Compounds such as Α′-1) can be used. In addition, U.S. Pat. The fluorescent dye releasing compounds described in 4,187 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 mol / mol of silver halide. used in X 1 0 _ ² ~ 1 mol of the range.

 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 Japanese Patent Application No. 64-1640. 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 5~5 mg Zm ^2.

 In the silver halide photographic light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder. However, if necessary, other gelatin, gelatin derivatives, gelatin and other polymers can be used as a graph 1 and a polymer. In addition, hydrophilic colloids such as proteins other than 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, a support having on its surface a polyolefin resin layer containing a white pigment is preferred. 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, sulfate of alkaline earth metal such as barium sulfate, carbonate of alkaline earth metal such as calcium carbonate, silica such as finely divided gay acid and synthetic silicate, calcium gaymate, 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 as a content in the water-resistant resin layer, and more preferably 13% or more. The content is preferably at least 15 mass%, more preferably at least 15 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, and preferably 0.10 or less, as the coefficient of variation described in the publication. More preferably, it is.

 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) Or one or more subbing layers to improve the properties, dimensional stability, rub resistance, hardness, antihalation properties, frictional properties or other properties.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and force coating, which can apply two or more layers simultaneously, are particularly useful as the coating method. Generally, silver halide photographic light-sensitive materials elute from the light-sensitive material into the developing solution from the light-sensitive material during the developing process, and the organic compounds (for example, the sensitizing dyes and inhibitors) elute and accumulate in the developing solution. As a result, it is known that the development reaction is suppressed. Therefore, it is necessary to reduce the amount of eluted substances in the developer and to maintain the concentration constant. In a normal development processing method, halo compounds and organic compounds are eluted from a photosensitive material into a developing solution, and further, a developing agent, a preservative and an alkali agent are consumed and reduced. Therefore, a replenisher is added to the developer to keep these concentrations substantially constant and maintain the development characteristics, and the added amount is allowed to flow out of the developer tank system as an overflow solution and accumulated in the developer. Halide ions and organic compounds are removed from 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, after the imagewise exposure of the silver halide photographic light-sensitive material, an overflow solution of a color developing solution generated during continuous processing is regenerated and reused in the processing of the silver halide photographic light-sensitive material. It is characterized by the following. By recycling and using the developer, 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, regeneration using the ion exchange resin described in JP-A-3-69936, JP-A-3-194552, JP-A-55-144240, JP-A-53-132343, JP-A-57-146249 and JP-A-61-95352. JP-A-5-85722, JP-A-5-172, and JP-A-51-85722. No. 37731, No. 56-1049, No. 56-27142, No. 56-33644, No. 56-149036, No. 61-10199, No. 61-52459 A method using electrodialysis is exemplified.

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

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

 CD-I) N, N—Jetil-p—Fenylenediamine

 CD— 2) 2—Amino 5—Jetilamino Toruen

 CD-3) 2-amino-5_ (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-droxitytyl) amino) aniline

 CD-5) 2-Methyl-41- (N-Ethyl-N- (S-Hydroxyshetyl) Amino) Anilin

 CD-6) 4-Amino 3-Methyl-N- (β- (Methanesulfonamide) ethyl) -Ryrin

 CD-7) N- (2-amino-5-ethylpyraminophenyl) methane sulfoneamide

 CD-8) N, N-dimethyl-p-phenylenediamine

 CD-9) 4-amino-3-methyl-1-N-ethyl-1N-methoxylaniline

 CD-10) 4-Amino-3-methyl-1-N-ethyl-N- (Ethoxyethyl) aniline

CD-11) 4-amino-3-methyl-N-ethyl-N- (β-y) Chill) Anilin

Color developing agent used in the present invention is usually developer 1 liter per 1 X 1 0 is used in one ² ~ 2 X 1 0- ¹ mols, from the viewpoint of rapid processing color developer 1 Li preferably used in Tsu torr per ^{1. 5 X 1 0- 2 ~2 X} 1 0 one ¹ mole range. The color developing agent used in the image forming method of the present invention may be used alone, or may be used in combination with other known P-phenylenediamine derivatives.

