JPH07117736B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing an exposed silver halide color photographic light-sensitive material, and more particularly to a light-sensitive material containing a silver halide emulsion combined with a coupler. The present invention relates to a processing method including a step of color development, which can quickly obtain a color image without impairing photographic performance.

(Prior Art) Generally, the basic steps of processing a color light-sensitive material are a color development step and a desilvering step. In the color developing step, the silver halide exposed by the color developing agent is reduced to produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to give a dye image. In the next desilvering process,
The action of an oxidizing agent (commonly called a bleaching agent) oxidizes the silver produced in the color development step, and then it is dissolved by a complexing agent of silver ions, which is commonly called a fixing agent.

This desilvering step may be performed using a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, or may be performed by bleach-fixing in which a bleaching agent and a fixing agent are allowed to coexist.

Further, if necessary, in addition to the above basic steps, various auxiliary steps such as maintaining the photographic and physical quality of the image or improving the storability of the image can be included. For example, a hardening bath, a stopping bath, an image stabilizing bath, a washing bath and the like.

Since such a color processing method requires a comparatively long time for processing, a technique for reducing the treatment bath and a technique for improving the treatment speed for reducing the residence time in each treatment bath have been studied.

In order to shorten the processing time of color development, it is effective to increase the activity of the color developing solution. As a means for this,
It is effective to increase the concentration of the color developing agent in the color developing solution, increase the pH value of the color developing solution, or increase the temperature of the color developing solution. However, in any of these cases, the undesirable decrease in photographic property, which is a marked increase in the minimum density, occurs, and therefore it was difficult to put it into practical use.

Air fog is one of the main causes of the increase in the minimum concentration. This means that the light-sensitive material is transported in the air while it leaves the color development bath and enters the next processing bath. During this time (crossover time), the light-sensitive material is impregnated. The fog that occurs as a result of the developing agent coming into contact with oxygen in the air and oxidizing.

It is known to increase the activity by increasing the temperature, pH and concentration of the main agent of the color developer.

However, there is no effective means for reducing the adverse effects caused by increasing the activity of the color developing solution, particularly air fog, and the present invention has to be awaited.

(Problems to be Solved by the Present Invention) Accordingly, an object of the present invention is to greatly shorten the time required for the color developing processing in a processing method including a step of color developing a color light-sensitive material. More specifically, it is to achieve this shortening of processing time without causing undesired deterioration of photographic properties.

(Means for Solving the Problem) The object of the present invention is to perform a desilvering process after color development of a color light-sensitive material containing at least a light-sensitive silver halide emulsion and a coupler in combination with it on a support. In, the temperature of the color developing bath is 39 ° C. or higher, the concentration of the color developing agent is 0.015 M or higher, and the water softener of the color developing solution is a combination of a phosphonic acid chelating agent and an aminocarboxylic acid chelating agent. Yes, and between the processing bath and the subsequent processing bath (that is, between the color developing bath and the bath having bleaching ability)
Was achieved by a treatment method characterized by a crossover time of less than 10 seconds.

(Developing Agent) In the present invention, the color developing agent used in the color developing solution is an aromatic primary amine compound, and includes known compounds widely used in various color photographic processes. However, preferably, (1) 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate (2) 4- (N-ethyl-N-β-methanesulfonamidoethyl) Amino) -2-methylaniline sulfate (3) 4- (N-ethyl-N-β-methoxyethylamino) -2-methylaniline-p-toluenesulfonate (4) 4- (N, N-diethylamino) ) -2-Methylaniline hydrochloride (5) 4- (N-ethyl-N-dodecylamino) -2
-Methylaniline sulfate (6) N, N-dialkyl-p-phenylenediamine type color developing agent such as N, N-diethyl-p-phenylenediamine hydrochloride. These compounds are preferably added to the color developer in the range of 0.015-0.03 mol / 1.

The above color developing agents may be used alone or in combination according to the purpose. Preferred examples of the combined use include (1) and (2), (1) and (3), (2) and (3) of the above color developing agents.

(Auxiliary Developer) In addition to the above-mentioned developing agents, an auxiliary developer may be added to the color developing solution of the present invention in order to accelerate development. As such an auxiliary developing agent, any one can be used as long as the oxidant produced as a result of development cross-oxidizes with the developing agent, but a phenidone derivative is preferably used. For more on these, see “The Theory of P” by James.
hotographic Process "(4th ed.),
Specific examples include 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone.

These auxiliary developing agents are added in a molar ratio of 1/5 to 1/1000 of the developing agent, preferably 1/10 to 1/100.

(Preservative) Further, the color developing solution includes hydroxylamine, diethylhydroxylamine, triethanolamine, compounds described in West German Patent (OLS) 2622950, and Japanese Patent Application No. 61-2.
The compounds described in 65149, preservatives such as sulfites are used.

(Chelating Agent) Further, various chelating agents are added for the purpose of softening water and hiding the metal, but in the present invention, the general formulas (II) and (II
I) or (III) and (IV) are used together.

