JP2630465B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an image forming method for a silver halide color photographic light-sensitive material, and more particularly to an image forming method relating to the image quality of a color photographic material.

(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 form silver, and the oxidized color developing agent is used as a color forming agent (coupler).
To give a dye image. In the subsequent desilvering step, silver produced in the color developing step is oxidized by the action of an oxidizing agent (commonly referred to as a bleaching agent), and thereafter dissolved by a silver ion oxidizing agent commonly called a fixing agent. . Through this desilvering step, only a dye image is formed on the color photographic material.

The above desilvering step is performed in two baths, a bleach bath containing a bleaching agent and a fixing bath containing a fixing agent, and in a single bath using a bleach-fixing bath in which a bleaching agent and a fixing agent coexist. There is.

The actual development process includes various auxiliary steps such as to maintain the photographic and physical quality of an image or to improve the storability of an image, in addition to the above basic steps. For example, there are a dura bath, a stop bath, an image stabilizing bath, and a washing bath.

In recent years, with the spread of small in-store processing service systems called mini-labs, there has been a strong demand for shortening the time required for the above processing in order to quickly respond to processing requests from customers.

In particular, the shortening of the desilvering step, which conventionally occupies most of the processing time, has been the most requested.

However, ferric ethylenediaminetetraacetic acid complex salt, which is mainly used as a bleaching agent used in a bleaching solution and a bleach-fixing solution, has a basic defect that its oxidizing power is weak.
Despite various improvements such as the combined use of bleaching accelerators, the above requirements have not been met.

On the other hand, red blood salts, dichromates, ferric chloride, persulfates, bromates, etc. are known as strong oxidizing bleaching agents. In view of the above, each of them has many disadvantages and cannot be widely used for in-store processing.

Under these circumstances, the bleaching solution containing a ferric complex of 1,3-diaminopropanetetraacetic acid and having a pH of about 6 described in JP-A-62-222252 is compared with a bleaching solution containing a ferric complex of ethylenediaminetetraacetic acid. Although it has a high oxidizing power and enables more rapid silver bleaching, it has a drawback that when it is bleached directly without an intermediate bath after color development, color fogging called bleaching fog occurs.

Apart from the problem of bleaching fog, if the bleaching solution is used for shortening the bleaching time, a new problem may occur in that the processed light-sensitive material greatly increases stains during storage. It was revealed.

As one means for solving the above problem, after image formation,
In other words, it is only necessary to reduce the components remaining in the film of the light-sensitive material immediately before the desilvering step and further after the completion of the entire processing, so that the number of washing and / or stabilizing processing steps is increased,
Longer processing times are acceptable, but this solution goes against lab operators, user-oriented, and faster processing in the industry and is unacceptable.

On the other hand, European Patent Publication No. 255,722 and
No. 58,662, No. 228,655, No. 230,048, U.S. Pat.
4,704,350 itself and / or
Alternatively, it has been proposed to prevent stain by a method using compounds which each react with an oxidized form of the developing agent to give a substantially colorless product.

However, the use of these compounds relates to magenta couplers, particularly pyrazoloazole-based magenta couplers, and although their effects are certainly observed, their effects are not sufficient. It was found that the sensitivity was lowered and the gradation was changed. Therefore, it is extremely difficult to use these compounds in color light-sensitive materials for photography, and at present, another approach must be considered in order to solve the above problems.

(Problems to be Solved by the Invention) It is an object of the present invention to provide a light-sensitive material having less bleaching fog even in rapid processing. Another object of the present invention is to provide a light-sensitive material in which the stain of an uncolored portion does not increase much even when the color image is stored for a long time. Another object of the present invention is to provide a processing method in which bleaching fog is reduced when rapid processing is performed using the photosensitive material.

(Means for Solving the Problems) The present inventor has found that the above object can be achieved by the following method.

After imagewise exposing a silver halide color photographic light-sensitive material having at least one red-sensitive silver halide photosensitive layer, a green-sensitive silver halide photosensitive layer and a blue-sensitive silver halide photosensitive layer on a support, color development, In the bleaching treatment method, a non-photosensitive layer including an antihalation layer is provided between the photosensitive layer closest to the support and the undercoat layer on the support, and the dry thickness of the non-photosensitive layer is 2.5 μm or less. Processing of a silver halide color photographic light-sensitive material, wherein the green-sensitive silver halide photosensitive layer contains a high-boiling organic solvent having a dielectric constant of 6.0 or less, and the pH of the processing bath for the bleaching treatment is 5.0 or less. Method.

Hereinafter, the photosensitive material and the image forming method of the present invention will be described.

The present invention relates to a photographic color negative photosensitive material for general use and for cinema (hereinafter simply referred to as a photosensitive material).

In the light-sensitive material of the present invention, the non-light-sensitive layer provided between the light-sensitive layer closest to the support and the undercoat layer of the support usually means that the silver halide light-sensitive layer is directly coated on the undercoat layer of the support. Means not to be. In the light-sensitive material, another layer different from the undercoat layer for improving film properties such as adhesion of the layer sequentially coated on the undercoat layer to the support and / or an antihalation layer is provided. At the time of photographing, light is transmitted while diffusing through the upper photosensitive layer (the layer where silver halide grains and coupler dispersion are present), and the light that reaches the support surface is partially or entirely reflected and returns to the photosensitive layer. Providing a layer to prevent re-exposure of points away from the point of initial incidence, and / or a dye, colloidal silver and other colloidal silver for antihalation purposes incorporated in the antihalation layer above the antihalation layer. A so-called intermediate layer is provided to prevent various compounds used for the purpose from adversely affecting the upper photosensitive layer which is sequentially coated. The non-photosensitive layer is a generic term for each of these layers. Specific examples of these layers include (support-undercoat layer) -intermediate layer (1) -antihalation layer-intermediate layer (2) (support-undercoat layer) -antihalation layer-intermediate layer (1) ( Support-undercoat layer)-intermediate layer (1)-antihalation layer (support-undercoat layer)-antihalation layer.

The total dry film thickness of the non-photosensitive layer provided between the photosensitive layer closest to the support of the photosensitive material and the undercoat layer of the support has a layer configuration as described in the above specific examples depending on the performance of the photosensitive material. It is selected and the film thickness is determined. At present, most photosensitive materials on the market have a dry film thickness of 2.5 μm or more. The dry film thickness described here will be described later.

With regard to image forming processing of photosensitive materials, intensive efforts have been made on the research day and night in order to respond to the speeding up of processing which is a strong demand of lab operators and users in the industry,
By shortening the processing time of the processing steps (water washing or rinsing step, desilvering step, water washing and / or stabilizing step) subsequent to the color developing step of the image forming step, the minimum exposure portion of the photosensitive material can be reduced. Problems such as an increase in the density (Dmin) (hereinafter referred to as bleaching fog) and a large increase in stain in the unexposed area during image storage after processing occurred, and it was found that this was a major obstacle to speeding up processing.

As a result of elucidating this factor, it was surprisingly found that the thickness of the non-photosensitive layer provided between the photosensitive layer closest to the support and the undercoat layer of the support in the layer constitution of the photosensitive material was large.
It was confirmed that the increase in in and the increase in stain during image storage were large.

From this fact, it is preferable to reduce the total thickness of the non-photosensitive layer provided between the photosensitive layer closest to the support and the undercoat layer of the support. In the present invention, the total thickness is preferably 2.5 μm.
m, preferably 2.0 μm or less, and most preferably 1.5 μm or less.

The lower limit of the total film thickness can be reduced within a range where these layers do not impair the performance of the light-sensitive material. Therefore, the lower limit is not particularly limited.

The thickness of the multilayer silver halide color photographic light-sensitive material of the present invention is measured by the following method.

The photosensitive material to be measured is stored at 25 ° C. and 50% RH for 7 days after the preparation of the photosensitive material. First, the total thickness of the photosensitive material was measured, and then the thickness of the coating layer on the support was removed and the thickness was measured again. Thickness. This thickness is measured, for example, by a film thickness measuring device (An
ritsu Electric Co. Ltd., K-402B Stand.). The removal of the coating layer on the support can be performed using an aqueous solution of sodium hypochlorite.