 In the preferred developer of the present invention, it is preferable that benzyl alcohol is not substantially contained. Here, “substantially not contained” means that benzyl alcohol is 2 m 1 ZL or less, and it is most preferable that benzyl alcohol is not contained at all in the present invention.

 The color developer used in the present invention may contain the following components in addition to the above components. As the alkaline agent, for example, sodium hydroxide, sodium hydroxide, sodium metaborate, potassium metaborate, sodium phosphate, sodium phosphate, potassium phosphate, borax, silicate, etc., alone or in combination Therefore, they can be used together within a range that does not cause precipitation and maintains the pH stabilizing effect. Furthermore, for the purpose of dispensing, or for the purpose of increasing ionic strength, etc., sodium hydrogen phosphate, sodium hydrogen phosphate, sodium bicarbonate, bicarbonate rim, Various salts such as borates can be used.

Further, the color developing solution according to the present invention includes, in place of hydroxylamin conventionally used as a preservative, JP-A-63-146043, JP-A-63-146042, JP-A-63-1604-2. Nos. 4,604, 1,63-146,040, 63-1,359,38,63,11,748, and hydroxylamine derivatives described in JP-A-64-62639, and JP-A-11-34343 Hydroxamic acids, hydrazines, hydrazides, phenols, monohydroxyketones, etc. described in No. 8, etc. —Aminoketones, sugars, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, thioximes, diamide compounds, fused ring amines, etc. are preferably used as organic preservatives. .

 These compounds can be used in combination with a conventionally used hydroxylamine and the above-mentioned organic preservative. However, it is more preferable not to use hydroxylamine 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, 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, 2,577,127 and Nonionic compounds such as polyethylene glycol and derivatives thereof and polythioethers described in JP-B-44-9504, organic solvents and organic amines, ethanolamines, ethylenediamines, and gelamines described in JP-B-44-9509. Includes tanolamine and triethanolamine. Also, phenethyl alcohol described in U.S. Pat. No. 2,304,925 and others, acetylene glycol, methyl ethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, and amines And the like.

Further, the color developing solution used in the present invention may be, if necessary, ethylene glycol, methyl cellulose solvent, methanol, acetone, dimethylformamide, 8-cyclodextrin, and other Japanese Patent Publication No. 47-33378. The compounds described in each of the publications are used as an organic solvent for increasing the solubility of the developing agent. 05152

24

 Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol sulfate, phenidone N, N'-getyl-p-aminophenol hydrochloride,, N ,， ', Ν'-tetramethyl- 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, competing couplers, fogging agents, development inhibitor releasing couplers (so-called DIR couplers), development inhibitor releasing compounds, etc. can be added. Various additives such as an inhibitor and a layering effect promoter 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 color solution used in the present invention is prepared by adding a concentrated aqueous solution containing a plurality of components each of which can stably coexist, or a solution prepared in advance in a small container in a solid state in water, and stirring the water. A developer can also be prepared.

The sulfite concentration in the color developing solution according to the present invention is preferably 1 × 10 ¹² mol / L or less. Particularly good when the following 7 X 10- ³ mole ZL comprises 0, preferred when the following 5 X 10_ ³ mol / L, especially including 0.

In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to pH 9.8. Used in the range of 12.0. The processing temperature of color development used in the present invention is preferably 35 ° C. or more and 7 CTC or less. The higher the temperature, the shorter the processing time is possible, which is preferable. However, it is preferable that the processing temperature is not too high from the viewpoint of the stability of the processing solution. The color development time is preferably 45 seconds or less 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 the 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.

Bleaching agents which can be used in the bleach-fixing solution used in the present invention is not limited force ^"5 'is preferably a metal complex salts of organic acids. The complex salts, polycarboxylic acids, § amino polycarboxylic acid or oxalic An organic acid such as an acid or citrate is coordinated to a metal ion such as iron, cobalt, copper, etc. The most preferred organic acid used to form a metal complex salt of such an organic acid is polycarboxylic acid. The polycarboxylic acid or aminopolycarboxylic 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-1-205262, pp. 58-59.