General formula (II) General formula (III) General formula (IV) In the formula, n represents 1 or 2, R represents a lower alkyl group, M may be the same or different, and represent a hydrogen atom, an alkali metal atom, or ammonium.

R is preferably a methyl group or an ethyl group, and M is preferably a hydrogen atom or a sodium atom.

For the purpose of softening in water, any of the above-mentioned aminocarboxylic acids or phosphonic acid compounds is effective, but for the purpose of the present invention, in order to suppress the increase of air fog by increasing the temperature of the color developing solution. With the reduction of crossover time, the specific combination of the above curing softeners is particularly effective.

Further, the combined use of the compounds of the general formulas (II) and (IV) is also preferable.

Specific examples of the compounds represented by formulas (II), (III) and (IV) are shown below.

The compound of the general formula (II) is used as a color developer and its replenisher.
It is added in the range of 0.0005-0.02 mol / l, preferably 0.001
-0.01 mol / l is added. Further, the compounds of the general formulas (III) and (IV) are similarly 0.002-0.1 mol / l, preferably 0.005-
It is added in the range of 0.05 mol / l.

When the compounds of general formulas (II) and (III) or (II) and (IV) are used in combination, the compound of (II) is 2 to 20 times the molar ratio of the compound of (III) or (IV), Preferably 3-15
Double, more preferably 3 to 10 times.

Among the above specific examples, particularly (II-1) and (III-1),
It is preferable to use (II-1) and (IV-1) and (III-1) and (IV-2) in combination.

In the color developer, in addition to the above compounds, a pH buffering agent such as alkali metal carbonate, borate or phosphate; a development inhibitor such as iodide, benzimidazoles, benzothiazoles or mercapto compounds. Or antifoggants; organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium, amines, thiocyanates; nucleating agents such as sodium polo hydride; viscosity imparting agents Or, in addition to the compounds represented by the general formulas (I) and (II), ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, Research Disclosure 18170 (1979) May 2007), various chelating agents such as organic phosphonic acid, etc. It can be used in combination.

The color developer is prepared by dissolving the above compounds in water, but the water used is preferably soft water, and the conductivity is 10 μs / cm, which has been deionized with a distillation or ion exchange resin or a reverse osmosis membrane. The following water is preferred.

(PH of developing solution) In the present invention, the pH of the color developing solution is 9.5 or more and 12.5 or less, preferably 10.0-11.5.

The temperature of the color developing solution is 39 ° C. or higher, preferably 40 ° C. to 45 ° C., in order to achieve rapid processing.

(Color development time) The color development time can be set between 1 minute and 5 minutes, but from the viewpoint of meeting the demand for rapid processing, it is preferable to perform processing at a high temperature for a short time, specifically at 39 ° C to 43 ° C. 1 to 3 minutes 30
The condition of seconds is preferable.

(Crossover Time) The time during which the light-sensitive material taken out of the color developing solution enters the next processing solution (crossover time) is 10 seconds or less in the present invention.

In the color development of the high temperature processing according to the present invention, when the light-sensitive material is still impregnated with the color-developing solution or is exposed to air for a long crossover time, oxygen in the air permeated from the film surface during The developing agent is easily oxidized and, in addition, the oxidized form of the developing agent reacts with the coupler, resulting in undesirable color fog.

However, as disclosed in the present invention, even when a high temperature color developer of 39 ° C. or higher is used, the crossover time is 10
By setting the time to be at least seconds, preferably 5 ″ or less, this air fog could be substantially suppressed.

Further, the effect of the present invention can be remarkably obtained when the crossover time is 1 second to 5 seconds.

In order to shorten the crossover time, a method of lowering the partition between liquids or a method of crossing over the photosensitive material below the liquid surface of the tank is preferable. In these cases, a space may be provided between the processing tanks as necessary to prevent the processing liquid from entering.

In order to convey the photosensitive material below the liquid level of the tank, the carry-in port and the carry-out port of the photosensitive material must be located below the liquid level.
If it is lower than the liquid surface, the liquid pressure will increase and it will be difficult to prevent liquid leakage.

Further, it is necessary to prevent liquid leakage of the tank liquid at the carry-out part or the carry-in part of the photosensitive material from the tank. As a means for preventing liquid leakage, it is most preferable to provide a squeeze that also serves as a liquid drainage, and an elastic wiper blade such as rubber is contacted from above and below to prevent liquid leakage, and liquid leakage when passing through the photosensitive material. It is preferable to do it. Urethane rubber and silicone rubber are most preferable as the material of the wiper blade.

The smaller the opening area of the carry-out section and the carry-in section, the more effectively the liquid leakage can be prevented. Therefore, the vertical length of the opening is 5 mm to 100
mm is preferable.

(Desilvering) Subsequent to the color development processing, desilvering processing for removing unnecessary developed silver and unreacted silver halide generated by development is performed.

The desilvering process may be a bleaching process in which developed silver is oxidized to form a silver salt, and a fixing process in which desilvering is dissolved and removed. Specifically, the following processing forms are adopted.