Subsequently, using a scanning electron microscope, a cross-sectional photograph of the photosensitive material is taken (preferably at a magnification of 3,000 or more),
The total thickness of each layer on the support and the thickness of each layer are measured, and the thickness of each layer can be calculated by comparing with the measured value of the total thickness (absolute value of the actually measured thickness) by the film thickness measuring device described above.

The swelling ratio (see the following formula) of the non-photosensitive layer provided between the photosensitive layer closest to the support and the undercoat layer on the support in the photosensitive material of the present invention is preferably 50 to 200%, and 70 to 150%. % Is more preferred.

T _1: 25 ℃, H ₂ equilibrium swollen film thickness at O in T _2: 25 ℃, becomes large residual amount of drying and the total thickness swelling ratio Hazu is from above figures developing agent at 55% RH, In addition, it adversely affects photographic performance, image quality such as desilvering properties, and film properties such as film strength.

However, even with a photosensitive material in which the total thickness of the non-photosensitive layer provided between the photosensitive layer closest to the support and the undercoat layer is reduced to 2.5 μm or less, the increase in Dmin and the increase in stain are still large. It is not fully deterred.

After investigating these causes, the processing steps after the color development processing step, especially the omission of washing or rinsing before or in the middle of the desilvering processing step and the shortening of the processing time,
It became clear that the increase of Dmin and the increase of stain were large.

Of these, the increase in Dmin is due to the ionization or rehalogenation of colloidal silver and silver in developed silver when the photosensitive material to be processed is transported to the bleaching bath in the desilvering process and the developing agent is present in the film. In the so-called silver bleaching process that performs silver,
The developing agent present is partially oxidized to form quinone diimine (T ⁺ ), which reacts with the uncolored coupler remaining in the film of the light-sensitive material to form a dye.
It was found that in increased. This fact can be easily confirmed from the fact that an increase in the magenta density is observed when the Dmin is measured with green light after performing various processes, and the increase in the magenta Dmin density is observed in other yellow and cyan Dmin. It can also be confirmed that it is larger than the increase in concentration.

Stain generated when the processed photosensitive material is stored for a long period of time is oxidized by oxygen permeating the developing agent remaining in the film through the film of the photosensitive material, and a part of the stain develops T ⁺ . Coupling reacts with the undeveloped residual coupler to form a dye, or T ⁺ forms another compound such as a dimer, and these compounds have absorption in the visible region, It is presumed to cause an increase in stain.

It is important to reduce the increase in magenta Dmin concentration because the increase in magenta Dmin concentration after processing is particularly large and human visibility is high in the magenta region. In order to reduce the increase in magenta Dmin concentration, it is considered that the amount of the developing agent remaining in the green sensitive layer may be reduced. For this purpose, the thickness of the green-sensitive layer may be reduced. However, if the thickness of the film is reduced, it is expected that the color-forming performance of the coupler will decrease and the gelatin film quality will deteriorate.

It has been found that the amount of developing agent remaining in the film increases as the amount of the high boiling organic solvent used to dissolve couplers and couplers and other organic materials increases,
When the amount of the high-boiling organic solvent is reduced, problems such as precipitation of a coupler occur. However, the relationship between the dielectric constant of the high-boiling organic solvent and the residual developing agent showed that the lower the dielectric constant, the smaller the amount of the residual developing agent and the less bleaching fog.

Further, the total thickness of the non-photosensitive layer provided between the photosensitive layer closest to the support and the undercoat layer of the support is 2.5 μm.
It has been found that the use of a high-boiling organic solvent (oil) having a low dielectric constant for the green-sensitive layer in the following light-sensitive materials can more significantly reduce the occurrence of bleaching fog.

Therefore, in the present invention, the high-boiling organic solvent for dissolving and dispersing the magenta coupler used in the green sensitive layer is a compound having a dielectric constant of 6.0 or less, more preferably a high-boiling organic solvent having a dielectric constant of 6.0 or less and 1.9 or more. It is. The high-boiling organic solvent may be a mixture of two or more.

The dielectric constant in the present invention indicates a dielectric constant at 25 ° C., and this value is determined by the transformer bridge method (Ando Electric Co., Ltd.).
It can be easily obtained by measuring with TRS-10T).

Examples of the high boiling point organic solvent used in the present invention include those represented by the following general formulas (A), (B), (C), (D) and (E).

General formula (A) General formula (B) W ₁ -COO-W ₂ General formula (C) General formula (D) Formula (E) W ₁ -OW ₂ (wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, and W ₄ Is W ₁ , OW ₁ or SW ₁
Wherein n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different. In the general formula (E), W ₁ and W ₂ form a condensed ring. You may. The high-boiling organic solvent used in the present invention is represented by the general formula (A):
In the high-boiling organic solvent represented by (B), (C), (D) or (E), the sum of the carbon atoms of the substituents W ₁ , W ₂ , W ₃ or W ₄ is represented by the general formula (A), Compounds of B), (C), (D) or (E) having a dielectric constant of about 8 or more and having a dielectric constant of 6.0 or less correspond to the compound.

When W ₁ , W _2, and W ₃ have a substituent in the general formulas (A), (B), (C), or (E), the substituent is one or more. It may be a group having a bonding group selected from -CON, -R ¹ (R ¹ is a divalent to hexavalent group obtained by removing a hydrogen atom from a phenyl group) and -0-.

General formula (A), (B), (C), (D) or (E)
In the above, the alkyl group represented by W ₁ , W ₂ , W ₃ or W ₄ may be linear or branched. For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like.

The substituents allowed for these alkyl groups will be described by taking the case of the general formula (A) as an example. Examples thereof include a halogen atom, a cycloalkyl group, an aryl group, and an ester group. Substitutes of halogen (F, Cl, Br) (-C ₂ HF ₄ , -C ₅ H ₃ F ₈ , -C ₉ H
_{3 F 16, -C 2 H 4} Cl, -C 3 H 6 Cl, -C 3 H 5 Cl 2, -C 3 H 5 ClBr, -C 3 H 5
Br ₂ etc.), substituted cycloalkyl group Aryl substitution Substituents that give esters _{-CH 2 CH 2 COOC 12 H 25} , - (CH 2) 4 COOCH 2 (CF 2) 4 H, - (CH 2) 7 COO
C ₄ H ₉ ,-(CH ₂ ) ₈ COOC ₄ H ₉ etc.), a substituent providing lactate ester, etc. Substituents that give citrate esters, etc. Substituents that give malate ester etc. (-CH ₂ CH (OH) -COOC ₆ H ₁₃ etc.), substituents that give tartaric acid ester etc. And so on.

Also in the general formulas (B) to (E), the general formula (A)
And the same substituents as in the alkyl group may be substituted by the alkyl group.

Further, in the general formula (E), W ₁ and W ₂ may be an oxirane ring, an oxolane ring, or an oxane ring forming a condensed ring.

The cycloalkyl group represented by W ₁ , W ₂ , W ₃ or W ₄ is, for example, And the substituted cyclohexyl group is, for example, And so on.

The aryl group represented by W ₁ , W ₂ , W ₃ or W ₄ is And the substituted aryl group is, for example, Such as phthalic acid, isophthalic acid, terephthalic acid, substituted benzoic acid esters such as trimellitic acid ester, and And so on.

Alkenyl groups _{-C 4 H 7, -C 5 H} 9, -C 6 H 11, -C 7 H 13, -C 8 H
₁₅ , -C ₁₀ H ₁₉ , -C ₁₂ H ₂₃ , -C ₁₈ H _{35 and the} like, and the substituted alkenyl group is, for example, a halogen atom (F, Cl, Br), -OC
_{8 H 17, -OC 12 H 25} , Substituted alkenyl group such _{as, -CH = CH-COOCH 2 CH} 2 C 4 H 9, And so on.

General formulas (A), (B), (C), (D) and (E)
The high-boiling organic solvent according to the present invention represented by the formula (1) may be used alone or in combination of two or more, or may be used in combination with other conventionally known high-boiling organic solvents as long as the object of the present invention can be achieved. Examples of these conventionally known high-boiling organic solvents include phosphate-based solvents such as tricresyl phosphate, tri-2-ethylhexyl phosphate, 7-methyloctyl phosphate, and tricyclohexyl phosphate, and 2,5-di-tert-amyl. Examples thereof include phenol solvents such as phenol and 2,5-di-sec-amylphenol.