These bleaches are used in an amount of 5 to 450 g, preferably 20 to 250 g, 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 optionally contains 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 (III) bleach and the silver halide fixing agent, A special bleach-fixing solution having a composition comprising a combination of an 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, potassium thiosulfate, thiosulfuric acid Representative examples thereof include thiosulfates such as sodium and ammonium thiosulfate, thiocyanates such as potassium thiocyanate and sodium thiocyanate, and 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 includes boric acid, borax, sodium hydroxide, sodium hydroxide, sodium carbonate, sodium carbonate, sodium bicarbonate, sodium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide. And the like can be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants can be contained. In addition, 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 and dimethyl sulfonamide Organic solvents such as dimethyl sulfoxide Etc. can be included as appropriate. The bleach-fixing solution used in the present invention includes JP-B-46-280, JP-B-45-85006, JP-B-46-556, Belgian Patent No. 770910, and JP-B-45-88. Various bleaching accelerators described in JP-A Nos. 36,53-9854, 54-71634 and 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 pH range of 5.0 to 8.5. The treatment temperature is 80 ° C or less, preferably 55 ° C or less, and the evaporation is suppressed. 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 5.5-10.0. The treatment temperature of the water washing treatment is preferably 15 ° (: to 60, more preferably 20 ° C to 45 ° C. The time of the water washing treatment is preferably 5 to 90 seconds. In the case of performing the treatment, 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, and it is particularly preferable that the treatment is sequentially performed with a treatment time increased by 20% to 50% of that of the front tank.

As a development 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, the endless belt type, in which the photosensitive material is fixed on a belt and transported, even if it is a transporter type that transports the photosensitive material between rollers placed in the processing tank. The processing tank may be formed into a slit, and the processing liquid may be supplied to this processing tank and the photosensitive material may be conveyed, the processing liquid may be sprayed, or the processing liquid may be sprayed. Etbu method by contact with carrier made by viscous treatment Etc. 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 and contamination between processing tanks ゃ evaporation of the processing solution are saturated and stabilized. This is especially effective when the treatment is performed later.

 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.

 Example 1

 << Silver halide color photographic 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)

 In one liter of a 2% aqueous gelatin solution kept at 40 ° C, add the following (Solution A) and (Solution B) over 30 minutes while controlling pAg to 7.3 and pH to 3.0. The following (Solution C) and (Solution D) were simultaneously added over 180 minutes while controlling the pAg to 8.0 and the pH to 5.5. 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 aqueous sodium hydroxide solution.

 (A liquid)

Sodium chloride 3. 42 _g bromide force helium 0. 03 g Water to make 200m l (Solution B)

 200 ml with 10 g water

(C solution)

Sodium chloride 102.7 g K ₂ I r C ₁₆ 4 X 10

K ₄ Fe (CN) 6 2 X 10 g Potassium bromide 1.0 g 600 ml with water (D solution)

 After adding 300 g of silver nitrate water and adding 600 ml of each 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, and then gelatin was added. Emulsion EMP-1 was obtained as a monodisperse cubic emulsion having an average particle size of 0.40; «m, a coefficient of variation of particle size distribution of 0.07, and a silver chloride content of 99.5 mol% by mixing with an aqueous solution. .

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

The above emulsion EMP-1 was optimally chemically sensitized at 60 ° C using the following compounds. Similarly, after optimal chemical sensitization of emulsion EMP-1B, sensitized emulsion EMP-1 and emulsion EMP-1B were mixed at a silver ratio of 1: 1. Thus, a red-sensitive silver halide emulsion (10 1 R) was obtained.