Bleaching process → Fixing process (2 steps) Bleaching process → Bleaching fixing process (2 steps) Bleaching fixing process (1 step) (Bleaching agent) As a bleaching agent used in a bleaching bath or a bleaching fixing bath, various oxidizing agents can be mentioned. , Prevention of water pollution and metal corrosion,
The aminopolycarboxylic acid ferric iron complex salt is most commonly used in terms of ensuring safety in handling and affecting photographic characteristics.

Specific examples thereof include ethylenediaminetetraacetic acid ferric ammonium, cyclohexylenediaminetetraacetic acid sodium ferric acid, and 1,3-diethylenepentaaminetetraacetic acid ferric ammonium.

(Fixing Agent) As the fixing agent used in the fixing bath or the fixing bleaching bath, any one can be used as long as it produces a soluble silver salt, but a thiocyanate salt or a thiosulfate salt is preferable, and a thiol salt is particularly preferable. Ammonium sulfate is preferred.

The bleaching bath and bleach-fixing bath of the present invention may contain, in addition to the bleaching agent and the above-mentioned compounds, a rehalogenating agent such as a chloride, for example, potassium chloride, sodium chloride or ammonium chloride. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid,
One or more inorganic acids having pH buffering ability such as phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, organic acids and salts thereof, further sodium thiosulfate, ammonium thiosulfate, sodium thiosulfate,
Compounds having a fixing ability such as thiosulfates such as potassium thiosulfate, sodium thiocyanate, ammonium thiocyanate, thiocyanates such as potassium thiocyanate, thiourea and thioether can be included.

Further, an accelerator may be added to accelerate the processing speed of bleaching or bleach-fixing. Such an accelerator is disclosed in Japanese Patent Application No. 62-261053.

In the present invention, various additives may be added to the bleaching bath, the bleach-fixing bath, etc., if necessary. For example, sodium sulfite, ammonium sulfite, and other sulfites, various antifoaming agents, or surfactants may be added, potassium iodide, sodium iodide, ammonium iodide, or other iodide, and hydroxylamidine. It is also possible to add bisulfite adducts of hydrazine and aldehyde compounds.

(Washing and / or Stabilization) After the bleach-fixing treatment, washing and stabilizing treatments are carried out. Depending on the type and use of the light-sensitive material, several methods can be selected, such as direct washing after washing with water, treatment with a stabilizing solution before drying, treatment with a stabilizing solution without drying with water and drying.

The washing liquid used in the present invention may be simple water such as tap water, well water, distilled water, deionized water, etc., but various known compounds such as sodium sulfate and magnesium chloride may be added to enhance the washing effect. . The pH of the washing solution is usually 5-8, but in order to promote washing with water, it may be adjusted to be acidic at pH 5 or lower or alkaline at pH 8 or higher. Further, as another means for promoting washing with water, an anionic or cationic surfactant can be added. In addition, Journal of Antibacterial and Antifungal Ages (J.
Antibact.Antifug.Agents) Vol.11, No.5, P.207-223 (19
83) and Hiroshi Horiguchi, “Chemistry of Antibacterial and Antifungal Chemistry” can be added. 5-chloro-2-methyl-
Isothiazoline compounds typified by 4-inchazolin-3-one, triazole derivatives typified by benzotriazole, and active halogen-releasing compounds typified by sodium dichloroisocyanurate are used to prevent water from spoiling when stored. Shows excellent effects. Other water softeners such as ethylenediaminetetraacetic acid and nitrilotriacetic acid are also used.

All the compounds that can be added to the washing solution can be added to the stabilizing solution, but compounds having an image stabilizing effect are further added. Examples of this include aldehyde compounds typified by formalin, ammonium compounds such as ammonium chloride, and fluorescent whitening agents. Stabilizer pH is usually 4-8
However, a low pH range of 3-5 may be preferably used depending on the type of sensitive material and the purpose.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, and the like.

The silver halide emulsion used in the present invention can be prepared by the method described in Research Disclosure, vol.176, Item No.17643, item [I].

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in the silver halide color photographic light-sensitive material used in the present invention. For high-sensitivity light-sensitive materials, silver iodobromide (silver iodide 3 to 20 mol%) is preferred.

The silver halide grains in the photographic emulsion may be so-called regular grains having regular crystal bodies such as cubes, octahedra, tetradecahedrons and rhombic dodecahedrons, and regular crystals such as spheres. It may have a shape, a crystal defect such as a twin plane, or a combination thereof.

The grain size of the silver halide may be fine grains of 0.1 micron or less, or large size grains having a projected area diameter of up to 10 microns, and may be a monodisperse emulsion having a narrow distribution or a monodisperse emulsion having a wide distribution.