Specific examples of the high-boiling organic solvent having a dielectric constant of 6.0 or less represented by the general formulas (A), (B), (C), (D), and (E) are shown below, but are not limited thereto. Absent.

(S-1) O = POC 6 H 13 -n ] ₃ epsilon = 5.86 (S-3) O = POC 8 H 17 -n ] _{3 ε = 4.95 (S-4} ) O = POC 9 H 19 -n ] ₃ epsilon = 4.71 (S-6) O = POC 9 H 19 -iso ] ₃ epsilon = 4.46 (S-8) O = POC 10 H 21 -n ] _{3 ε = 4.21 (S-9} ) O = POC 10 H 21 -iso ] _{3 ε = 4.26 (S-10} ) O = POC 12 H 25 -n ] _{3 ε = 3.87 (S-11} ) O = POC 13 H 27 -iso ] _{3 ε = 3.95 (S-12} ) O = POC 14 H 29 -n ] ₃ epsilon = 4.01 The high boiling point organic solvent of the present invention can be used by adding to a layer containing green-sensitive silver halide and an adjacent non-photosensitive layer. The amount used is preferably from 0.01 to 20, and more preferably from 0.03 to 10, by weight based on the total amount of the coupler contained in the layer containing green-sensitive silver halide and the adjacent non-photosensitive layer. Is particularly preferred.

Dispersing a coupler and / or other organic materials in these high-boiling organic solvents and dispersing them in a gelatin solution using mechanical or ultrasonic waves as an anionic surfactant, a nonionic surfactant, And a cationic surfactant can be used. When an organic material such as a coupler is dissolved in a high-boiling organic solvent, a low-boiling solvent such as ethyl acetate, butyl acetate, or ethyl propionate can be used as an auxiliary solvent.

 Next, the image forming method of the present invention will be described.

The pH of the bleaching solution used in the present invention is 5.0 or less. As described above, the bleaching solution containing the ferric complex salt of 1,3-diaminopropanetetraacetic acid (1,3-DPTA.Fe) has a pH of 6.0 from both the viewpoints of securing the bleaching speed and preventing the cyan dye from recoloring failure. Near zero has been considered optimal. However, by using an oxidizing agent such as 1,3-DPTA.Fe by using the light-sensitive material having the constitution of the present invention, the pH is adjusted to 5.
By performing bleaching treatment at 0 or less, stain after treatment,
It was found that the processing could be speeded up without causing color reversal failure. As a result, rapid processing with less post-processing stain was realized. It has also been surprisingly found that when the light-sensitive material of the present invention is processed by the above-described processing method, surprisingly, the effect of reducing stain increase during image storage after processing is great. The pH range of this bleaching solution is 5.0 or less, more preferably 4.0 or less.

As the oxidizing agent used in the bleaching bath of the present invention, 1,3-diaminopropanetetraacetic acid ferric complex (1,3-DPTA.Fe), 1,4
-Ferric butylenediaminetetraacetic acid complex, ferric glycol ether diaminetetraacetic acid complex, ferric iminodiacetic acid complex, ferric methyliminodiacetic acid complex, ferric N- (2-acetamido) iminodiacetic acid complex salt, diethylenethioether Ferric tetraacetic acid complex salt, ferric ethylenediaminetetraacetic acid complex salt (EDTA.Fe), ferric diethylenetriaminetetraacetic acid complex salt, trans-1,2-cyclohexanediaminetetraacetic acid ferric complex salt and the like can be used. Of these, particularly preferred oxidizing agents have an oxidation-reduction potential at pH 6.0 of 150.
It is more than mV (vs. NHE).

Specifically, 1,3-DPTA.Fe and glycol ether diaminetetraacetic acid ferric complex are particularly excellent in terms of oxidizing power and are very effective in accelerating the bleaching treatment. Further, when EDTA • Fe conventionally used is used, since the oxidation-reduction potential is lower than 150 mV and the oxidizing power is weak, there is a problem in desilvering at the time of rapid processing, which is not so preferable.

Therefore, in the present invention, using 1,3-DPTAFe or glycol ether diaminotetraacetic acid ferric complex, the pH 5.0
Processing of the light-sensitive material of the present invention in the following is most preferable from the viewpoint of reduction of bleaching fog and desilvering properties.

The oxidation-reduction potential at pH 6.0 used in the present invention was determined by Transacti.
ons of the Faraday Society, 55 (1959).

Aminopolycarboxylic acid secondary represented by 1,3-DPTA.Fe
The preferred total amount of the iron complex salt is 0.1 mol to 1.0 mol / l, more preferably 0.15 mol to 0.7 mol / l, most preferably 0.25 mol / l.
Mol to 0.7 mol / l.

To maintain the pH of the bleaching solution at 5.0 or less, organic acids such as acetic acid, citric acid, and malonic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid can be used. Acids having a pKa in the range of 2.5 to 5.5 are preferred in terms of imparting buffering properties to the region of the present invention. In addition to the acetic acid, citric acid, and malonic acid, benzoic acid, formic acid, butyric acid, malic acid, tartaric acid,
Various organic acids such as oxalic acid, propionic acid and phthalic acid can be mentioned. Of these, acetic acid is particularly preferred.

The amount of these acids to be used is preferably 1.0 mol or more, more preferably 1.5 mol or more, per bleaching solution.

The oxidizing agent used in the bleaching solution may be used alone or in combination with another oxidizing agent.

Aminopolycarboxylic acid ferric complex (1,3-DPTA.
Fe, EDTA.Fe, etc.) are usually preferably used in the form of an alkali metal salt or an ammonium salt, and an ammonium salt is particularly preferable in terms of excellent solubility and bleaching power.

The bleaching solution or the bleach-fixing solution containing the above-mentioned ferric ion complex salt may contain a metal ion complex salt such as cobalt and copper other than iron.

Furthermore, it is preferable to add an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, or an alkali metal salt or ammonium salt thereof to the bleaching solution of the present invention, in addition to the above-mentioned ferric aminopolycarboxylic acid complex salt. In particular, it is preferable to add the same type of aminopolycarboxylic acid as the compound used as the bleaching agent. The preferable addition amount of these aminopolycarboxylic acids is 0.0001 mol / l to 0.1 mol / l, more preferably 0.003 to 0.05 mol / l.

Various bleaching accelerators can be added to the bleaching solution of the present invention.

For such bleaching accelerators, for example, U.S. Patent No. 3,893,858, German Patent No. 1,290,812, British Patent No. 1,138,842, JP-A-53-95630, Research Disclosure No. 17129 (1978
A compound having a mercapto group or a disulfide group, a thiazolidine derivative described in JP-A-50-140129, a thiourea derivative described in U.S. Pat. The iodides described in 16235, the polyethylene oxides described in German Patent No. 2,748,430, the polyamine compounds described in JP-B-45-8836, and the like can be used. Particularly preferred are mercapto compounds as described in British Patent No. 1,138,842. The bleaching solution of the present invention preferably contains bromine ions as a rehalogenating agent. The preferable addition amount of bromine ion is 1.2 mol / l or more, particularly preferably 1.5 to 2.0 mol / l.

Further, the bleaching solution may contain chlorine ion or iodine ion in addition to the above bromine ion. These halogen ions can be added as an alkali metal salt or an ammonium salt, but it is particularly preferable to add them as an ammonium salt.

Also, nitrates such as ammonium nitrate and sodium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate,
One or more known additives which can be generally used in a bleaching solution, such as one or more inorganic acids and organic acids having a pH buffering capacity of tartaric acid, their salts, and metal corrosion inhibitors such as ammonium sulfate can be added.

The bleaching solution is preferably subjected to aeration in order to oxidize the ferrous complex formed by the bleaching process or the reaction with the color developing solution brought in by the photosensitive material. The aeration may be performed only during the processing, may be performed only during the temperature control of the automatic developing machine, or may be performed all day long.

In the present invention, after processing with the bleaching solution, processing is performed in a processing bath having a fixing ability. Immediately after processing with the bleaching solution, processing with a processing bath having fixing ability is preferred because the effects of the present invention are remarkably exhibited. After processing with bleach,
Although it is not preferable to perform the treatment in a treatment bath having a fixing ability after performing a water washing treatment or the like, the number of steps is increased, or the processing speed and compactness of the processing machine are not preferable. It may be performed in the sense of assisting.