Chio sodium sulfate 1 X 10- ⁴ Mo g chloroauric acid 2 X 10 one ⁴ Mo g X Stabilizer: STAB- 1 3 X 10- g X Stabilizer: STAB- 2 3 X 10- g X Stabilizer: STAB- 3 3 X 10- ⁴ mode g X sensitizing dyes: RS - 1 1 X 10 gX sensitizing ^{dyes: RS - 2 1 X 10_ 4} g

S TAB— 1: 1— (3-acetamidodenyl) -1-5-mercaptotetrazole

 S TAB— 2: 1-Phenyl-5-mercaptotetrazole

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

Also the red-sensitive emulsion, 1 SS- 1 silver halide mole 2. 0 X 10 - ³ were added.

 (Preparation of green photosensitive silver halide emulsion)

In the preparation of the above emulsion EMP-1, the average particle size was 0.40 m 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. The emulsion EMP_2 was obtained as a monodisperse cubic emulsion having a coefficient of variation of 0.08 and a silver chloride content of 99.5%. Next, in the preparation of the emulsion EMP-1, the average particle size was adjusted 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. Emulsion EMP-2B was obtained as a monodisperse cubic emulsion having a particle diameter of 50 ^ m, a coefficient of variation of 0.08 and a silver chloride content of 99.5%. The emulsion EMP-2 prepared above was subjected to optimal chemical sensation at 55 ° C. using the following compounds. Similarly, after optimal chemical sensitization of emulsion EMP-2B, sensitized emulsion EMP-2 and emulsion EMP-2B were mixed at a silver ratio of 1: 1. Thus, a green light-sensitive silver halide emulsion (101 G) was obtained.

Chio sodium sulfate 1 X 10- ⁴ mol / mol A g X chloroauric acid 1. X 10- ⁴ mol / mol A g X Stabilizer: S TAB- 1 2. 5 X 10 _4 mol / mol A g X stable agent: S tAB- 2 3. 1 X 10- 4 mol / mol A g X stabilizer: S tAB- 3 3. 1 X 10_ 4 mol / mol A g X增感dye: GS- 1 ⁴ X 10- 4 Mol Z mol A g X

(Preparation of blue-sensitive silver halide silver halide emulsion)

 In the preparation of Emulsion EMP-1, the average particle size was 0.7 mm 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. The emulsion EMP-3 was obtained as a monodisperse cubic emulsion having a size of μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5%. Also, in the preparation of the emulsion EMP-1, the average particle size was adjusted 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. Emulsion EMP-3B was obtained as a monodisperse cubic emulsion having a length of 64 m, a coefficient of variation of 0.08 and a silver chloride content of 99.5%.

 The above emulsion EMP-3 was optimally chemically sensitized at 6 CTC using the following compounds. Similarly, after optimally chemical sensitizing Emulsion EMP-3B, 增 Emulsified EMP-3 and EMP-3B were mixed at a silver ratio of 1: 1. Thus, a blue-sensitive silver halide emulsion (10 1 B) was obtained.

Sodium thiosulfate 1 X 10_ ⁴ mol Z mol A g X Gold chloride acid 2 X 10- ⁴ mol / mol A g X Stabilizer: STAB- 1 2 X 10 one ⁴ Mo g X Stabilizer: STAB- 2 2. X 10 g X Stabilizer: STAB- 3 2. 1 X 10 g X增感^{dye: BS- 1 4 X 10- 4 g} X增感dye: BS- 2 1 X 10 ^-4 Mo g X

GS-1

RS-1

10 《Preparation of silver halide photographic light-sensitive material》

A reflective support was produced by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 gZm ² . However, on the side to which the photosensitive layer was applied, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by mass was laminated.

15 After subjecting this reflective support to corona discharge treatment, a gelatin undercoat layer was provided, and further, each layer having the following constitution was provided thereon, to prepare Sample 101 which is a silver halide 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) 3.20 34 g, (ST-2) 3, 34 g, (ST-5) 3.34 g, stin prevention 0.34 g of agent (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) and ethyl acetate 60 m Add 1 to dissolve, and add this solution to 10% containing 20% surfactant (SU-1) 7 ml A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of an aqueous gelatin solution using an ultrasonic homogenizer. This yellow coupler dispersion was mixed with the blue-sensitive silver halide emulsion (101B) prepared above to prepare a coating solution for the first layer.