Monodisperse emulsions are silver halide grains having an average grain diameter of greater than about 0.1 micron, at least about 95
Emulsions are typically such that the weight percent is within ± 40% of the average grain diameter. An average particle diameter of about 0.25 to 2 microns, at least about 95% by weight or at least about 95% in quantity
An emulsion in which the above silver halide grains are within the range of average grain diameter ± 20% can be used in the present invention.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146,
U.S. Pat.Nos. 3,505,068, 4,444,877 and JP-A-60
-143331 etc. Further, silver halides having different compositions may be joined by epitaxial joining.

By using tabular grains in the silver halide photographic emulsion used in the present invention, improvement in sensitivity including improvement in color sensitizing efficiency by a sensitizing dye, improvement in relationship between sensitivity and graininess, improvement in sharpness, Improvement of development progress, improvement of covering power, improvement of crossover, etc. can be achieved. Here, the tabular silver halide grains have a diameter / thickness ratio of 5 or more, for example, more than 8, or 5 or more and 8 or more.
There are the following:

The tabular grains may have a uniform halogen composition or two or more phases having different halogen compositions. For example, when silver iodobromide is used, the tabular silver iodobromide grains having a layered structure composed of a plurality of phases each having a different iodide content can be used. JP-A-58-113928 and JP-A-59-99433 disclose preferable examples of the halogen composition of tabular silver halide grains and the distribution of halogen within the grains.

The preferred use of tabular silver halide grains in the present invention is Research Disclosure No. 22534.
(January 1983) and No. 25330 (May 1985), for example, a use method based on the relationship between tabular grain thickness and optical properties is disclosed.

The silver halide photographic emulsion which can be used in the present invention can be produced by a known method, for example, Research Disclosure (RD), No. 17643 (December 1978), pp. 22-23, "I. Emulsion production ( Emulsion preparation and types) ”and the same
No. 18716 (November, 1979), p.648 can be followed.

The various photographic additives that can be used in the present invention are described, for example, in Research Disclosure No. 17643, pages 23 to 28 and No. 18716, pages 648 to 651. The types of these additives and their detailed descriptions are given below: Various color couplers can be used in the light-sensitive material that can be used in the processing of the present invention. Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers which can be used in the present invention are cited in Research Disclosure (RD) 17643 (December 1978) Section VII-D and 18717 (November 1979). Described in the patent.

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. A two-equivalent coupler in which a coupling-active group is substituted with a coupling-off group is more preferable than a four-equivalent coupler in which the coupling active position is a hydrogen atom, because the coated silver amount can be reduced. Further, couplers in which the color-forming dye has an appropriate diffusibility, uncolored couplers, or DIR couplers that release a development inhibitor with a coupling reaction or couplers that release a development accelerator can also be used.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat. No. 2,407,21.
No. 0, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a 2-equivalent yellow coupler, and U.S. Pat.Nos. 3,408,194 and 3,447,9 are used.
No. 28, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers described in JP-B-58-10739, U.S. Patent No. 4,401,752, No. 4,326,0
No. 24, RD18053 (April 1979), British Patent No. 1,425,020
Representative examples thereof include nitrogen atom-releasing yellow couplers described in West German Application Publication Nos. 2,219,917, 2,261,361, 2,329,587, and 2,433,812. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Examples of the magenta coupler that can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type couplers, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolone triazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole-based coupler, US Pat.
Pyrazolobenzimidazoles described in 1,432, preferably pitizolo (5,1) described in U.S. Pat.No. 3,725,067
-C] [1,2,4] triazoles, Research Disclosure 24220 (June 1984) and JP-A-60-33552
And the research discloser 24230 (June 1984) and JP-A-60-
The pyrazolopyrazoles described in 43659 are mentioned.
The imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630 are preferable in view of the small amount of yellow sub-absorption of a coloring dye and light fastness, and the pyrazolo [1,5- b] [1,2,4] triazole is particularly preferred.

Further, as the magenta coupler, it is preferable to use a pyrazol-eliminating compound described in US Pat. No. 4,367,282.
Equivalent magenta coupler and U.S. Pat.
Arylthio-elimination 2-equivalent magenta couplers such as those described in No. 22,915 are also used.

Cyan couplers include oil-protected naphthol-based and phenol-based couplers, naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212, 4,146,396 and 4,4.
Representative examples thereof include oxygen atom elimination type two-equivalent naphthol couplers described in Nos. 228,233 and 4,296,200. Further, specific examples of the phenol-based couplers include U.S. Pat. Nos. 2,369,929, 2,801,171, and 2,772,162.
No. 2,895,826 and the like. Humidity and temperature robust cyan couplers are preferably used in the present invention, typical examples of which are U.S. Pat.
A phenolic cyan coupler having an alkyl group of ethyl group or more at the meta-position of the phenol nucleus described in 002, U.S. Pat.Nos. 2,772,162, 3,758,308, and 4,
126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and European Patent 121,365 and the like, 2,5-diacylamino-substituted phenol couplers and U.S. Pat.Nos. 3,446,622 and 4,333,999.
Nos. 4,451,559 and 4,427,767, and the like, and phenol-based couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position. The cyan couplers described in Japanese Patent Application Nos. 59-93605, 59-264277 and 59-268135 in which the 5-position of naphthol is substituted with a sulfonamide group or an amide group are also excellent in the fastness of a color image, It can be preferably used in the present invention.