The processing bath having the fixing ability of the present invention refers to a bleach-fixing bath or a fixing bath.

As a fixing agent of a processing solution used in a processing bath having these fixing capabilities, thiosulfates (eg, sodium thiosulfate, sodium sodium thiosulfate, potassium thiosulfate), thiocyanates (eg, sodium thiocyanate, thiocyanic acid) Ammonium, potassium thiocyanate), thioether compounds, thioureas, a large amount of iodide, etc., but the use of thiosulfate has a high fixing speed and the effect of the present invention is most remarkably exhibited. Therefore, it is preferable. Particularly, ammonium thiosulfate is preferred from the viewpoint of solubility and fixing speed. It may be used in combination with another fixing agent.

The amount of these fixing agents is preferably 1.1 mol / l or more,
Particularly preferably, it is 1.3 to 1.7 mol / l. In a preferred range, the effects of the present invention are remarkable.

When the bath having the fixing ability of the present invention is a bleach-fixing bath,
In addition to the above-mentioned bleaching agents, known bleaching agents can be contained.

In the bath having the fixing ability of the present invention, sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), hydroxylamine, hydrazine, bisulfites of aldehyde compounds (for example, sodium acetaldehyde bisulfite) are used as preservatives. Or a carbonyl bisulfite adduct, a sulfinic acid compound, or the like. Further, various fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol can be contained. Especially as a preservative,
The sulfinic acid compounds described in JP-A-62-143048 can be used.

The bath having the fixing ability of the present invention contains 1,3-DPTA.Fe due to the introduction of the bleaching solution of the prebath with the photosensitive material, but in this case, the stability of the processing solution having the fixing ability is slightly lowered. Tend to. In order to improve the stability of the processing solution having a fixing ability, it is preferable to add an aminopolycarboxylic acid-based chelating agent or an organic phosphonic acid-based chelating agent. Examples of the organic phosphonic acid-based chelating agent include compounds represented by the following general formulas (1), (2) and (3).

General formula (1) General formula (2) General formula (3) In the formula, M represents a hydrogen atom, lithium, sodium, potassium, or ammonium, and is preferably a hydrogen atom. R ₁ represents an alkyl group or alkenyl group having 1 to 6 carbon atoms, and R ₂ represents an alkylene group having 2 to 8 carbon atoms. These substituents may be linear or branched. R ₁
And R ₂ preferably have 1 to 3 and 2 to 6, respectively.
It is. a, b, c, d, e, f, and g are each an integer of 1 to 3, and are preferably 1.

As a specific example, 1-hydroxyethylidene-1,1-
Diphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, N, N, N ', N'-ethylenediaminetetraphosphonic acid, N, N, N', N'-propylenediaminetetraphosphonic acid, N, N , N ', N'-hexylenediaminetetraphosphonic acid, N, N, N', N'-butylenediaminetetraphosphonic acid, N, N, N-nitrilotrimethylenephosphonic acid and
N, N, N-nitrilotripropylenephosphonic acid and their salts (for example, ammonium and sodium salts).

The amount of the chelating agent added to the processing solution having a fixing ability is 0.
01 mol / l or more, particularly preferably 0.02 to 0.1 mol / l
The addition of l is preferable because the stability of the processing solution having a fixing ability can be remarkably improved.

In particular, after treatment with a bleaching solution containing 1,3-DPTA-Fe,
The effect is great when processing with a fixer immediately.

Particularly preferred chelating agents include organic phosphonic acid-based chelating agents. Among them, 1-hydroxyethylidene-1,1-diphosphonic acid or a salt thereof (for example, ammonium or sodium salt) is most preferred.

The pH of the processing solution having fixing ability of the present invention is 3 to 9, preferably 5 to 8.

The shorter the total time of the desilvering step of the present invention, the more remarkable the effect of the present invention can be obtained. The preferred time is 1 minute to 4 minutes, more preferably 1 minute 30 seconds to 3 minutes. The processing temperature is 25 ℃
-50 ° C, preferably 35 ° C-45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the desilvering step of the present invention, it is preferable that stirring is strengthened as much as possible in order to more effectively exert the effects of the present invention.

As a specific method of strengthening stirring, JP-A-62-183460,
No. 62-183461, a method of impinging a jet of a processing solution on the emulsion surface of a photosensitive material, a method of increasing the stirring effect by using a rotating means of Japanese Patent Application Laid-Open No. 62-183461, There are a method of improving the stirring effect by moving the photosensitive material while bringing the wiper blade into contact with the emulsion surface to make the emulsion surface turbulent, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed.

The means for improving the agitation is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The crossover time from each processing solution of the present invention to the next processing solution (the air time from when the photosensitive material leaves the processing solution to when it enters the next processing solution) is preferably within 10 seconds, more preferably 5 seconds. Within.

The automatic developing machine used in the present invention is disclosed in JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 60-191258 and 60-191259. JP-A-60-191
As described in No. 257, such a transporting means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

 Hereinafter, the color developing solution of the present invention will be described.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- [β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N-
[Β- (methanesulfonamido) ethyl] aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino- 3-methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, particularly preferred is Exemplified Compound D-5.

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The amount of the aromatic primary amine developing agent to be used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to 10 g, per developer.

Further, as a preservative, a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is added to the color developer as necessary. be able to. However, in order to improve the color developability of the color developer, it is preferable to reduce the sulfite ion as much as possible.

The preferable addition amount of the preservative is 0.
It is 5 g to 10 g, more preferably 1 g to 5 g.

In addition to sulfurous acid, various compounds that directly preserve the color developing agent include various hydroxylamines,
Hydroxamic acids described in 63-43138, hydrazines and hydrazides described in 63-146041 and 63-170642,
The phenols described in JP-A-63-44657 and JP-A-63-58443,
It is preferable to add α-hydroxyketones and α-aminoketones described in 63-44656 and / or various saccharides described in 63-36244. Further, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254, JP-A-63-21647, JP-A-63-14
Monoamines described in Nos. 6040, 63-27841 and 63-25654, 63-30845, 63-146040, 63-43139
No. 63-21647 and 63-26655
No. 63-44655, polyamines described in JP-A-63-53551, nitroxy radicals described in JP-A-63-53551, 63-4
Alcohols described in Nos. 3140 and 63-53549, 63-566
It is preferable to use the oximes described in No. 54 and the tertiary amines described in 63-239447.

As other preservatives, JP-A-57-44148 and JP-A-57-537
Various metals described in No. 49, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349,
An aromatic polyhydroxy compound described in U.S. Pat. No. 3,746,544 may be contained as necessary. Particularly, addition of an aromatic polyhydroxy compound is preferred.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer is preferably at least 0.1 mol / l, particularly preferably from 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.

As the chelating agent, an organic acid compound is preferable.For example, Japanese Patent Publication Nos. 48-30496 and 44-30232, aminopolycarboxylic acids, JP-A-56-97347, JP-B-56-39359 and West German Patent No. 2,227,639 Organic phosphonic acids described in JP-A-5
2-102726, 53-42730, 54-121127, 55-1262
Examples thereof include the phosphonocarboxylic acids described in JP-A Nos. 41 and 55-659506, and the compounds described in JP-A Nos. 58-195845 and 58-203440 and JP-B No. 53-40900.
Specific examples are shown below, but the present invention is not limited thereto.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid,
1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid. These chelating agents may be used in combination of two or more as necessary.

These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, 1
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer as needed. However, it is preferred that the color developer of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation and prevention of color contamination. Here, “substantially” means that the developer does not contain 2 ml or less, preferably no developer, at all.

Other development accelerators include JP-B-37-16088 and 37
-5987, 38-7826, 44-12380, 45-9019 and U.S. Pat.No.3,813,247, thioether compounds represented by JP-A-52-49829 and JP-A-50-15554. P-phenylenediamine-based compound, JP-A-50-13772
No. 6, JP-B-44-30074, JP-A-56-156826 and JP-A-52-4
Quaternary ammonium salts represented by No. 3429, U.S. Pat. No. 2,494,903, Japanese Patent Publication No. 41-11431, U.S. Pat.
03, JP-B-41-11431, U.S. Patent No. 2,482,546,
Amine compounds described in 2,596,926 and 3,582,346, JP-B-37-16088, JP-B-42-25201, U.S. Pat.
No. 8,183, JP-B-41-11431, JP-B-42-23883 and U.S. Pat.No.3,532,501.Polyalkylene oxides, other 1-phenyl-3-pyrazolidones, imidazoles, etc. are added as necessary. be able to.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be mentioned as typical examples.