 (Preparation of coating solution for 2nd to 7th layers)

 The coating liquids for the second layer to the fifth layer were prepared using the following additives in the same manner as in the preparation method of the first layer coating liquid.

 (Configuration of sample 101)

<7th layer: protective layer> gZm ² gelatin 0.70

 D I D P 0.005 Silicon dioxide 0.003 6th layer: UV absorbing layer>

 Gelatin 0.30 UV absorber (ϋV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Stain inhibitor (HQ-5) 0 . 04

 Ρ V Ρ (polyvinyl pyridine) 0.03 Anti-irradiation dye (AI-1) 0.01 5th layer: red-sensitive layer>

Gelatin 1.20 Red photosensitive silver halide emulsion (10 1 R) 0.2 1 Cyan coupler (C-1) 0,25 Cyan coupler (C-2) 0,08 Dye image stabilizer (ST-1) 0,10 Sting inhibitor (HQ-1) 0,004

D B P 0, 10

D O P 0 20

<4th 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 10 Anti-irradiation dye (AI-1) ) 0 02 <3rd layer: green photosensitive layer>

Gelatin 1 20 Green photosensitive silver halide emulsion (10 1 G) 0 1 Magenta coupler (M-1) 0 20 Dye image stabilizer (ST-3) 0 20 Dye image stabilizer (ST-4) 0 17 DIDP 0 1 3

DBP 0 13 Anti-irradiation dye (AI-2) 0 2 1st layer: middle 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 23 DIDP 0 06 Fluorescence enhancement Whitening agent (W-1) 0 10 Anti-irradiation dye (AI-3) 0 1 1st layer: Blue photosensitive layer>

 Gelatin 1 10 Blue-sensitive silver halide emulsion (101B) 0 26 Yellow coupler (Y-1) 0 70 Dye image stabilizer (ST-1) 0 10 Dye image stabilizer (ST-2) 0 10 Stin Inhibitor (HQ-1) 0 0 1 Dye image stabilizer (ST-5) 0 10 Image stabilizer A 0 1 5 DN P 0 05

DBP 0.10 Support: Reflective support 1 Polyethylene laminated paper (containing a trace amount of colorant) The amount of each silver halide emulsion added was expressed in terms of silver. In addition, (H-1) 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. Also, Preservative F-1 was added as appropriate.

 S U-1: Tree i-propyl naphthalene sulfonate

 S C-1: Sodium decyl sulfonate

 DBP: dibutyl phthalate

 DN P: dinonyl phthalate

 D 0 P: Dioctylphthalate

 D I D P: G i-decyl phthalate

 H—1: Tetrakis (vinylsulfonylmethyl) methane

 H—2: 2,4-dichloro-6-hydroquinone s—triazine′sodium HQ—1: 2,5—di-t-one-year-old octylhydroquinone

 HQ—2: 2,5—Gee sec—Dodecylhydroquinone

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

 HQ—4: 2-sec-dodecyl 5-—sec-tetradecylhydroquinone

 H Q—5: 2,5-di [(1 dimethyl-4-1-hexyloxycarbonyl) butyl] hydroquinone

 Image stabilizer A: P-t-octylphenol

Y-1

ε— 丄 s

Z— 丄 S

Les s

3-0

 8S

ZSTS00 / C00Zdf / X3d S60 contract OAV

ε-Λη

3-ΛΠ

Ray ΛΠ

s— 丄 s

 — 丄 S

6S

ZSTSOO / COOZdf / X3d S60 contract OAV AI-1

Al— 2

Al— 3

W-1

F-1

(50%) (46%) (4%) molar ratio Next, in the above configuration, the type of the surfactant to be added to each layer (the same molar amount was added), the phenolic compound to be added at the time of dispersing the magenta coupler in the third layer, and the calcium content (gelatin Change type: use lime-processed lime-processed bone gelatin and the total amount of gelatin used in all layers (keep the amount of coated gelatin in all layers and the coating amount ratio of each layer of sample 101) (Changes) were changed as shown in the table below to prepare samples 102 to 107. (In the table, Ca: calcium, Ge1: gelatin)