In order to correct unnecessary absorption in the short wavelength region which the dyes formed from the magenta and cyan couplers have, it is preferable to use a colored coupler in combination with the color negative photosensitive material for photographing. U.S. Pat.No. 4,163,670 and JP-B-57-3941
Typical examples include yellow-colored magenta couplers described in U.S. Pat. No. 3 or the like, or magenta-colored cyan couplers described in U.S. Pat. Nos. 4,004,929 and 4,138,258 and British Patent 1,146,368.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such blur couplers are described in U.S. Pat.No. 4,366,237 and British Patent 2,125,570.
No. 96,5 for a specific example of a magenta coupler.
No. 70 and West German Publication No. 3,234,533 have yellow,
Specific examples of magenta or cyan couplers are described.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of the polymerized magenta coupler include British Patent No. 2,102,173, U.S. Patent No. 4,367,282, Japanese Patent Application No. 60-75041, and No. 60-11.
It is described in 3596.

Various couplers may be used in combination of two or more in the same layer of the light-sensitive layer, or the same compound may be introduced in two or more different layers in order to satisfy the properties required for the light-sensitive material. .

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler, and 0.003 to 0.3 mol for the cyan coupler. It is 0.002 to 0.3 mol.

The present invention may include a coupler which releases a development inhibitor upon development, a so-called DIR coupler.

As the DIR coupler, for example, those releasing a heterocyclic mercapto type development inhibitor described in U.S. Pat. No. 3,227,554; those releasing a benzotriazole derivative described in JP-B-58-9942 as a development inhibitor; Kosho 51-16141
So-called colorless DIR couplers described in JP-A-52-90.
Release of nitrogen-containing heterocyclic development inhibitor with decomposition of methylol after removal as described in US Pat. No. 4,24.
Release of development inhibitor with intramolecular nucleophilic reaction after elimination described in JP-A-8,962 and JP-A-57-56837;
56-114946, 57-154234, 57-188035, 58-98
728, 58-209736, 58-209737, 58-209738
Nos. 58-209739 and 58-209740, which release a development inhibitor by electron transfer through a conjugated system after separation; described in JP-A-57-151944 and 58-217932. Which releases a diffusible development inhibitor whose development inhibiting ability is deactivated in the present solution; a film at the time of development, which releases the reactive compound described in Japanese Patent Application Nos. 59-38263 and 59-39653. Examples thereof include those that generate a development inhibitor by a medium reaction or deactivate the development inhibitor. Among the above-mentioned DIR couplers, more preferable ones in combination with the present invention are the developer inactivating type represented by JP-A-57-151944; US Pat. No. 4,248,962 and JP-A-57-154234. A typical timing type; a reaction type represented by Japanese Patent Application No. 59-39653, and among them, particularly preferable one is JP-A-57-1
51944, 58-217932, 60-218644, 60-225156
And deactivation type DIR described in No. 60-233650, etc.
Coupler and reaction type described in Japanese Patent Application No. 59-39653
It is a DIR coupler.

As the light-sensitive material which can be used in the present invention, a compound capable of releasing a nucleating agent or a development accelerator or a precursor thereof (hereinafter, referred to as "development accelerator") in an image during development can be used. . Typical examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188, which release a development inhibitor or the like by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. It is a coupler, that is, a DAR coupler.

The development accelerator or the like released from the DAR coupler preferably has an adsorption group for silver halide, and specific examples of such a DAR coupler are disclosed in JP-A-59-157638 and JP-A-59-170840. No. DAR couplers which generate N-acyl-substituted hydrazines having a monocyclic or condensed-ring heterocycle as an adsorptive group, which leaves from the coupling active position of a photographic coupler at a sulfur atom or a nitrogen atom are particularly preferable. Specific examples are described in JP-A-60-128446.

A compound having a development accelerator moiety in a coupler residue
JP-A-60-37556, which releases a development accelerator or the like by a redox reaction with a compound described in JP-A-60-37556 or a developing agent.
The compounds described in -107029 can also be used in the light-sensitive material of the present invention.

The DAR coupler is preferably incorporated in the light-sensitive silver halide emulsion layer of the light-sensitive material, and among the photographic constituent layers as described in JP-A-59-172640 or JP-A-60-128429. It is preferred to use substantially non-photosensitive silver halide grains in at least one layer.

The light-sensitive material used in the present invention is, as a color antifoggant or color mixing inhibitor, a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamide phenol derivative, etc. May be contained, or a known anti-fading agent may be used. Known anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p
-Alkoxyphenols and bisphenols, mainly hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ethers obtained by silylating and alkylating the phenolic hydroxyl groups of these compounds. Alternatively, an ester derivative can be given as a representative example. In addition, (bissalicylaldoximato) nickel complex and (bis-N, N-
A metal complex represented by a dialkyldithiocarbamate) nickel complex can also be used.