The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, a 4,4'-diamino-2,2'-disulfostilbene compound is preferable.
The addition amount is 0 to 5 g / l, preferably 0.1 g to 4 g / l.

If necessary, various surfactants such as alkylsulfonic acid, arylsulfonic acid, alkylphosphonic acid, arylphosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developer of the present invention is from 20 to 50 ° C, preferably from 30 to 45 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. It is preferable that the replenishment amount is small,
Photosensitive material 1 m ² per, 100~1500ml, preferably 100~800m
l. More preferably, it is 100 ml to 400 ml.

Also, the color developing bath is divided into two or more baths as necessary,
Replenish the color developer replenisher from the last bath or the last bath,
The development time and the replenishment amount may be reduced.

The processing method of the present invention can also be used for color reversal processing. In the present invention, a so-called black-and-white first developing solution used for reversal processing of a color photographic light-sensitive material which is generally known as a black-and-white developing solution used at this time, or a solution used for processing a black-and-white photosensitive material can be used. In addition, various well-known additives generally added to a black-and-white developer can be contained.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, methol and hydroquinone, preservatives such as sulfites, and accelerators composed of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate. , Potassium bromide, 2-methylbenzimidazole,
Examples thereof include an inorganic or organic inhibitor such as methylbenzthiazole, a water softener such as a polyphosphate, a trace amount of iodide, and a development inhibitor comprising a mercapto compound.

The processing method of the present invention comprises the above-described processing steps such as color development, bleaching, bleach-fixing and fixing. here,
After the processing step having the fixing ability, it is generally performed to perform processing steps such as washing and stabilization,
After the bath having the fixing ability, a simple processing method in which a stabilization treatment is performed without substantial washing with water can be used.

Known additives can be added to the washing water used in the washing step, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, fungicides and fungicides that prevent the growth of various bacteria and algae (eg, isothiazolone, organochlorine fungicides, benzotriazole, etc.) , A drying load and a surfactant for preventing unevenness can be used. Or LEWes
t, “Weter Quality Criteria”, Phot. Sci. and Eng., vol.
9, No. 6, pages 344 to 359 (1965) and the like can also be used.

As the stabilizing solution used in the stabilizing step, a processing solution that stabilizes the dye image is used. For example, a liquid having a buffer capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), or the like can be used. The stabilizing solution may include, if necessary, a metal compound such as an ammonium compound, Bi, or Al, a fluorescent whitening agent, a chelating agent (for example, 1-hydroxyethylidene-1,1-diphosphonic acid), a bactericide, a fungicide,
Hardening agents, surfactants and the like can be used. Here, formalin can be removed from the stabilizer and used. In this case, reduction of environmental pollution (reduction of pollution load),
It is preferable in terms of improving the working environment.

In the washing step and the stabilizing step, a multi-stage countercurrent system is preferable, and the number of stages is preferably two to four. The replenishing amount is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

Water used in these washing or stabilizing steps is not limited to tap water, and may be C
a, It is preferable to use water that has been deionized to an Mg concentration of 5 mg / l or less, water that has been sterilized by halogen, an ultraviolet germicidal lamp, or the like.

In the above-described processing steps of the photosensitive material, when the continuous processing is performed by the automatic developing machine, the processing solution may be concentrated due to evaporation, particularly when the processing amount is small or the opening area of the processing solution is large. Becomes In order to correct such concentration of the processing solution, it is preferable to replenish an appropriate amount of water or a correction solution.

In addition, the amount of waste liquid can also be reduced by using a method in which the overflow solution in the washing step or the stabilization step is flowed into a bath having a fixing ability, which is a pre-bath.

The amount of the developing agent remaining in the film of the photosensitive material after processing can be determined according to the method described in JP-B-63-23529. That is, after the unexposed sample is developed, the developing agent extracted from the sample with an organic solvent (eg, ethyl acetate) is added to a solution comprising the following dispersion containing a cyan coupler and an aqueous solution of red blood salt to form a developing agent. The concentration of the cyan dye can be measured and determined by an absorbance method.

The light-sensitive material of the present invention may be provided with at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. There is no particular limitation on the number and order of the emulsion layers and the non-light-sensitive layers. A typical example is to have a blue-sensitive, green-sensitive and red-sensitive photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. This is a silver halide photographic light-sensitive material. In general, the arrangement of unit light-sensitive layers is provided in the order of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer in order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer, JP-A-61-43748, JP-A-59-113438,
No. 59-113440, No. 61-20037, couplers as described in the specification of No. 61-20038, and may contain a DIR compound, etc., and contain a color mixing inhibitor as usually used. Is also good.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of the high-speed emulsion layer and the low-speed emulsion layer
A layer configuration can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, 62-20
As described in JP-A Nos. 0350, 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) ) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) or BH / B
They can be installed in the order of L / GL / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Also, as described in Japanese Patent Publication No. 55-34932,
From the farthest side from the support, blue light-sensitive layers / GH / RH / GL / RL can be arranged in this order. JP-A-56-25738, 62
As described in -63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. An arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and three layers having different sensitivities are sequentially reduced in sensitivity toward a support, may be mentioned. Even when such a three-layer structure having different sensitivities is used, Japanese Patent Application Laid-Open No.
As described in the specification of JP-A No. 464, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in the same color-sensitive layer from the side away from the support.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

As described above, the arrangement may be changed even in the case of four or more layers.

No. 4,663,271 to improve color reproduction
No. 4,705,744, 4,707,436, JP-A-62-160
A donor layer (CL) with a multilayer effect having a different spectral sensitivity distribution from the main photosensitive layer such as BL, GL, RL described in the specifications of JP-A Nos. 448 and 63-89580 is disposed adjacent to or close to the main photosensitive layer. Is preferred.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be one having regular crystals such as tetradecahedron, one having irregular crystal forms such as spherical or plate-like, one having crystal defects such as twin planes, or a complex form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion layer that can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (1978).
December, p. 22-23, "I. Emulsion preparat
ion and types) ”, and No. 18716 (November 1979),
648 pages, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemic et Phisique Photogr
aphique, Paul Montel, 1967), Duffin's "Photoemulsion Chemistry", Focal Press (GFDuffin, Photographi)
c Emulsion Chemistry (Focal Press, 1966)), "Manufacture and coating of photographic emulsions" by Zerikman et al., Published by Focal Press (VLZelikman et al., Making and Coating Photog).
raphic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,2
No. 26, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,157 can be easily prepared.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

 Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,503
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in (1) to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-C to G.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat.
Preferred are those described in 968, 4,314,023, 4,511,649, EP 249,473A, and the like.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552
No., Research Disclosure No.24230 (June 1984)
Mon), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730
No. 55-118034, No. 60-185951, U.S. Pat.
No. 630, No. 4,540,654, No. 4,556,630, International Publication W
Those described in O88 / 04795 and the like are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453
A, U.S. Pat.Nos. 3,446,622, 4,333,999,
No. 4,775,616, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212, No. 4,296,199,
Those described in JP-A-61-42658 are preferred.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No. 17643, VII-
Section G, U.S. Patent No. 4,163,670, JP-B-57-39413, U.S. Patent Nos. 4,004,929, 4,138,258, UK Patent No. 1,14
Those described in 6,368 are preferred. Also, U.S. Pat.
A coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 74,181, or a dye precursor group capable of forming a dye by reacting with a developing agent described in U.S. Pat. It is also preferable to use a coupler having

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, British Patent 2,10
No. 2,173.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, VII-F above.
Patents described in the paragraph, JP-A-57-151944, 57-154234
And Nos. 60-184248, 63-37346 and 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
Preferred are those described in JP-A-31-188, JP-A-59-157638 and JP-A-59-170840.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618, multi-equivalent couplers described in
No. 185950, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound described in JP-A-62-24252, etc. Coupler that releases coloring dye, RD No. 1144
9, 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat.No. 4,553,477, etc., and leuco dyes described in JP-A-63-75747 are released. Couplers and couplers that release a fluorescent dye described in U.S. Pat. No. 4,774,181 are exemplified.