Bit fee Surfactant Total G e 1 Remarks

No. phenol Ca content type m ²

 System compound mg / m "

1 0 1 None 2 1 0 S C— 1 6.5 Comparative example

1 0 2 A— 2— 9 2 1 0 S C— 1 6.5 Comparative example

1 0 3 A— 2— 9 9 S C-16.5 The present invention

1 04 A— 2— 9 0 S C— 16.1 Comparative Example

1 0 5 A— 2— 9 9 S— 36.1 The present invention

1 06 A— 2— 9 7 S—36.1 The present invention

107 A—2—97 S—35.7 The present invention Each of the obtained samples was exposed to white light with an exposure time of 0.5 seconds by a conventional method, and then developed by the following developing process. Processing was performed.

Use a small automatic processor for each sample to regenerate the color developer The processing was continued until the replenishment amount of the developing processor became three times the capacity of the developing tank.

 Treatment process Treatment temperature Time Tank capacity

 Color development 35.0 ± 0.3 ° C 45 seconds Ό Lo 1 m 1 / m 'Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds 4 L2 15 ml in Rinse 30-34 ° C 90 seconds 4 L 248m lm 'Dry 60 ~ 80 ° C 6◦sec

 The composition of the developing solution is shown below.

 [Color developer tank solution and replenisher] Tank solution Replenisher Pure water 800 ml 800 ml l bromide rim 0.02 g

 Potassium chloride 2.0 g

 Potassium sulfite 0.25 g 0.5 g

N-ethyl-N- (monomethanesulfonamidoethyl) —3-methyl-14-aminoaminosulfonic acid salt 4.5 g 9.2 g

N, N-Jetylhydroxylamine 5. Og 9.0 g Triethanolamine 10. Og 15. Og Diethylenetriaminepentaacetic acid pentasodium salt 2. Og 2.0 g Fluorescent whitening agent (4, '' Diaminostilbene disulfonic acid derivative)

2.0 g 2.5 g Potassium carbonate 27 g 30 g Add water to bring the total volume to 1 liter. Adjust the tank liquid to pH = 10.10 and the replenisher to pH = 10.60. (Bleach-fixer tank solution and replenisher)

 Ferric ammonium diethylenetriaminepentaacetate dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3, thiadiazole 2.0 g ammonium sulfite ( (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust the pH to 6.5 with carbonated lime or glacial acetic acid.

 (Stabilizing solution tank solution and replenisher solution)

 0—phenylphenol 1.0 g

5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1— Hydroxyethylidene 1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate / hydrate 0.2 g

PVP 1.0 g Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

 [Regeneration method of color developer]

As a result of replenishing 6 L of color developer, 4.8 L of overflow solution was collected and anion exchange resin (Rohm's Haas Co.) Validate IRA-400) 80-minutes per minute in a plastic cylindrical column (12.5 cm inside diameter, resin layer height about 4 Ocm) packed with 5 L; Received.

 N, N-Jetylhydroxylamine, N-ethyl-N-(/ 3 methansulfonamidoethyl) -1,3-methyl-14-aminoaminophosphoric acid sulfate, triethanolamine, optical brightener (4,4 'diaminostilbene) Sulfonic acid derivative) and carbonic acid lime were quantified, and when water was added to make a total volume of 6 L, the replenisher was prepared so as to have the above-mentioned composition. Further, 2.4 g of sodium diethylenetriaminepentaacetate was added to the total volume of 6 L, and pH was adjusted to the same value as the replenisher with potassium hydroxide and sulfuric acid. The solution prepared in this manner was used as a replenisher thereafter, and was regenerated and used in the same manner as above each time 6 L of replenishment was completed.