In the light-sensitive material used in the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer. For example, benzotriazoles substituted with an aryl group described in U.S. Pat.Nos. 3,553,794, 4,236,013, JP-B-51-6540 and European Patent 57,160, U.S. Pat.
No. 229 and 4,195,999 butadienes, U.S. Pat.Nos. 3,705,805 and 3,707,375 cinnamic acid esters, U.S. Pat.No. 3,215,530 and British Patent No. 1,321,355 benzophenones US Pat. Nos. 3,761,272 and 4,431,726 may be used as a polymer compound having an ultraviolet absorbing residue. The UV-absorbing fluorescent brighteners described in US Pat. Nos. 3,499,762 and 3,700,455 may also be used. A typical example of an ultraviolet absorber is RD24239 (1
June 984) and the like.

Other coating aids, antistatic, smoothness improvement, emulsion dispersion,
One or more surfactants may be included for various purposes such as prevention of adhesion and improvement of photographic properties (for example, development acceleration, hardening, sensitization).

Further, a water-soluble dye may be contained in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation or halation. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, phthalocyanine dyes are also useful. . The oil-soluble dye can be emulsified by the oil-in-water dispersion method and added to the hydrophilic colloid layer.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

The steps of the latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

(Example) Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Example 1 Subbed cellulose triacetate film support 1.5 × 10 ^-5 mol Coupler EX-1 ... 0.04 mol coupler / silver 0.04 mol coupler EX-2 ... 0.003 mol coupler / mol silver ...... 0.0006 mol 4th layer per 1 mol of silver; high-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 10 mol%) ...... Silver coating amount 1.4 g / m ² Sensitizing dye I ...... 3 × 10 ⁻⁵ mol Sensitizing Dye II to 1 mol of silver 1.2 × 10 ⁻⁵ mol to 1 mol of silver 7th layer; high sensitivity green emulsion layer Silver iodobromide emulsion (silver iodide: 10 mol%) ...... 0.8 × 10 ^-5 mol per 2.5 × 10- ⁵ mol sensitizing dye IV ...... silver mole with respect to silver coverage of 1.3 g / m ² sensitizing dye III ...... 1 mol of silver Coupler EX-7: 0.017 mol per mol of silver Coupler EX-6: 0.003 mol per mol of silver Coupler EX-8: 0.003 mol per mol of silver Eighth layer: yellow filter layer Gelatin water Gelatin layer containing yellow colloidal silver and emulsified dispersion of 2,5-di-t-octylhydroquinone in the liquid Ninth layer: low-sensitivity blue emulsion layer Silver iodobromide emulsion (silver iodide: 4 mol%) ...... Coating silver amount 0.7g / m ² Coupler EX-4 …… 0.01 mol to 1 mol silver Coupler EX-10 …… 0.01 mol to 1 mol silver Fifth layer; Intermediate layer Same as second layer 6 layers: low-sensitivity green-sensitive emulsion layer Monodisperse silver iodobromide emulsion (silver iodide: 4 mol%) Coating silver amount 1.2 g / m ² Sensitizing dye III: 3 × to silver 1 mol 10 ^-5 mol Sensitizing dye IV: 1 mol of silver 1 x 10 ^-5 mol Coupler EX-5: 0.05 mol of silver 1 mol Coupler EX-6: 0.08 mol of silver 1 mol Coupler EX-3: 0.0015 mol per mol of silver Coupler EX-9: 0.25 mol per mol of silver Coupler EX-3: 0.015 mol per mol of silver 10th layer; high sensitivity blue feeling Emulsion layer Odor Silver (silver iodide: 6 mol%) ... 11th layer against 0.06 mole coupler EX-6 ... silver mole with respect to silver coverage of 0.6 g / m ² Coupler EX-9 ...... 1 mol of silver; First protective layer Silver iodobromide (silver iodide 1 mol%, average particle size 0.07 μ) ... Coating amount 0.5 g Gelatin layer containing emulsion dispersion of UV absorber UV-1 12th layer; 2nd protective layer Layer A gelatin layer containing trimethylmethanoacrylate particles (diameter about 1.5μ) was applied.

In addition to the above composition, a gelatin hardening agent H-1 and a surfactant were added to each layer.

Compounds used to make samples Sensitizing dye I: Anhydro-5,5'-dichloro-3,3'-di-
(Γ-Sulfopropyl) -9-ethyl-thiacarbocyanine hydroxide / pyridinium salt Sensitizing dye II: anhydro-9-ethyl-3,3′-di- (γ
-Sulfopropyl) -4,5,4'-5'-dibenzothiacarbocyanine hydroxide triethylamine salt Sensitizing dye III: anhydro-9-ethyl-5,5'-dichloro-3,3'-di- ( γ-Sulfopropyl) oxacarbocyanine sodium salt Sensitizing dye IV: Anhydro-5,6,5 ′, 6′-tetrachloro-
1,1'-diethyl-3-3'-di- {β- [β- (γ-
Sulfopropyl) ethoxy] ethylimidazolocarbocyanine hydroxide sodium salt EX-1 EX-2 EX-3 EX-4 EX-5 EX-6 EX-7 EX-8 EX-9 EX-10 H-1 CH ₂ = CH-SO ₂ -CH ₂ -CONH- (CH ₂ ) ₂ NHCOCH ₂ SO ₂ CH = CH ₂ The color negative film produced as described above was cut to a width of 35 mm, and then 5 CMS was passed through an optical wedge at a color temperature of 4800K.
Was exposed to light and processed in a processor having a processing tank shown in FIG. The crossover time was changed by changing the distance between the bathtubs of the processor.