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

Examples of high-boiling solvents other than the high-boiling organic solvent of the present invention used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably 50 ° C. or more and about 160 ° C. or less of an organic solvent can be used, typical examples are ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

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

In the color light-sensitive material of the present invention, JP-A-63-257747
No. 62-272248 and JP-A-1-80941, 1,2-
Benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-
Dimethylphenol, 2-phenoxyethanol, 2-
It is preferable to add various preservatives or fungicides such as (4-thiazolyl) benzimidazole.

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

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 647 of No.18716
It is described in the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is 28 μm or less, preferably 23 μm or less, more preferably 20 μm or less. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling speed T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (A. Green) et al.
otogr. Sci. Eng.), Vol. 19, No. 2, pp. 124-129 can be measured by using a serometer (swelling meter), and T _1/2 is 30 ° C. in a color developing solution. 90% of the maximum swollen film thickness reached when the treatment is performed for 3 minutes and 15 seconds is defined as a saturated film thickness, and defined as the time required to reach the film thickness of T _1/2 .

The film swelling speed T1 _{/ 2} can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging conditions of the coating solution. The swelling ratio is 15
0-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness−film thickness) /
It can be calculated according to the film thickness.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, 3,342,599, Schiff base-type compounds described in Research Disclosure 14,850 and 15,159, aldol compounds described in 13,924, and metals described in U.S. Pat.No.3,719,492 Salt complexes and urethane compounds described in JP-A-53-135628 can be exemplified.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-1154.
No. 38, etc.

(Examples) Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example 1 On a cellulose triacetate film support having an undercoat, Sample 1 which was a multilayer color photographic material composed of each layer having the following composition was prepared.

(Composition of photosensitive layer) The coating amount is silver g / g for colloidal silver.
The amounts expressed in m ² units, gelatin, a coupler, an amount for the organic material, expressed in units of g / m ² such as oil, but the number of moles of halide per 1 mole of the same layer for a sensitizing dye Indicated by

The numerical value in parentheses at the end of each layer indicates the dry film thickness (unit: μm).

First layer: Antihalation layer Black colloidal silver Silver coating amount 0.20 Gelatin 2.15 UV-1 0.10 UV-2 0.20 Cpd-1 0.05 Solv-1 0.01 Solv-2 0.01 Solv-3 0.08 (2.1) Second layer: Intermediate layer Fine particles Silver bromide (sphere equivalent diameter 0.07 μm) Silver coating amount 0.15 Gelatin 1.00 Cpd-2 0.20 (1.0) Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, spherical) 0.7 μm equivalent diameter, coefficient of variation of equivalent spherical diameter of 14%, tetrahedral grains) Silver coating amount 0.50 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter)
0.4 μm, coefficient of variation of equivalent sphere diameter 22%, tetrahedral particles) Silver coating amount 0.40 Gelatin 2.00 ExS-1 4.5 × 10 ^-4 ExS-2 1.5 × 10 ^-4 ExS-3 0.4 × 10 ^-4 ExS-4 0.3 × 10 ^-4 ExC-1 0.33 ExC-2 0.009 ExC-3 0.023 ExC-6 0.14 (2.3) Fourth layer: Second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 16 mol%, internal high AgI type, spherical) Equivalent diameter
1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter /
Thickness ratio 4.0) Silver coating amount 0.80 Gelatin 1.30 ExS-1 3 × 10 ^-4 ExS-2 1 × 10 ^-4 ExS-3 0.3 × 10 ^-4 ExS-4 0.3 × 10 ^-4 ExC-3 0.05 ExC-4 0.10 ExC-6 0.08 (1.5) Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, sphere equivalent diameter 1.2 μm, coefficient of variation of sphere equivalent diameter 28%, plate shape Particles, diameter / thickness ratio 6.0) Silver coating amount 1.10 Gelatin 1.20 ExS-1 2 × 10 ^-4 ExS-2 0.6 × 10 ^-4 ExS-3 0.2 × 10 ^-4 ExC-4 0.07 ExC-5 0.06 Solv-1 0.12 Solv-2 0.12 (1.6) 6th layer: Intermediate layer Gelatin 1.30 Cpd-4 0.10 (1.1) 7th layer: 1st green sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent to sphere) 0.7μm diameter, sphere equivalent diameter variation coefficient 14%, tetrahedral grains) Silver coating amount 0.20 Silver iodobromide emulsion (AgI 4.0mol%, internal high AgI type, sphere equivalent diameter)
0.4 μm, sphere equivalent coefficient of variation 22%, tetrahedral particles) Silver coating amount 0.10 Gelatin 1.40 ExS-5 5 × 10 ^-4 ExS-6 2 × 10 ^-4 ExS-7 1 × 10 ^-4 ExM-1 0.41 ExM-2 0.10 ExM-5 0.03 Solv-1 0.20 (1.9) Eighth layer: Second green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter)
1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter /
Thickness ratio 3.0) Silver coating amount 0.50 Gelatin 0.45 ExS-5 3.5 × 10 ^-4 ExS-6 1.4 × 10 ^-4 ExS-7 0.7 × 10 ^-4 ExM-1 0.09 ExM-3 0.01 Solv-1 0.15 (0.8) No. Nineth layer: Intermediate layer Gelatin 0.50 (0.4) Tenth layer: Third green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter 1.2 μm, coefficient of variation of equivalent spherical diameter 28%) , Plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 1.20 Gelatin 1.40 ExS-5 2 × 10 ^-4 ExS-6 0.8 × 10 ^-4 ExS-7 0.8 × 10 ^-4 ExM-3 0.01 ExM-4 0.14 ExM -1 0.04 ExC-4 0.005 Solv-1 0.2 (1.8) 11th layer: yellow filter layer Cpd-3 0.05 gelatin 0.50 Solv-1 0.10 (0.5) 12th layer: middle layer gelatin 0.50 Cpd-2 0.10 (0.5) 13th layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter)
0.7 μm, coefficient of variation of equivalent sphere diameter 14%, tetrahedral grain) Silver coating amount 0.15 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent sphere diameter)
0.4 μm, coefficient of variation of equivalent sphere diameter 22%, tetrahedral particles) Silver coating amount 0.08 Gelatin 1.20 ExS-8 3 × 10 ^-4 ExY-1 0.62 ExY-2 0.02 Solv-1 0.40 (1.9) 14th layer: 2 Blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, variation coefficient of equivalent sphere diameter 16%, tetradecahedral grains) Silver coating amount 0.30 Gelatin 0.30 ExS-8 2 × 10 ^-4 ExY-1 0.22 Solv-1 0.07 (0.7) Fifteenth layer: Intermediate layer Fine grain silver iodobromide (AgI 12 mol%, uniform type, equivalent sphere diameter 0.13)
Silver coating amount 0.20 Gelatin 0.36 (0.4) 16th layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, equivalent spherical diameter 1.5 μm, coefficient of variation of equivalent spherical diameter 28) %, Plate-like particles, diameter / thickness ratio 5.0) Silver coating amount 1.20 Gelatin 0.90 ExS-8 1.5 × 10 ^-4 ExY-1 0.20 Solv-1 0.07 (1.3) 17th layer: 1st protective layer Gelatin 1.80 UV-1 0.10 UV-2 0.20 Solv-1 0.01 Solv-2 0.01 (1.7) 18th layer: 2nd protective layer Fine particle silver bromide (sphere equivalent diameter 0.07 μm) Silver coating amount 0.18 Gelatin 1.05 Polymethyl methacrylate particles (diameter 1.5 μm) 0.20 W-1 0.02 H-1 0.40 Cpd-5 1.00 (2.1) Next, the layer structure, the compound used for each layer and its coating amount, the emulsion type and its coating amount were the same without changing Sample 1.
However, the coating amounts of the first layer and the second layer were changed for each layer, and the hardener H-1 based on the total amount of gelatin was added in the same ratio as that of the sample 1, and the first layer and the second layer were added as shown in Table 1. As shown in Table 1, the oil used for the green layer (the seventh layer, the eighth layer, and the tenth layer) in which the total film thickness of the two layers was changed and the oil used for the green layer (the seventh layer, the tenth layer) were changed with the same coating amount as the sample 1. The added samples 2 to 15 were prepared.