 First treatment of anion exchange resin: 6 L of 0.5 MZL sodium bicarbonate solution is passed through the column at 80 ml / min, followed by washing with 6 L of distilled water at 160 ml / min And used for regeneration of the developer.

 From the second time on: 4.8 L of developing solution was used. After washing, 6 L of distilled water was passed through at a rate of 160 m 1 per minute, washed and treated in the same manner as the first time, and used for regenerating the developing solution. .

 《Evaluation》

The processing was performed using the above-mentioned running solution in an amount of 500 m ² for each of the silver halide color photosensitive materials. At this time, the number of surface defects per 10 m ² of the neutral image was measured.

A magenta image sample was prepared, and the initial reflection density of 1.0 was exposed to sunlight on an outdoor exposure table for 30 days, and the green reflection density before and after the irradiation was measured to measure the fading rate. The above results are shown in the table below. Sample Number of surface defects Fading rate (%) Remarks

 N 0 0 m

10 1 1 19 35 Comparative example

 102 259 17 Comparative example

 103 38 The present invention

 104 69 2 Comparative example

 105 15 7 The present invention

 106 1 1 6 The present invention

 107 9 9 present invention From the above table, in the sample according to the present invention, the number of surface defects was small, and a good image was obtained. This is an effect not expected in the prior art.

 Further, the effect of preventing light fading was larger than that of the comparative sample.

 Example 2

 Using the samples 101 to 107 manufactured in Example 1, the following processing was performed. When the overflow solution of the color developing solution was stocked (stock solution), and the replenisher solution was replenished with 16 L, the stock amount became 9.8 L. Next, the following formulation was added to 9.8 L of the stock solution, and water was added to make 16 L, which was reused as a regeneration replenisher.

 (Regeneration replenisher formulation)

 Stock liquid 9.8 L

N-Ethyl-1-N- (; 8-Methanesulfonamidoethyl) -1-Methyl-4-1 Aminoaniline sulfate 57 g

N, N-Jetylhydroxylamine 56 g Triethanolamine 93 g Nethylentriamine sodium pentaacetate 12 g Optical brightener (4,4 'diaminostilbene sulfonic acid derivative) 16 g Potassium carbonate 186 g Add water to bring the total volume to 16 liters and adjust to pH = 10.60 with KOH.

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

 By the above processing, the same evaluation as in Example 1 was performed for each sample. The results obtained are shown in the table below. Sample Number of surface defects Fading rate (% Remarks

 N 0 0 m

10 1 1 89 18 Comparative example

 102 33 1 25 Comparative example

 103 37 1 1 The present invention

 104 65 16 Comparative example

 105 1 7 The present invention

 106 10 6 The present invention

107 9 6 The present invention In the regenerating process, the comparative sample has many surface defects, whereas the present invention has a small number of surface defects and a large improvement. Also, as in Example 1, the effect of preventing light fading was greater than that of the comparative sample. Industrial potential

 As described above, with the constitution specified in the present invention, it is possible to provide a silver halide photographic light-sensitive material and a processing method which are less likely to cause image surface defects even in a large amount of development processing and have excellent image stability. Can be.

Claims

The scope of the claims

1. 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 contains a fuynol derivative compound. A silver halide photographic light-sensitive material characterized in that the total calcium content in the coating layer of the silver halide photographic light-sensitive material is 10 mg / Zm ^{2 to} 0.01 mg / m ² .

 2. The silver halide photographic material according to claim 1, further comprising an anionic surfactant having a benzene ring or a naphthalene ring.

3. After the imagewise exposure of the silver halide photographic photosensitive material according to claim 1 or 2 is performed, the overflow of the color developing solution generated during continuous processing is regenerated, and the halogenation is performed. A method for processing a silver halide photographic light-sensitive material, wherein the method is used for recycling the silver photographic light-sensitive material.