(Color developer) Water 800 ml Chelating agent described in Table-1 (described in Table-2) Sodium sulfite 4.5 g Potassium carbonate 37.0 g Potassium bromide 1.6 g 1-Phenyl-3-pyrazolidinone 50 g Potassium iodide 1.4 g Hydroxylamine Sulfate 2.6g 4- (N-ethyl-N-β-sidroxyethylamino)
-2-Methylaniline sulphate 5.4g Add water 1000ml pH 10.50 (bleaching solution) Ethylenediaminetetraacetic acid Ferric ammonium ammonium dihydrate Described in Table-2 Ethylenediaminetetraacetic acid di-Natri sodium salt 10.0g Ammonium bromide Ammonium nitrate 30.0g Bleach accelerator (Compound I-2) Ammonia water (27%) 3.0g Add water 1000ml pH 5.50 (bleach-fixing solution) Ethylenediaminetetraacetic acid Ferric ammonium ammonium dihydrate 1.2 × 10 ^-2mol Ethylenediaminetetraacetic acid disodium salt 6.0g Sodium sulfite 13.0g Ammonium thiosulfate 1.3 mol Ammonium water (27%) 5.0 g Water is added to 1000 ml pH 6.72 (Washing solution) Tap water is H type strong acid cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion. Water is passed through a mixed-bed column packed with exchange resin (Amberlite IR-400) to reduce the concentration of calcium and magnesium ions to 3 mg / L or less, followed by 20 mg / l sodium diisocyanurate dichloride and sodium sulfate. 0.15 g / l was added.

The pH of this solution was in the range 6.5-7.5.

(Stabilization liquid) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Ethylenediaminetetraacetic acid disodium salt 0.05 g Water 5.0 to 8.0 by sensitometry The obtained results are shown in Table 2.

When the treatment is carried out at the treatment temperature of the present invention or less, the increase of Fmin due to the increase of the fog is small, but the maximum concentration is insufficient by the treatment for a short time. (No.3). When the processing temperature is increased, the maximum density reaches a satisfactory level, but in this case, the fog is greatly increased. (No.4
Comparative Example) On the other hand, according to the treatment (No. 1, No. 2) of the present invention,
It can be seen that a sufficient maximum concentration and a low minimum concentration can be obtained by shortening the crossover time even during high temperature treatment.

Further, it can be seen that this effect is more preferable when used in combination with a phosphonic acid compound as compared with the case where an aminocarboxylic acid compound is used alone as a chelating agent. (Comparison with No. 5) Example-2 A photosensitive element having the following composition was prepared in place of the photosensitive material of Example 1.

On the undercoated cellulose triacetate film support, each layer having the composition shown below was coated in multiple layers to prepare a multilayer color light-sensitive material 101.

(Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount in g / m ² unit, and for silver halide, the coating amount in terms of silver.
However, for sensitizing dyes, silver halide 1 in the same layer
The coating amount per mol is shown in mol.

1st layer (antihalation layer) Black colloidal silver 0.2 Gelatin 1.0 UV absorber UV-1 0.05 Same UV-2 0.1 Same UV-3 0.1 Dispersion oil OIL-1 0.02 Second layer (intermediate layer) Fine silver bromide (average) Grain size 0.07μ) 0.15 Gelatin 1.0 Third layer (first red-sensitive emulsion layer) Monodisperse emulsion (6 mol% silver iodide, average grain size 0.4 μm, coefficient of variation 1.5% 1.42 Gelatin 0.9 Sensitizing dye A 2.0 × 10 ^-4 sensitizing dye B 1.0 x 10 ^-4 sensitizing dye C 0.3 x 10 ^-4 Cp-b 0.35 Cp-c 0.052 Cp-d 0.047 D-1 0.023 D-2 0.035 HBS-1 0.10 HBS-2 0.10 4th Layer (intermediate layer) Gelatin 0.8 Cp-b 0.10 HBS-1 0.05 Fifth layer (second red sensitive emulsion layer) Monodisperse emulsion (silver iodide 6 mol%, average grain size 0.5 μm, variation coefficient 15%) 1.38 Gelatin 1.0 sensitizing dye A 1.5 × 10 ^-4 sensitizing dye B 2.0 × 10 ^-4 sensitizing dye C 0.5 × 10 ^-4 Cp-b 0.150 Cp-d 0.027 D-1 0.005 D-2 0.010 HBS-1 0.050 HBS- 2 0.060 6th layer Third red-sensitive emulsion layer) Monodisperse emulsion (7 mol% silver iodide, average grain size 1.1 μm, coefficient of variation 16%) 2.08 Gelatin 1.5 Cp-a 0.060 Cp-c 0.024 Cp-d 0.038 D-1 0.006 HBS- 1 0.12 7th layer (intermediate layer) Gelatin 1.0 Cpd-A 0.05 HBS-2 0.05 8th layer (1st green sensitive layer) Monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain size 0.4μ)
m, coefficient of variation 19%) 0.64 Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.7μ)
m, coefficient of variation 18%) 1.12 Gelatin 1.0 Sensitizing dye D 1 × 10 ^-4 Sensitizing dye E 4 × 10 ^-4 Sensitizing dye F 1 × 10 ^-4 Cp-h 0.20 Cp-f 0.61 Cp-g 0.084 Cp -K 0.035 Cp-1 0.036 D-3 0.041 D-4 0.018 HBS-1 0.25 HBS-2 0.45 Ninth layer (second green emulsion layer) Monodisperse silver iodobromide emulsion (7 mol% silver iodide, average) Particle size 1.0μ
m, coefficient of variation 18%) 2.07 Gelatin 1.5 Sensitizing dye D 1.5 × 10 ^-4 Sensitizing dye E 2.3 × 10 ^-4 Sensitizing dye F 1.5 × 10 ^-4 Cp-f 0.007 Cp-h 0.012 Cp-g 0.009 HBS -2 0.088 10th layer (intermediate layer) Yellow colloidal silver 0.06 Gelatin 1.2 Cpd-A 0.3 HBS-1 0.3 11th layer (1st blue sensitive emulsion layer) Monodisperse silver iodobromide emulsion (6 mol% silver iodide, Average particle size 0.4μ
m, coefficient of variation 20%) 0.31 monodisperse silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.9μ)
m, coefficient of variation 17%) 0.38 Gelatin 2.0 Sensitizing dye G 1 × 10 ^-4 Sensitizing dye H 1 × 10 ^-4 Cp-i 0.63 Cp-j 0.57 D-1 0.020 D-4 0.015 HBS-1 0.05 12th Layer (second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (8 mol% silver iodide, average grain size 1.3 μm)
m, coefficient of variation 18%) 0.77 gelatin 0.5 sensitizing dye G 5 × 10 ^-5 sensitizing dye H 5 × 10 ^-5 Cp-i 0.10 Cp-j 0.10 D-4 0.005 HBS-2 0.10 13th layer (intermediate layer) ) Gelatin 0.5 Cp-m 0.1 UV-1 0.1 UV-2 0.1 UV-3 0.1 HBS-1 0.05 HBS-2 0.05 14th layer (protective layer) Monodisperse silver iodobromide emulsion (4 mol% silver iodide, average) Particle size 0.05μ
m, variation coefficient 10%) 0.1 Gelatin 1.5 Polymethylmethacrylate particles (average 1.5 μm) 0.1 S-1 0.2 S-2 0.2 Other surfactants K-1 and gelatin hardener H-1 were added.

The obtained light-sensitive element was exposed in the same manner as in Example 1 and processed in a processor having four processing tanks of the form shown in FIG.

As in Example 1, the crossover time was changed by changing the distance between the processing tanks, and changes in photographic properties were examined.

The processing steps are shown in Table-3.

(Color developer) and (Stabilizer) Same as in Example 1 (bleaching solution) 1,3-Propanediaminetetraacetic acid Ferric ammonium 50 g Ethylenediaminetetraacetic acid Ammonium ferric acid 90 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 200 g Ammonium nitrate 20g pH = 5.0 (fixing solution) Ammonium thiosulfate 168g Ammonium sulfite 20g Disodium ethylenediaminetetraacetate 13g pH6.5 As in Example 1, by setting the crossover time to 10 seconds or more, there is substantially no air fog, which is good. I was able to obtain photographic quality.

[Brief description of drawings]

1 and 2 show a part of the cross section of the automatic developing apparatus of the present invention. Reference numeral in the figure 1 ... Photosensitive material 2 ... Transport roller 3 ... Liquid seal and squeeze 4 ... Floating pig 5 ... Liquid level 6 ... Liquid sag receiving member 7 ... Transport roller 8 ... Photosensitive material 9: Transport roller 10: Liquid seal and squeeze 11: Treatment liquid tank 12: Treatment liquid

Claims (1)

[Claims] 1. A processing method in which at least a light-sensitive silver halide emulsion and a color light-sensitive material containing a coupler, which is combined with the light-sensitive silver halide emulsion, are color-developed on a support and then desilvered. 39 ° C. or higher, the color developing agent concentration is 0.015 M or higher, the water softener of the color developing solution is a combination of a phosphonic acid type chelating agent and an aminocarboxylic acid type chelating agent, and the treatment bath A method of processing a silver halide color photographic light-sensitive material, characterized in that the crossover time with a subsequent processing bath is 10 seconds or less.