Each of the prepared samples 1 to 15 was cut and processed into a width of 35 mm, subjected to wet exposure with white light (color temperature of light source: 4800 ° K), and processed by the following processing method 1.

Further, as a comparison process, the following process 2 was performed in the same manner as process 1. The processing method 2 is a processing in which the bleaching fog after the processing can be regarded as substantially zero.

Processing method 1: Process processing time Processing temperature replenishment amount ^* Color development 3 minutes 15 seconds 37.8 ℃ 20 ml Bleaching 40 seconds 38.0 ℃ 5 ml Fixing 1 minute 30 seconds 38.0 ℃ 30 ml Rinse (1) 30 seconds 38.0 ℃-Rinse (2) 30 seconds 38.0 ° C 30 ml Stable 30 seconds 38.0 ° C 20 ml Drying 1 minute 00 seconds 55 ° C * Washing of photosensitive material per 35mm width 1m length The cascade method from (2) to (1) below Is shown.

The replenisher and the mother liquor were common.

(Color developing solution) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- (N -Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5 Add water 1.0l pH 10.05 (Bleaching solution) (Unit: g) Ferric ammonium 1,3-diaminopropanetetraacetate-water salt 144.0 Ferric ammonium-water salt 1,3 −Diaminopropanetetraacetic acid 2.8 Ammonium bromide 84.0 Ammonium nitrate 25.0 Acetic acid (98%) 110.0 Add water to 1.0 l pH (adjusted with ammore water (27%)) 4.0 (Fixing solution) (Unit: g) Salt 1.7 Ammonium sulfite 14.0 Aqueous solution of ammonium thiosulfate 340.0ml (700g / l) Add water 1.0l pH 7.0 (wash water) Tap water is mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) Calcium and magnesium ion concentrations were reduced to 3 mg / l or less by passing water through a mixed-bed column filled with OH-type strongly basic anion exchange resin (Amberlite IRA-400). Sodium isocyanurate 20mg / l and sodium sulfate 150mg / l
l was added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing Solution) (unit: g) of formalin (37%) 1.2 ml Surfactant 0.4 _{C 10 H 21 -OCH 2 CH 2} O 10 H ] 1.0 l pH 5.0-7.0 processing method 2 by addition of ethylene glycol 1.0 Water : In processing method 1, 1% between color developing bath and bleaching bath
A treatment method exactly the same as treatment method 1 except that an acetic acid aqueous solution bath was added for 2 minutes.

These treated samples obtained by treatment methods 1 and 2 are referred to as group A and group R, respectively.

The densities of these samples were measured, and the Dmin measured at the green light density was read from the obtained characteristic curves.

The evaluation is based on the Dmin of the sample in the R group, Was calculated.

 The results are shown in Table 2.

From the results shown in Table 2, the total thickness of the non-photosensitive layer provided between the photosensitive layer closest to the support and the undercoat layer of the support, which satisfies the components of the photosensitive material of the present invention, is 2.5 μm or less. In addition, photosensitive materials (samples 7 to 15) in which a high-boiling organic solvent having a dielectric constant of 6.0 or less is used for the green sensitive layer have a small Dmin and are excellent. In comparison, Comparative Samples 1 to 6 have a higher Dmin and are clearly inferior.

That is, the comparative sample 6 is a sample in which the oil is the same as that of the sample 7 of the present invention, but the thickness of the first layer + the second layer exceeds 2.5 μm, so that Dmin is significantly increased. ing.

When the comparative sample 2 was compared with the samples 7 and 11 to 15 of the present invention, the thickness of the first layer + the second layer was the same, but the oil used for the green sensitive layer was the same as that of the samples 7 and 11. At ~ 15, the dielectric constant is 6.
It is 0 or less, and exceeds 6.0 in Sample 2. For this reason, the sample of the present invention is excellent, but Dmin is clearly high and inferior in Comparative Sample 2.

Further, when looking at Comparative Samples 1 to 5, since the oil having a dielectric constant of more than 6.0 is used for the green sensitive layer,
Even if the film thickness of the layer + the second layer was reduced, Dmin could not be significantly reduced.

Example 2 The pH of the bleaching solution of the processing method 1 used in Example 1 was 3.7 and 4.
Bleaching solutions were prepared in exactly the same manner as in Treatment Method 1 except that ammonia water was separately prepared at 0, 4.5, 5.0, 5.5 and 6.0.

Except for using these bleaching solutions, the processing of Sample 7 prepared in Example 1 was carried out in the same manner as the processing of Group A above except for the other processing solutions and processing steps.

The density of the processed sample was measured, the Dmin measured at the green light density was read from the obtained characteristic curve, and the bleaching fog was determined by the difference from the Dmin of the sample 7 (sample R in the R group) processed by the processing method 2. evaluated.

The results are shown in Table 3.

The results in Table 3 show that when the pH of the bleaching solution exceeds 5.0, the level of bleaching fog increases significantly. That is,
When processed using the light-sensitive material of the present invention, the pH of the bleaching solution is
5.0 or less is desirable. Further more preferably, the pH is 4.0 or less. When the light-sensitive material of the present invention is processed by setting the pH of the bleaching solution to 4.0 or less, bleaching fog is at a level at which substantially no problem occurs.

Example 3 In the processing method 1 of Example 1, the acetic acid concentration of the bleaching solution was
Bleaching solutions were prepared at 40 g / l, 55 g / l, 60 g / l, 80 g / l, 110 g / l, and 220 g / l, respectively.

For the other treatment liquids and treatment steps, the treatment of Sample 7 prepared in Example 1 was performed in the same manner as the treatment of Group A above.

The density of the processed sample was measured, and Dmin measured at the green light density was read from the obtained characteristic curve, and processing method 2 was performed.
The bleaching fog was evaluated based on the difference from Dmin of the sample 7 (sample R in the R group) treated with.

The results are shown in Table 4.

As is clear from Table 4, the acetic acid concentration in the bleaching solution was 1.0.
Below mol / l, bleach fog levels are significantly worse. When the amount is 1.0 mol / l or more, bleaching fog is at a level at which substantially no problem occurs when processing the light-sensitive material of the present invention.

Therefore, the acetic acid concentration in the bleaching solution is preferably 1.0 mol / l or more.

Example 4 The bleaching solution used in Example 1 was replaced with an oxidizing agent (ammonium ferric 1,3-diaminopropanetetraacetate-hydrate) and a chelating agent (1,3-diaminopropanetetraacetic acid), respectively.
A bleaching solution was prepared by replacing the oxidizing agent and the chelating agent shown in the table with the same moles.

Using this bleaching solution, the bleaching time was set to 35 seconds, and the other conditions were made exactly the same as the processing method 1 of Example 1, and the sample 7 of Example 1 was processed. It was quantified by the X-ray method.

 Table 6 shows the results.

As is clear from Table 6, the oxidizing agent in the bleaching solution having an oxidation-reduction potential of 0.15 V or more, which is within the range of the present invention, is very excellent in desilvering properties. On the other hand, when the oxidizing agent is smaller than 0.15 V, the amount of residual silver is extremely large, which is not preferable from the viewpoint of the amount of residual silver.

Example 5 Samples 1 to 15 prepared in Example 1 were replaced with pH 4 in Example 2.
Processing was carried out in processing method 1 using bleach solutions of 0, 5.0 and 6.0.

The obtained sample was stored under the following conditions, and an increase in stain in an unexposed portion was evaluated.

Dark moisture heat preservability: 60 ° C, 70% RH, 10 days Evaluation method was measured by Dmin measured with green light after storage under the above conditions and green light before test start under the above conditions
The difference from Dmin (ΔD) was shown.

 ΔDmin = (Dmin after test) − (Dmin before test) The results are collectively shown in Table 7.

From Table 7, the pH of the bleaching solution satisfying the constitutional requirements of the present invention is 5.
It can be seen that the photographic materials processed at 0 or less, Samples 7 to 15, have a very small increase in stain in image storage after processing.

Example 6 On a cellulose triacetate film support having an undercoat, each layer having the following composition was applied in multiple layers to prepare Sample 21 as a multilayer color photosensitive material.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount is expressed in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer. The numerical value in parentheses at the end of each layer indicates the dry film thickness (unit: μ)
m).

(Sample 21) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.50 (1.2) Second layer (Intermediate layer) 2,5-di-t-pentadecyl 0.18 Hydroquinone EX-1 0.07 EX-3 0.02 EX- 12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.40 (1.7) Third layer (first red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion B silver 0.25 Sensitizing dye I 6.9 × 10 ^-5 sensitizing dye II 1.8 × 10 ^-5 sensitizing dye III 3.1 × 10 ^-4 EX-2 0.335 EX-10 0.020 HBS-1 0.060 Gelatin 1.20 (1.5) 4th layer (2nd red-sensitive emulsion layer) Emulsion G Silver 1.0 Sensitizing dye I 5.1 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.3 × 10 ^-4 EX-2 0.400 EX-3 0.050 EX-10 0.015 HBS-1 0.060 Gelatin 1.55 (2.0) Fifth layer (third red-sensitive emulsion layer) Emulsion D silver 1.60 Sensitizing dye I 5.4 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.4 × 10 ^-4 EX-3 0.010 EX -4 0.080 EX-2 0.097 HBS-1 0.22 HBS- 0.10 gelatin 1.85 (2.4) 6th layer (intermediate layer) EX-5 0.040 HBS-1 0.020 gelatin 1.15 (1.0) 7th layer (first green-sensitive emulsion layer) Emulsion A silver 0.15 Emulsion B silver 0.15 sensitizing dye V 3.0 × 10 ^-5 sensitizing dye VI 1.0 × 10 ^-4 sensitizing dye VII 3.8 × 10 ^-4 EX-6 0.260 EX-1 0.021 EX-7 0.030 EX-8 0.025 HBS-1 0.100 Gelatin 1.25 (1.5) 8th layer (Second green-sensitive emulsion layer) Emulsion C Silver 0.45 Sensitizing dye V 2.1 × 10 ^-5 Sensitizing dye VI 7.0 × 10 ^-5 Sensitizing dye VII 2.6 × 10 ^-4 EX-6 0.094 EX-8 0.018 EX-7 0.026 HBS-1 0.160 Gelatin 0.70 (1.0) Ninth layer (third green sensitive emulsion layer) Emulsion E Silver 1.2 Sensitizing dye V 3.5 × 10 ^-5 Sensitizing dye VI 8.0 × 10 ^-5 Sensitizing dye VII 3.0 × 10 ^-4 EX-13 0.015 EX-11 0.100 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 gelatin 1.75 (2.2) 10th layer (yellow filter layer) Yellow colloidal silver silver 0.05 EX-5 0.08 HBS-1 0.03 gelatin 1.10 (1.0) 11th layer (1st blue-sensitive emulsion layer) Emulsion A silver 0.08 Emulsion B silver 0.07 Emulsion F silver 0.07 Sensitizing dye ^{VIII 3.5 × 10 -4 EX-9} 0.721 EX-8 0.042 HBS-1 0.28 Gelatin 1.25 (2.0) 12 layer (second blue-sensitive emulsion layer) Emulsion G silver 0.45 sensitizing dye VIII 2.1 × 10 ^-4 EX-9 0.154 EX-10 0.007 HBS-1 0.05 gelatin 0.95 (1.1) 13th layer (third blue-sensitive emulsion layer) Emulsion H silver 0.77 sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.90 (1.2) 14th layer (first protective layer) Emulsion I Silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.05 Gelatin 1.30 (1.5) 15th layer ( Second protective layer) Polymethyl acrylate particles (about 1.5 μm in diameter) 0.54 AS-1 0.20 Gelatin 1.25 (2.0) In addition to the above components, gelatin hardener H-1 and a surfactant were added.

HBS-1 Tricresyl phosphate HBS-2 Di-n-butyl phthalate Next, the layer structure, the compound used in each layer and its coating amount, the type of emulsion and its coating amount were changed without changing Sample 21.
However, the coating amounts of the first layer and the second layer were changed for each layer, and the hardener H-1 based on the total amount of gelatin was added in the same ratio as that of the sample 21, and as shown in Table 8, the hardening agent H-1 was added to the first layer. A sample in which the total thickness of the second layer was changed, and a green sensitive layer (the seventh layer, the eighth layer)
As shown in Table 8, samples 22 to 35 were prepared in which the oil used for the layer and the ninth layer was changed and the same amount of oil as that of the sample 21 was added.

These prepared samples 22 to 35 were cut and processed to a width of 35 mm, subjected to wet exposure with white light (color temperature of light source: 4800 ° K), and processed by processing methods 1 and 2 of Example 1.

These processed samples obtained by the processing methods 1 and 2 are referred to as a B group and an S group, respectively. The densities of these samples were measured, and the resulting characteristic curves were measured at green light densities.
Dmin was read.

The obtained results were evaluated by the same evaluation method as in Example 1. As in Example 1, samples 27 to 27 satisfying the constitution of the present invention were obtained.
35 had a lower Dmin than Samples 21 to 26 and was clearly superior.

Therefore, using an oil with a dielectric constant of 6.0 or less for the green sensitive layer,
In addition, when the thickness of the first layer + the second layer (all layers provided between the photosensitive layer closest to the support and the undercoat layer of the support) is 2.5 or less, it is very effective in reducing bleach fog. high.

Example 7 Six bleaching solutions used in Example 2 (pH of 3.7, 4.0, 4.
Sample 27 prepared in Example 6 was treated in the same manner as in Example 2 using the bleaching solutions (5, 5.0, 5.5, and 6.0). The sample obtained here was compared with the sample of group S by Dmin, as in Example 2.
The Dmin was higher in the bleaching treatment at pH 5.5 and pH 6.0, but the photosensitive material (Sample 27) satisfying the components of the present invention was used in the treatment at pH 5.0 or lower. If so, the height of Dmin was at a level that did not matter.

Therefore, in the bleaching treatment of the present invention, the pH is preferably 5.0 or less, and more preferably the pH is 4.0 or less.

Example 8 The same procedure as in Example 3 was carried out except that the sample 27 prepared in Example 6 was used.
The treatment was carried out using a bleaching solution in which the concentration of acetic acid was changed as described in 1).

The concentration of these samples was measured, Dmin was read from the obtained characteristic curve in the same manner as in Example 6, and the same evaluation was performed as in Example 3. As in Example 3, the concentration of acetic acid in the bleaching solution was measured. When treated with a bleaching solution of 1.0 mol / l or more, it was found that bleaching fog was small and particularly excellent.

Example 9 The same processing as in Example 4 was performed using the sample 27 prepared in Example 6 under the five types of processing conditions used in Example 4, and the amount of residual silver in each of the obtained samples was measured by X-ray fluorescence. Quantified by the method.

As a result, when a bleaching agent having a redox potential of 0.15 V or more is used (1,3-DPTA-Fe, GEDTA-Fe),
It was found that the desilvering property was particularly excellent.

Example 10 Samples 21 to 35 prepared in Example 6 were treated with bleach at pH 4.0, 5.0 and 6.0 in the same manner as in Example 5, and the resulting samples were treated in the same manner as in Example 5 (dark and wet heat). Storage: 60 ° C, 70% R
H, 10 days) and evaluated for the increase in stain in the unexposed areas. The evaluation was performed in the same manner as in Example 5.

As a result, when a light-sensitive material satisfying the constitution of the present invention was processed with a bleaching solution having a pH of 5.0 or less, an increase in stain in image preservation after processing was clearly small.

Claims (2)

(57) [Claims] A silver halide color photographic light-sensitive material having at least one red-sensitive silver halide light-sensitive layer, a green light-sensitive silver halide light-sensitive layer and a blue light-sensitive silver halide light-sensitive layer on a support. Thereafter, in a processing method of color development and bleaching, a non-photosensitive layer including an antihalation layer is provided between the photosensitive layer closest to the support and the undercoat layer on the support, and the dry thickness of the non-photosensitive layer Is 2.5 μm or less,
A method for processing a silver halide color photographic light-sensitive material, wherein the green-sensitive silver halide photosensitive layer contains a high-boiling organic solvent having a dielectric constant of 6.0 or less, and the pH of the processing bath for the bleaching treatment is 5.0 or less. 2. A ferric aminopolycarnate having a acetic acid concentration of 1 mol / l or more in a bleaching treatment bath and an oxidation-reduction potential of 150 mV or more at pH 6.0 of 0.1 mol / l. 3. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein: